2022年07月, 物質・デバイス共同研究賞
国内学会・会議・シンポジウム等の賞

Diversity of oxidation state in copper complexes with phenolate ligands
Tomoyuki Takeyama; Yuichi Shimazaki, ラスト(シニア)オーサー, The Cu-phenolate complexes show various electronic structures, such as phenoxyl radical binding Cu^I complexes and Cu^IV–phenolate species in the formal oxidation state, which give rise to characteristic properties and reactivities of the complexes., Royal Society of Chemistry (RSC)
Dalton Transactions, 2024年01月, ［査読有り］, ［招待有り］

Syntheses, Characterizations, Crystal Structures, and Protonation,Reactions of Dinitrogen Chromium Complexes Supported with,Triamidoamine Ligands
Yoshiaki Kokubo; Kazuki Tsuzuki; Hikari Sugiura; Shunsuke Yomura; Yuko Wasada-Tsutsui; Tomohiro Ozawa; Sachiko Yanagisawa; Minoru Kubo; Tomoyuki Takeyama; Takahide Yamaguchi; Yuichi Shimazaki; Shinichi Kugimiya; Hideki Masuda; and Yuji Kajita, American Chemical Society (ACS)
Inorganic Chemistry, 2023年04月, ［査読有り］

〔主要な業績〕Non-innocent redox behavior of Cu(II)-p-dimethylaminophenolate complexes: formation and characterization of the Cu(I)-phenoxyl radical species.
Yuto Shima; Takashi Suzuki; Hitoshi Abe; Tatsuo Yajima; Seiji Mori; Yuichi Shimazaki, ラスト(シニア)オーサー, Cu complexes with p-dimethylaminophenolate ligands were synthesized by the reaction of Cu-II ions with the ligands under inert gas atmosphere and characterized. The complexes showed a valence state change from Cu-II-phenolate to Cu-I-phenoxyl radical on loss of the coordinated solvent. The Cu-I-phenoxyl radical species showed the characteristic properties and reactivities., ROYAL SOC CHEMISTRY
Chem. Commun., 2022年05月, ［査読有り］

〔主要な業績〕Solid State Characterization of One- and Two-Electron Oxidized CuII-salen Complexes with para-Substituents: Geometric Structure-Magnetic Property Relationship
Tomoyuki Takeyama; Takashi Suzuki; Misa Kikuchi; Misato Kobayashi; Hiromi Oshita; Kyohei Kawashima; Seiji Mori; Hitoshi Abe; Norihisa Hoshino; Satoshi Iwatsuki; Yuichi Shimazaki, ラスト(シニア)オーサー
European Journal of Inorganic Chemistry, 2021年10月, ［査読有り］

〔主要な業績〕Formation of the Ni(II)-Phenoxyl Radical Complexes by O2: A Mechanistic Insight into the Reaction of Ni(II)-Phenol Complexes with O2
Takashi Suzuki; Akari Sato; Hiromi Oshita; Tatsuo Yajima; Fumito Tani; Hitoshi Abe; Kaoru Mieda-Higa; Sachiko Yanagisawa; Takashi Ogura; Yuichi Shimazaki, ラスト(シニア)オーサー,

The reaction of Ni(ii)-(phenol)(phenolate) complexes with O₂ gave the Ni(ii)-phenoxyl radical complexes assisted by CH₃OH. This reaction was concluded to undergo via the proton transfer–electron transfer type mechanism without redox of the Ni ion.

, Royal Society of Chemistry (RSC)
Dalton Trans., 2021年03月, ［査読有り］

Recent Advances in One-electron Oxidized CuII-Diphenoxide Complexes as Models of Galactose Oxidase: Importance of the Structural Flexibility in the Active Site
Hiromi Oshita; Yuichi Shimazaki, ラスト(シニア)オーサー, The phenoxyl radical plays important roles in biological systems as cofactors in some metalloenzymes, such as galactose oxidase (GO) catalyzing oxidation of primary alcohols to give the corresponding aldehydes. Many metal(II)-phenoxyl radical complexes have hitherto been studied for understanding the detailed properties and reactivities of GO, and thus the nature of GO has gradually become clearer. However, the effects of the subtle geometric and electronic structural changes at the active site of GO, especially the structural change in the catalytic cycle and the effect of the second coordination sphere, have not been fully discussed yet. In this Review, we focus on further details of the model studies of GO and discuss the importance of the structural change at the active site of GO., WILEY-V C H VERLAG GMBH
Chem. Eur. J., 2020年07月08日, ［査読有り］, ［招待有り］

Benzyl alcohol oxidation mechanisms by one- and two-electron oxidized species of Cu(II)-salen complexes with para-R-substituents, [Cu(R-salen)]n+ (R = MeO, MeS; n = 1, 2)
責任著者
Inorganica Chimica Acta, 2020年06月24日, ［査読有り］

Formation of the CuII-phenoxyl radical by reaction of O2 with the CuII-phenolate complex via the CuI-phenoxyl radical
Takashi Suzuki; Hiromi Oshita; Tatsuo Yajima; Fumito Tani; Hitoshi Abe; Yuichi Shimazaki, Reaction of Cu(ClO4)(2).6 H2O with a tripodal 2N2O ligand, H2Me2NL, having a p-(dimethylamino)phenol moiety, in CH2Cl2/MeOH (1:1 v/v) under basic conditions under an inert gas atmosphere gave [Cu(Me2NL)(H2O)] (1). The same reaction carried out under aerobic conditions gave [Cu(Me2NL)(MeOH)]ClO4 (2), which could be obtained also from the isolated complex 1 by reaction with O-2 in CH2Cl2/MeOH. The X-ray crystal structures of 1 and 2 revealed similar square-pyramidal structures, but 2 showed the (dimethylamino)phenoxyl radical features. Complex 1 exhibits characteristic Cu-II EPR signals of the dx2-y2 ground state in CH2Cl2/MeOH at 77 K, whereas 2 is EPR-silent. The EPR and X-ray absorption fine structure (XAFS) results suggest that 2 is assigned to the Cu-II-(dimethylamino)phenoxyl radical. However, complex 1 showed different features in the absence of MeOH. The EPR spectrum of the CH2Cl2 solution of 1 exhibits distortion from the dx2-y2 ground state and a temperature-dependent equilibrium between the Cu-II-(dimethylamino)phenolate and the Cu-I-(dimethylamino)phenoxyl radical. From these results, Cu-II-phenoxyl radical complex 2 is concluded to be formed by the reaction of 1 with O-2 via the Cu-I-phenoxyl radical species., WILEY-V C H VERLAG GMBH
Chem. Eur. J., 2019年11月, ［査読有り］

The effect of π–π stacking interaction of the indole ring with the coordinated phenoxyl radical in a nickel(II)-salen type complex. Comparison with the corresponding Cu(II) complex
Hiromi Oshita; Takashi Suzuki; Kyouhei Kawashima; Hitoshi Abe; Fumito Tani; Seiji Mori; Tatsuo Yajima; Yuichi Shimazaki, In order to gain new insights into the effect of the pi-pi stacking interaction of the indole ring with the phenoxyl radical moiety as seen in the active form of galactose oxidase, we have prepared Ni(s) complexes of a methoxy substituted salen-type ligand containing a pendent indole ring on the dinitrogen chelate backbone and characterized their one-electron oxidized forms. The X-ray crystal structure analysis and the other physicochemical experiments of the Ni(s) complex revealed no significant intramolecular interaction of the indole ring with the coordination plane. On the other hand, the X-ray crystal structures of the oxidized Ni(ii) complex exhibited the pi-pi stacking interaction of the indole ring mainly with one of the two phenolate moieties. While the phenoxyl radical electron was delocalized on the two phenolate moieties in the Ni(s)-salen coordination plane, the phenolate moiety in close contact with the indole moiety was considered to be the initial oxidation locus, indicating that the indole ring interacted with the phenoxyl radical by pi-pi stacking. The UV vis NIR spectrum of the oxidized Ni(ii) complex with the pendent indole ring was different from that of the complex without the side chain indole ring, but the differences were rather small in comparison with the oxidized Cu(ii)-salen complexes with the pi-pi stacking interaction of the indole ring. Such differences are due to the electronic structure difference, the localized radical electron on one of the phenolate moieties in the oxidized Cu(ii) complexes being more favorable for then pi-pi stacking interaction., ROYAL SOC CHEMISTRY
Dalton Trans., 2019年08月, ［査読有り］

π-π Stacking Interaction in an Oxidized Cu(II)-salen Complex with a Side Chain Indole Ring. An Approach to the Function of the Tryptophan in the Active Site of Galactose Oxidase
Hiromi Oshita; Takashi Suzuki; Kyouhei Kawashima; Hitoshi Abe; Fumito Tani; Seiji Mori; Tatsuo Yajima; Yuichi Shimazaki, In order to gain new insights into the effect of the pi-pi stacking interaction of the indole ring with the Cu-II-phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a Cu-II complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized Cu-II complex exhibited the pi-pi stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the pi-pi stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized Cu-II complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical-indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the pi-pi stacking interaction., WILEY-V C H VERLAG GMBH
Chem. Eur. J., 2019年06月, ［査読有り］

Electronic Structure and Reactivity Studies of a Nonsymmetric One-Electron Oxidized CuII Bis-phenoxide Complex　　　　　　　　　　　　　　　
Linus Chiang; Erik C. Wasinger; Yuichi Shimazaki; Victor Young; Jr.e Tim Storr; T. Daniel; P. Stack
Inorg. Chim. Acta, 2018年, ［査読有り］

Characterization of the one‑electron oxidized Cu(II)‑salen complexes with a side chain aromatic ring: the effect of the indole ring on the Cu(II)‑phenoxyl radical species
Hiromi Oshita; Takayoshi Yoshimura; Seiji Mori; Fumito Tani; Yuichi Shimazaki; Osamu Yamauchi, To gain insights into the role of the proximal indole ring in the redox-active metal center as seen in galactose oxidase, we prepared the Cu(II)-salen-type complexes having a pendent indol-3-ylmethyl (1), methyl (2) or benzyl (3) group substituted on the ethylenediamine moiety and investigated the structures and redox properties by various physicochemical methods and theoretical calculations. Neutral complexes 1, 2, and 3 showed no significant difference in the UV-Vis-NIR and EPR spectra. One-electron oxidation of 1, 2, and 3 by addition of 1 equiv. of thianthrenyl radical gave [1]SbCl (6) , [2]SbCl (6) , and [3]SbCl (6) , respectively, which could be assigned to relatively localized phenoxyl radical species. The cyclic and differential pulse voltammograms of [1]SbCl (6) showed two redox waves with a large separation between the first and second redox potentials compared with the separations observed for [2]SbCl (6) and [3]SbCl (6) . This suggests that [1]SbCl (6) is more stabilized than [2]SbCl (6) and [3]SbCl (6) . The NIR band of [1]SbCl (6) showed a larger blue shift than that of [2]SbCl (6) and [3]SbCl (6) . The EPR spectrum of [2]SbCl (6) exhibited an intense signal at the g value of 2 due to partial disproportionation to form the EPR active two-electron oxidized complex [2] (2+) , while the EPR intensity of [1]SbCl (6) was much weaker than that of [2]SbCl (6) . These results indicate that the pendent indole moiety stabilizes the Cu(II)-phenoxyl radical in [1]SbCl (6) most probably by stacking with the phenoxyl moiety, which is further supported by DFT calculations., SPRINGER
J. Bio Inorg. Chem., 2018年01月, ［査読有り］, ［招待有り］

Characterization of Group 10-Metal-p-Substituted Phenoxyl Radical Complexes with Schiff Base Ligands.
Hiromi Oshita; Misa Kikuchi; Kaoru Mieda; Takashi Ogura; Takayoshi Yoshimura; Fumito Tani; Tatsuo Yajima; Hitoshi Abe; Seiji Mori; Yuichi Shimazaki, Methylthiophenoxyl radical plays an important role as the active form of galactose oxidase (GO), which catalyzes oxidation of a primary alcohol to the corresponding aldehyde. Although many metal(II)-phenoxyl radical species have been reported, only a few studies have been reported on the properties of methylthiophenoxyl radical-metal complexes. We have prepared the group 10 metal (Ni, Pd and Pt) complexes of a salen-type ligand with a methylthio group at para-position of the two phenolate moieties and characterized them by X-ray crystal structure analyses and various spectroscopic methods in order to understand the role of the methylthio moiety in phenoxyl radical metal complexes. The corresponding pmethoxy substituted derivatives have been also characterized for comparison. All the one-electron oxidized group 10 metal methylthiophenolate complexes have a relatively localized radical site on one of the two phenolate moieties in comparison to the one-electron oxidized complexes of pmethoxy derivatives and exhibit different properties dependent on the central metal ions., WILEY-V C H VERLAG GMBH
CHEMISTRYSELECT, 2017年10月, ［査読有り］

Electronic Structure Evaluation of an Oxidized Tris(methoxy)-Substituted Ni Salen Complex
Linus Chiang; Ryan M. Clarke; Khrystyna Herasymchuk; Mathew Sutherland; Kathleen E. Prosser; Yuichi Shimazaki; Tim Storr, The Ni salen complex N,N-bis(2,3,4-trimethoxysalicylidene)-1,2-cyclohexane-(1R,2R)-diamine nickel(II) (1), containing ortho-, meta-, and para-methoxy-substituted phenolate moieties, was prepared. Electrochemical studies revealed that the first oxidation of 1 occurs at a similar potential to a previously reported Ni salen complex NiSal(tBu,OMe), employing an ortho-tBu and para-methoxy substitution pattern (M. Orio et al., Angew. Chem. Int. Ed.2010, 49, 4989), demonstrating the counteracting effects of the methoxy substituent depending on ring location (ortho/para vs. meta). The second oxidation occurred at a much lower potential (E-1/2(2) - E-1/2(1) = 0.11 V) for 1, in comparison to NiSal(tBu,OMe), suggesting significant localization of the ligand radical. The one-electron oxidized form was prepared and studied using a number of experimental and theoretical methods. A localized ligand radical electronic structure was confirmed by the shape and intensity of the NIR bands, which was further verified by the presence of both phenolate and phenoxyl signatures in the resonance Raman spectrum. Theoretical calculations provided insight into the degree of ligand radical localization, and the nature of the low energy bands observed in the Vis/NIR experiment. Overall, the oxidation of 1 results in a localized ligand radical complex, with further oxidation processes easily accessible due to resonance stabilization afforded by the methoxy substituents., WILEY-V C H VERLAG GMBH
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2016年01月

Asymmetric Michael addition of thiols to beta-nitrostyrenes using a novel phenylpyrrolidine-based urea catalyst
Souichirou Kawazoe; Kazuki Yoshida; Yuichi Shimazaki; Takeshi Oriyama, The catalyst 1-[ (3R,4S)-1-benzyl-4-phenyl-pyrrolidin-3-yl]-3-[3,5-bis(trifluoromethyl)phenyl]urea (8) designed based on 1-[ (3R)-1-benzylpyrrolidin-3-yl]-3-[3,5-bis(trifluoromethyl)phenyl]thiourea (4) and 1,3-bis[ (3R,4S)-1-benzyl-4-phenylpyrrolidin-3-yl]urea (7) exhibited potent catalytic activity for the asymmetric Michael addition of thiols to beta-nitrostyrenes. A mere 2 mol % of the catalyst afforded 2-nitro-1-phenylethylsulfides in high yields of up to 93% ee. (C) 2014 Elsevier Ltd. All rights reserved., PERGAMON-ELSEVIER SCIENCE LTD
Tetrahedron Letters, 2015年, ［査読有り］

Properties of the indole ring in metal complexes. A comparison with the phenol ring,
Y. Shimazaki; O. Yamauchi, Tryptophan (Trp), an essential amino acid, has an indole ring with a high electron density and is frequently seen at the proximal position of the metal site in metalloproteins. For example, the indole ring of Trp has been reported to interact weakly with Cu(I) in a Cu chaperone CusF. Another aromatic amino acid, tyrosine (Tyr), has a phenol ring, which is an important metal binding site in various metalloproteins. Although the structures of the aromatic rings are different, they both have a weakly acidic moiety and perform some similar roles in biological systems, such as radical formation and electron transfer. In this review, we focus on these and other properties of the indole and phenol rings in metal-containing systems. (C) 2015 Elsevier Inc. All rights reserved., ELSEVIER SCIENCE INC
J. Inorg. BioChem., 2015年, ［査読有り］, ［招待有り］

Properties of the One-Electron Oxidized Copper(II) Salen-Type Complexes: Relationship between Electronic Structures and Reactivities
Yuichi Shimazaki, The Cu(II)-phenoxyl radical formed during the catalytic cycle of galactose oxidase (GO) attracted much attention, and the structures and properties of a number of metal-phenoxyl radical complexes have been studied. Some of the functional model systems of GO reported previously have shown that the Cu complexes oxidize primary alcohols to aldehydes and that the Cu(II)-phenoxyl radical species is formed in the catalytic cycle. Many Cu(II)-phenoxyl radical species have been produced by one-electron oxidation of the Cu(II)-phenolate complexes. On the other hand, one-electron oxidation of a Cu(II)-phenolate complex has the possibility to give different electronic structures, one of which is the Cu(III)-phenolate. From these points of view, this micro review is focused on the one-electron oxidized square-planar Cu(II) complexes of the salen-type ligands. Introduction of substituents into the phenolate moieties and conversion from a 5- to a 6-membered chelate backbone alter the electronic structure of the one-electron oxidized Cu(II) complexes and give rise to a different reactivity of benzyl alcohol oxidation. The relationship between the electronic structure and the reactivity is herein discussed., WALTER DE GRUYTER GMBH
Pure and Applied Chemistry, 2014年, ［査読有り］, ［招待有り］

Kinetic studies on cyclopalladation in,palladium(II) complexes containing an indole,moiety
Satoshi Iwatsuki; Takuya Suzuki; Syogo Tanooka; Tatsuo Yajima and Yuichi Shimazaki, Various Pd-C complexes have been developed to date, affording deep insights into the reaction intermediates in useful catalytic reactions in organic syntheses. Cyclopalladation is one of the most famous Pd-C bond formation reactions to generate the palladacycles. Indole is an electron-rich aromatic ring involved in the side chain of an essential amino acid, tryptophan (Trp), and Trp and its derivatives are important in biological systems, such as electron transfer in protein, cofactors for conversion of biological molecules and so on. Pd catalysts are also useful for syntheses of such indole derivatives, and the mechanisms are considered to be through the Pd-C intermediates. However, the detailed properties and formation mechanisms of Pd-indole species are still unclear. With these points in mind, we focus on Pd(II)-indole-C2 carbon bond formations using various Pd(II) complexes having an indole moiety, especially on the recent studies on the kinetic analyses for these cyclopalladation reactions and their detailed mechanisms., WALTER DE GRUYTER GMBH
Pure and Applied Chemistry, 2014年, ［査読有り］, ［招待有り］

Characterization of One-Electron Oxidized Copper(II)-Salophen-Type Complexes; Effects of Electronic and Geometrical Structures on Reactivities
Kazutaka Asami; Akiko Takashina; Misato Kobayashi; Satoshi Iwatsuki; Tatsuo Yajima; Amélie Kochem; Maurice van Gastel; Fumito Tani; Takamitsu Kohzuma; Fabrice Thomas and Yuichi Shimazaki, One-electron oxidized salophen-type complexes, [Cu(salophen)](+) (H(2)salophen = N, N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminobenzene), and its methoxy derivatives, [Cu(MeO-salophen)](+) and [Cu(salophen-(MeO)(2))](+) (H2MeO-salophen = N, N'-bis(3-tert-butyl-5-methoxysalicylidene)-1,2-diaminobenzene, H(2)salophen-(MeO)(2) = N, N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diamino-4,5-dimethoxybenzene), have been synthesized and structurally characterized, and their reactivities have been investigated. The solid state structures of the one-electron oxidized forms of these complexes suggested that [Cu(salophen)](+) and [Cu(MeO-salophen)](+) can be assigned to relatively localized Cu(II)-phenoxyl radical complexes, while [Cu(salophen-(MeO)(2))](+) is the diiminobenzene radical complex. On the other hand, [Cu(salophen)](+) in solution showed a different electronic structure from that of the solid sample, the radical electron being delocalized over the whole pi-conjugated ligand. The reaction of these oxidized complexes with benzyl alcohol has been investigated in the presence of a large excess of substrate, which revealed the difference in the kinetic behavior between the complexes. The mechanisms of the oxidation have been discussed on the basis of the electronic and geometrical structures and the reaction kinetics., ROYAL SOC CHEMISTRY
Dalton Trans., 2014年, ［査読有り］

FeIII Bipyrrolidine Phenoxide Complexes and Their Oxidized,Analogues
Linus Chiang; Didier Savard; Yuichi Shimazaki; Fabrice Thomas; and Tim Storr, Fe-III complexes of the symmetric (2S,2'S)-[N,N'-bis(1-(2-hydroxy-3,5-di-tert-butylphenylmethyl))1-2,2'- bipyrrolidine (H2L1) and dissymmetric (2S,2'S)-[N,N'-(1-(2-hydroxy-3,5-di-tert-butylphenylmethyl))-2-(pyridylmethyl)]- 2,2'-bipyrrolidine (HL2) ligands incorporating the bipyrrolidine backbone were prepared, and the electronic structure of the neutral and one-electron oxidized species was investigated. Cyclic voltammograms (CV) of (FeLCl)-Cl-1 and (FeLCl2)-Cl-2 showed expected redox waves corresponding to the oxidation of phenoxide moieties to phenoxyl radicals, which was achieved by treating the complexes with 1 equiv of a suitable chemical oxidant. The clean conversion of the neutral complexes to their oxidized forms was monitored by UV-vis-NIR spectroscopy, where an intense pi-pi* transition characteristic of a phenoxyl radical emerged [ (FeLCl)-Cl-1](+center dot): 25 500 cm(-1) (9000 M-1 cm(-1)); [ (FeLCl2)-Cl-2](+center dot): 24 100 cm-1 (8300 M-1 cm(-1)). The resonance Raman (rR) spectra of [ (FeLCl)-Cl-1](+center dot) and [ (FeLCl2)-Cl-2](+center dot) displayed the characteristic phenoxyl radical nu(7a) band at 1501 and 1504 cm(-1), respectively, confirming ligand-based oxidation. Electron paramagnetic resonance (EPR) spectroscopy exhibited a typical high spin Fe-III (S = 5/2) signal for the neutral complexes in perpendicular mode. Upon oxidation, a signal at g 9 was observed in parallel mode, suggesting the formation of a spin integer system arising from magnetic interactions between the high spin Fe-III center and the phenoxyl radical. Density functional theory (DFT) calculations further supports this formulation, where weak antiferromagnetic coupling was predicted for both [ (FeLCl)-Cl-1](+center dot) and [ (FeLCl2)-Cl-2](+center dot)., AMER CHEMICAL SOC
Inorg. Chem., 2014年, ［査読有り］

Symmetric Urea-Catalyzed Asymmetric Michael Addition of Thiols to β-Nitrostyrenes
Souichirou Kawazoe; Kazuki Yoshida; Yuichi Shimazaki; Takeshi Oriyama, Several pyrrolidine- and piperidine-based organocatalysts were evaluated for the asymmetric Michael addition of thiols to beta-nitrostyrenes. We found a structure-activity relationship between the catalyst and a higher catalytic activity for 1,3-bis [ (3R,4S)-1-benzyl-4-phenylpyrrolidin-3-yl]urea., CHEMICAL SOC JAPAN
Chem. Lett., 2014年, ［査読有り］

Influence of Ligand Flexibility on the Electronic Structure of Oxidized NiIII-Phenoxide Complexes
Minoru Kawai; Takahide Yamaguchi; Shigeyuki Masaoka; Fumito Tani; Takamitsu Kohzuma; Linus Chiang; Tim Storr; Kaoru Mieda; Takashi Ogura; Robert K. Szilagyi; Yuichi Shimazaki, One-electron-oxidized Ni-III-phenoxide complexes with salen-type ligands, [Ni(salen)py(2)](2+) ([1(en)-py](2+)) and [Ni(1,2-salcn)py(2)](2+) ([1(cn)-py](2+)), with a five-membered chelate dinitrogen backbone and [Ni(salpn)py(2)](2+) ([2(pn)-py](2+)) with a six-membered chelate backbone, have been characterized with a combination of experimental and theoretical methods. The five-membered chelate complexes [1(en)-py](2+) and [1(cn)-py](2+) were assigned as Ni-III-phenoxyl radical species, while the six-membered chelate complex [2(pn)-py](2+) was concluded to be a Ni-II-bis(phenoxyl radical) species with metal-centered reduction in the course of the one-electron oxidation of the Ni-III-phenoxide complex [2(pn)-py](+). Thus, the oxidation state of the one-electron-oxidized Ni-III salen-type complexes depends on the chelate ring size of the dinitrogen backbone., AMER CHEMICAL SOC
Inorg. Chem., 2014年, ［査読有り］

Pd–C bond formation with the indole ring in palladium complexes of N,N,O-donor ligands. Effect of the nitrogen donor properties
Syogo Tanooka; Takuya Suzuki; Tatsuo Yajima; Tadashi Shiraiwa; Satoshi Iwatsuki; Yuichi Shimazaki, The Pd(II) complexes of three new N,N,O-donor ligands with a pendent indole ring and participation of the indole ring in Pd(II) binding have been studied by synthetic, structural, and kinetic methods. The reactions of ligands, 2-[N-2-(1-methylimidazolyl)methyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethyl-3-indole (Hieip), 2-[N-2-(1,4,5-trimethylimidazolyl) methyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino] ethyl-3-indole (HMe3-ieip) and 2-[N-2-(6-methypyridyl)-methyl-N-2-hydroxy-3,5-di(tert-butyl) benzylamino]ethyl-3-indole (HMe-iepp), with [PdCl2(CH3CN)(2)] at room temperature gave the complexes [Pd(ieip)Cl], [Pd(Me-3-ieip)Cl] and [Pd(Me-iepp)Cl], respectively, as reddish-brown crystals. The X-ray crystal structure analyses and H-1 NMR spectra revealed that all the complexes have a phenolate coordination in a square-planar geometry and that the pendent indole ring has no characteristic intramolecular interaction with the Pd(II) ion and the coordinated pyridine and imidazole moieties. The distortion of the coordination plane is in the order [Pd(ieip)Cl] < [Pd(Me-3-ieip)Cl] < [Pd(Me-iepp)Cl]. Heating a solution of each of the phenolate complexes gave yellow crystals, which were shown to be the indole-C2 binding complex by X-ray analysis. The Pd(II)-O(phenolate) to Pd(II)-C(indole) conversion characteristics of these complexes depends on the nitrogen donor properties of the trans position of the coordinated indole moiety, and the order of the conversion rate of Pd-indole binding complexes is in good correlation with the coordination plane distortion. On the basis of kinetic studies, the influence of the aromatic nitrogen donors to form the indole-C2 binding complexes and the detailed mechanism of the conversion were discussed. Crown Copyright (c) 2013 Published by Elsevier B.V. All rights reserved., ELSEVIER SCIENCE SA
Inorganica Chimica Acta, 2013年10月, ［査読有り］

Double oxidation localizes spin in a Ni bis-phenoxyl radical complex
Tim J. Dunn; Michael I. Webb; Khatera Hazin; Pratik Verma; Erik C. Wasinger; Yuichi Shimazaki and Tim Storr, The electronic structure of a doubly oxidized Ni salen complex NiSal tBu (SaltBu = N,N′-bis(3,5-di-tert- butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) has been investigated by both experimental and theoretical methods. The doubly oxidized product was probed by resonance Raman spectroscopy, UV-vis-NIR, and EPR to determine the locus of oxidation as well as the spectroscopic signature of the complex. It was determined that double oxidation of NiSaltBu affords a bis-ligand radical species in solution via the presence of phenoxyl radical bands at ν7a (1504 cm-1) and ν8a (1579 cm -1) in the Raman spectrum, and the loss of the intense NIR transition reported for the mono-radical complex (Angew. Chem., Int. Ed., 2007, 46, 5198). Spectroscopic experiments, complemented by DFT calculations, show that the two radical spins are predominantly localized on the phenolate moieties, in opposition to the extensive delocalization over the ligand framework observed for the mono-radical analogue. © 2013 The Royal Society of Chemistry., Royal Society of Chemistry
Dalton Trans., 2013年, ［査読有り］

Recent Advances in X-ray Structures of Metal-Phenoxyl Radical Complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
Advances in Materials Physics and Chemistry (Review), 2013年, ［査読有り］, ［招待有り］

One-Electron Oxidized Copper(II) Salophen Complexes: Phenoxyl versus Diiminobenzene Radical Species
Amélie Kochem; Olivier Jarjayes; Benoit Baptiste; Christian Philouze; Hervé Vezin; Kazuaki Tsukidate; Fumito Tani; Maylis Orio; Yuichi Shimazaki; Fabrice Thomas, WILEY-V C H VERLAG GMBH
Chem. Eur. J., 2012年, ［査読有り］

Supramolecular Structures of Inclusion Complexes of Cyclic Porphyrin Dimers and [6,6]-Phenyl-C 61-Butyric Acid Methyl Ester (PCBM)
Hirofumi Nobukuni; Takuya Kamimura; Hidemitsu Uno; Yuichi Shimazaki; Yoshinori Naruta; Fumito Tani, Cyclic nickel and free-base porphyrin dimers (Ni-2-CPDpy and H-4-CPDpy) include [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) both in solution and in the crystals. In the crystal packing of the inclusion complex of Ni-2-CPDpy and PCBM, a nanotubular structure is constructed through the self-assembly of the porphyrin moiety. The PCBM molecules are linearly arranged in the inner channel of the nanotube to give a supramolecular peapod. On the other hand, in the crystal of the inclusion complex of H-4-CPDpy and PCBM, a dimeric structure of the PCBM molecules is formed through pi-pi interaction between their phenyl groups., CHEMICAL SOC JAPAN
Bull. Chem. Soc. Jpn., 2012年, ［査読有り］

Synthesis, Characterization, and Small Hydrocarbon Encapsulation of Dicavitand-Porphyrins
Jun Nakazawa; Jun Hagiwara; Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta, New host molecules "Dicavitand-Porphyrins" [H2C2P(syn,syn) (3), H2C2P(syn,anti) (4)] with small cavities on one or both sides of the porphyrin plane were synthesized from 5,10-bis(2,6-dihydroxyphenyl)-15,20-diphenylporphyrin and bis(chloromethyl)cavitand in 15 and 34% yield, respectively. Similarity of guest size selectivity of the host 4 in comparison with the reported "Cavitand-porphyrin" [H2CP(syn) (1)] suggests that these hosts have the same cavity size. The 1:1 and 1:2 association constants (K-11 and K-12) of the guest encapsulations into 3 were also obtained by H-1 NMR titration and nonlinear least square fittings. The guest size dependences of K-11, and K-12 values of 3 show that the initial cavity prefers larger guests such as ethane, while the second one does not. The induced-fit type very small structural changes (estimated within 1 angstrom) upon first guest encapsulation of the host 3 affects the guest encapsulation of the other cavity through the covalent linkages., CHEMICAL SOC JAPAN
Bull. Chem. Soc. Jpn., 2012年, ［査読有り］

Synthesis and properties of charge-transfer solids with cluster units [Mo6X14]2 (X . Br, I)
Gunzi Saito; Hidemasa Hosoda; Yukihiro Yoshida; Jun Hagiwara; Kazukuni Nishimura; Hideki Yamochi; Akihiro Otsuka; Takaaki Hiramatsu; Yuichi Shimazaki; Kaplan Kirakci; Stephane Cordier; Christiane Perrin, The preparation of charge-transfer (CT) solids using [Mo6X14](2-) (X = Br, I) cluster units and several organic electron donor molecules (D) including a variety of tetrathiafulvalene (TTF) derivatives was studied. Galvanostatic electrochemical oxidation afforded single crystals of the cation radical salts of (tetrathionaphthacene)Mo6Br14(PhCN)(3) (1, PhCN: benzonitrile), (hexamethylene-TTF)(2)Mo6I14(PhCN)(4) (2), (bis(ethylenedioxy)-TTF)(2)Mo6Br14(PhCN)(4) (3), (tetrakis(methylthio)-TTF)(2)Mo6Br14 (4), (perylene)(6)Mo6Br14 (5), and powders from several TTF derivatives combined with other kinds of electron donors. In 1, the donor molecules were in the diamagnetic dicationic state and formed two-dimensional D(2+)A(2-) (A = Mo6Br14) layers. Moreover, in 2-4, the donor molecules were in the monocationic radical state. The structural analysis of 3 indicated the presence of isolated cation radical molecules, whereas in 2 and 4, the donor cation radicals formed segregated stacks with dimerized units. Donor dimers and [Mo6I14](2-) cluster units in 2 formed a CsCl-related structural pattern with solvent molecules occupying the free space in the crystal. The donor dimers and [Mo6Br14](2-) cluster units in 4 formed infinite alternating stacks parallel to each other. The static magnetic susceptibility of 2 exhibited singlet-triplet behavior with vertical bar J vertical bar/k(B) = 190 K, whereas the radical spins in 4 were strongly coupled antiferromagnetically. There were two kinds of perylene molecules in 5: one formed segregated columns with weakly dimerized units having a charge of approximately +0.5, while the other enclosed the columns with parallel molecular planes having nearly zero charge. 5 was similar to that of a dimer-type Mott insulator. The electrochemical reaction of N-(3-perylenylmethyl)-N, N-bis(2-pyridylmethyl)amine (perbpa), which is a perylene-pendant tridentate ligand, and CuCl2 in the presence of (Bu4N)(2)Mo6Br14 in PhCN afforded a dinuclear Cu(II) complex [Cu-2(mu-Cl)(2)(perbpa)(2)]Mo6Br14(PhCN)(4) (6). The perylene groups in 6 were in a neutral electronic state. The temperature-dependent magnetic susceptibility measurement of 6 showed a weak ferromagnetic exchange interaction between the Cl-bridged Cu(II) cores with the S = 1 ground state (g = 2.14, J = +0.56 K) based on H = -2JS(1.)S(2). The boundary between the neutral and ionic ground states of the CT solids of [Mo6Br14](2-) shifted to the negative side by 0.5 V and 0.3-0.6 V from those of the TTF.p-quinone and TTF.TCNQ system, respectively, with respect to the redox potential differences between the donor and acceptor species., ROYAL SOC CHEMISTRY
J. Mater. Chem., 2012年, ［査読有り］

Non-innocent ligand behaviour of a bimetallic Cu complex employing a bridging catecholate.
Tim J Dunn; Linus Chiang; Caterina F Ramogida; Michael I Webb; Didier Savard; Miyuki Sakaguchi; Takashi Ogura; Yuichi Shimazaki; Tim Storr, The geometric and electronic structure of a bimetallic Cu Schiff-base complex and its one-electron oxidized form have been investigated. The two salen units in the neutral complex 1 are linked via a bridging catecholate function, and the coupling between the two Cu(II) d(9) centres was determined to be weakly antiferromagnetic on the basis of solid-state magnetic studies (J = -3 cm(-1)), and variable-temperature electron paramagnetic resonance (EPR) (J = -3 cm(-1)). Theoretical calculations (DFT) were in agreement with the experimental results (J = -7 cm(-1)), and provided insight into the coupling mechanism for the neutral system. One-electron oxidation provided [1](+) which was observed to have limited stability in solution. The oxidized complex was determined to be a ligand radical species in solution, with the electron hole potentially localized on the redox-active dioxolene, the phenolate ligands, or delocalized over the entire ligand system. Electrochemical experiments and UV-vis-NIR spectroscopy, in combination with density functional theory (DFT) calculations, provided insight into the locus of oxidation and the degree of delocalization in this system. The ligand radical for [1(.)](+) was determined experimentally to be localized on the dioxolene bridge with a small amount of spin density on the outer phenolate moieties predicted by the calculations. This assignment was aided via comparison to data for the Ni analogue (Inorg. Chem., 2011, 50, 6746). The resonance Raman spectrum of [1(.)](+) (lambda(ex) = 413 nm) in CH2Cl2 solution clearly exhibited a new band at 1308 cm(-1) in comparison to 1, supporting semiquinone formation. Variable-temperature EPR on the three-spin system [1(.)](+) did not provide definitive information on the coupling interaction, possibly due to a very small difference in energy between the S = 3/2 and S = 1/2 states and/or a very small zero-field splitting, in combination with significant line-broadening. The data is consistent with a description of the overall electronic structure of [1(.)](+) as a bimetallic Cu(II) complex with a bridge-localized semiquinone ligand radical species., ROYAL SOC CHEMISTRY
Dalton trans., 2012年, ［査読有り］

Group-10 metal complexes of biological molecules and related ligands: structural and functional properties
Yuichi Shimazaki; Osamu Yamauchi, The complexes of group-10 metals, Ni, Pd, and Pt, with biological molecules and related ligands have been attracting increasing attention in recent years due to their reactivities and functions, such as catalysts and drugs, and their biological relevance. The well-defined structures and kinetic inertness especially of Pt complexes have been used as the sites for weak interactions with other molecules. The Ni complexes have been reported as models not only for Ni enzymes but also for other metalloenzyme active sites for deeper understanding of the reactivities such as oxygen activations and detailed electronic structures. Pd Complexes are widely known for their catalytic activities in conversions of various organic molecules including useful biological molecules, such as Suzuki?Miyaura cross-coupling, while Pt complexes have been intensively studied for their antitumor activities. We focus in this review on our recent results on weak interactions and reactivities of the group-10 metal complexes with biological molecules and related compounds, and discuss their structural features and some new properties pointing to functional possibilities., WILEY-V C H VERLAG GMBH
Chemistry & biodiversity(Review), 2012年, ［査読有り］, ［招待有り］

Radical Localization in a Series of Symmetric Ni(II) Complexes with Oxidized Salen Ligands.
Linus Chiang; Amélie Kochem; Olivier Jarjayes; Tim J Dunn; Hervé Vezin; Miyuki Sakaguchi; Takashi Ogura; Maylis Orio; Yuichi Shimazaki; Fabrice Thomas; Tim Storr, Square-planar nickel(II) complexes of salen ligands,N,N'-bis(3-tert-butyl-(5R)-salicylidene)-1,2-cyclohexanediamine), in which R = tert-butyl (1), OMe (2), and NMe2 (3), were prepared and the electronic structure of the one-electron-oxidized species [1-3](+center dot) was investigated in solution. Cyclic voltammograms of [1-3] showed two quasi-reversible redox waves that were assigned to the oxidation of the phenolate moieties to phenoxyl radicals. From the difference between the first and second redox potentials, the trend of electronic delocalization 1(+center dot)>2(+center dot)>3(+center dot) was obtained. The cations [1-3](+center dot) exhibited isotropic g tensors of 2.045, 2.023, and 2.005, respectively, reflecting a lower metal character of the singly occupied molecular orbital (SOMO) for systems that involve strongly electron-donating substituents. Pulsed-EPR spectroscopy showed a single population of equivalent imino nitrogen atoms for 1(+center dot), whereas two distinct populations were observed for 2(+center dot). The resonance Raman spectra of 2(+center dot) and 3(+center dot) displayed the nu(8a) band of the phenoxyl radicals at 1612 cm(-1), as well as the nu(8a) bands of the phenolates. In contrast, the Raman spectrum of 1(+center dot) exhibited the nu(8a) band at 1602 cm(-1), without any evidence of the phenolate peak. Previous work showed an intense near-infrared (NIR) electronic transition for 1(+center dot) (Delta nu(1/2) = 660 cm(-1), epsilon = 21700 M(-1)cm(-1)), indicating that the electron hole is fully delocalized over the ligand. The broader and moderately intense NIR transition of 2(+center dot) (Delta nu(1/2) = 1250 cm(-1), epsilon = 12800 M(-1)cm(-1)) suggests a certain degree of ligand-radical localization, whereas the very broad NIR transition of 3(+center dot) (Delta nu(1/2) = 8630 cm(-1), epsilon = 2550 M(-1)cm(-1)) indicates significant localization of the ligand radical on a single ring. Therefore, 1(+center dot) is a Class III mixed-valence complex, 2(+center dot) is Class II/III borderline complex, and 3(+center dot) is a Class II complex according to the Robin-Day classification method. By employing the Coulomb-attenuated method (CAM-B3LYP) we were able to predict the electron-hole localization and NIR transitions in the series, and show that the energy match between the redox-active ligand and the metal d orbitals is crucial for delocalization of the radical SOMO., WILEY-V C H VERLAG GMBH
Chem. Eur. J., 2012年, ［査読有り］

New Insights into the Electronic Structure and Reactivity of One-Electron Oxidized Copper(II)-(Disalicylidene)diamine Complexes.
Kazutaka Asami; Kazuaki Tsukidate; Satoshi Iwatsuki; Fumito Tani; Satoru Karasawa; Linus Chiang; Tim Storr; Fabrice Thomas; Yuichi Shimazaki, The neutral and one-electron oxidized Cu(II) six-membered chelate 1,3-Salcn (1,3-Salcn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-cyclohexanediamine) complexes have been investigated and compared with the five-membered chelate 1,2-Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) complexes. Cyclic voltammetry of Cu(1,3-Salcn) showed two reversible redox waves at 0.48 and 0.68 V, which are only 0.03 V higher than those of Cu(1,2-Salcn). Reaction of Cu(1,3-Salcn) with 1 equiv of AgSbF6 afforded the oxidized complex which exists as a ligand-based radical species in solution and in the solid state. The X-ray crystal structure of the oxidized complex, [Cu(1,3-Salcn)]SbF6, exhibited an asymmetric metal binding environment with a longer Cu-O bond and quinoid distortion in the phenolate moiety on one side, demonstrating at least partial ligand radical localization in the solid state. The ligand oxidation is also supported by XPS and temperature dependent magnetic susceptibility. The electronic structure of the [Cu(1,3-Salcn)](+) complex was further probed by UV-vis-NIR, resonance Raman, and electron paramagnetic resonance (EPR) measurements, and by theoretical calculations, indicating that the phenoxyl radical electron is relatively localized on one phenolate moiety in the molecule. The reactivity of [Cu(1,3-Salcn)](+) with benzyl alcohol was also studied. Quantitative conversion of benzyl alcohol to benzaldehyde was observed, with a faster reaction rate in comparison with [Cu(1,2-Salcn)](+). The kinetic isotope effect (KIE = k(H)/k(D)) of benzyl alcohol oxidation by [Cu(1,3-Salcn)](+) was estimated to be 13, which is smaller than the value reported for [Cu(1,2-Salcn)](+). The activation energy difference between [Cu(1,2-Salcn)](+) and [Cu(1,3-Salcn)](+) was in good agreement with the energy calculated from KIE. This correlation suggests that the Cu(II)-phenoxyl radical species, characterized for [Cu(1,2-salcn)](+) is more reactive for hydrogen abstraction from benzyl alcohol in comparison to the 1:1 mixture of Cu(III)-phenolate and Cu(II)-phenoxyl radical species, [Cu(1,2-Salcn)](+). Thus, the Cu(II)-phenoxyl radical species accelerates benzyl alcohol oxidation in comparison with the Cu(III)-phenolate ground state complex, in spite of the similar activated intermediate and oxidation pathway., AMER CHEMICAL SOC
Inorg.Chem., 2012年, ［査読有り］

Recent advances in metal-phenoxyl radical chemistry
Y. Shimazaki; O. Yamauchi, The phenolate ligand is well-known as one of the non-innocent ligands. It is typically shown in biological systems as the ligand of a single copper enzyme galactose oxidase, forming a relatively stable Cu(II)-phenoxyl radical intermediate. On the other hand, some of the one-electron oxidized metal-phenolate complexes are revealed to be high valent metal-phenolate complexes, which are isoelectronic with the metal-phenoxyl radical complexes. Therefore, characterization of the one-electron oxidized metal-phenolate complexes has recently been the subject of intense studies aiming at understanding their oxidation states under the given conditions. This review focuses on metal-phenolate complexes and their one-electron oxidized species and compares the properties of the metal-phenoxyl and high-valent metal-phenolate complexes., NATL INST SCIENCE COMMUNICATION-NISCAIR
Ind. J. Chem. A. (Review), 2011年, ［査読有り］, ［招待有り］

Influence of the chelate effect on the electronic structure of one-electron oxidized group 10 metal(II)-(disalicylidene)diamine complexes
Yuichi Shimazaki; Natsumi Arai; Tim J. Dunn; Tatsuo Yajima; Fumito Tani; Caterina F. Ramogida; Tim Storr, The neutral and one-electron oxidized group 10 metal, Ni(II), Pd(II) and Pt(II), six-membered chelate Salpn (Salpn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-propanediamine) complexes have been investigated and compared to the five-membered chelate Salen (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethanediamine) and Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) complexes. Reaction of the Salpn complexes with 1 equivalent of AgSbF6 affords the oxidized complexes which exist as ligand radical species in solution and in the solid state. The solid state structures of the oxidized complexes have been determined by X-ray crystal structure analysis. While the Ni and Pt analogues exhibit an essentially symmetric coordination sphere contraction upon oxidation, the oxidized Pd derivative exhibits an asymmetric metal binding environment demonstrating at least partial ligand radical localization. In comparison to the oxidized Salen and Salcn complexes, the propyl backbone of the Salpn complexes leads to a larger deviation from a planar geometry in the solid state. The electronic structure of the oxidized Salpn complexes was further probed by UV-vis-NIR measurements, electrochemistry, EPR spectroscopy, and theoretical calculations. The intense NIR band for the one-electron oxidized Salpn complexes shifts to lower energy in comparison to the 5-membered chelate analogues, which is attributed to lower metal d(xz) character in the beta-LUMO for the Salpn series. The reactivity of the one-electron oxidized Salpn complexes with exogenous ligands was also studied. In the presence of pyridine, the oxidized Ni analogue exhibits a shift in the locus of oxidation to a Ni(III) species. The oxidized PtSalpn complex rapidly decomposes in the presence of pyridine, even at low temperature. Interestingly, electronic and EPR spectroscopy suggests that the addition of pyridine to the oxidized Pd analogue results in initial dissociation of the phenoxyl radical ligand, likely due to the increased flexibility of the propyl backbone., ROYAL SOC CHEMISTRY
DALTON TRANSACTIONS, 2011年, ［査読有り］

Non-Innocent Ligand Behavior of a Bimetallic Ni Schiff-Base Complex Containing a Bridging Catecholate
Tim J. Dunn; Caterina F. Ramogida; Curtis Simmonds; Alisa Paterson; Edwin W. Y. Wong; Linus Chiang; Yuichi Shimazaki; and Tim Storr, The geometric and electronic structure of a bimetallic Ni Schiff-base complex and its one-electron oxidized form have been investigated in the solid state and in solution. The two salen units in the neutral complex 1 are linked via a bridging catecholate function. The one-electron oxidized form [1](+) was determined to exist as a ligand radical species in solution, with the electron hole potentially localized on the redox-active dioxolene, the phenolate ligands, or delocalized over the entire ligand system. Electrochemical experiments and UV-vis-NIR spectroscopy, in combination with density functional theory (DFT) calculations, provide insight into the locus of oxidation and the degree of delocalization in this system. The one-electron hole for [1](+) was determined experimentally to be localized on the dioxolene bridge with a small amount of spin density on the outer phenolate moieties predicted by the calculations. The resonance Raman spectrum of [1](+) (lambda(ex) = 413 nm) in CH2Cl2 solution clearly exhibited a new band at 1315 cm(-1) in comparison to 1, which is predicted to be a combination of dioxolene ring and C-O bond stretching modes, consistent with oxidation of the bridging moiety in [1](+). Analysis of the NIR bands for [1](+), in association with,time-dependent DFT calculations, suggests that the low energy bands are ligand to ligand charge transfer transitions from the terminal phenolates to the central dioxolene unit. In combination, this data is consistent with a description of the overall electronic structure of [1](+) as a bridge-localized semiquinone ligand radical species. This is in contrast to the mixed-valence ground state description for many one-electron oxidized Ni salen monomer systems, and analysis in terms of intervalence charge transfer (IVCT) theory., AMER CHEMICAL SOC
Inorg. Chem., 2011年, ［査読有り］

Concentration-dependent palladium(II)–indole bond formation in complexes with a 2N-donor ligand containing an indole moiety: Synthesis, characterization, and reaction analysis
Satoshi Iwatsuki; Takuya Suzuki; Tatsuo Yajima; Tadashi Shiraiwa; Osamu Yamauchi; Yuichi Shimazaki, The Pd(II) complexes of a 2N-donor ligand containing a pendent indole, 3-(2-pyridylmethylamino)ethylindole (L), were synthesized and characterized. Reaction of the ligand with [PdCl(2)(CH(3)CN)(2)] at room temperature gave [Pd(L)Cl(2)] (1) as pale yellow crystals. The X-ray crystal structure analysis and (1)H NMR spectrum of 1 revealed that the complex has a 2N2Cl-donor set in a square-planar geometry and that the pendent indole ring has no characteristic intramolecular interaction with the Pd(II) ion and the coordinated pyridine moiety. Refluxing a solution of 1 in CH(2)Cl(2)/DMF for a few hours under basic conditions gave yellow crystals, which were shown to be an indole-C2 binding complex [Pd(L)Cl] (2) by X-ray analysis. Conversion of complex 1 to 2 in DMSO was observed upon dilution of the solution of complex 1. From solution equilibrium and kinetic studies the initial step of the conversion by dilution has been assigned to the replacement of a coordinated Cl ion with the DMSO molecule. The ligand replacement easily occurred at low concentrations of 1. The complex with a coordinated solvent molecule exhibited a high reactivity and formed a stable Pd-C bond with the indole ring located close to the Pd(II) center. We discussed the concentration dependent formation of the indole-C2 binding complex 2 and its detailed mechanism. (C) 2011 Elsevier B. V. All rights reserved., ELSEVIER SCIENCE SA
Inorg.Chim.Acta, 2011年, ［査読有り］

Supramolecular Structures of Inclusion Complexes of C70 and Cyclic Porphyrin Dimers
Hirofumi Nobukuni; Takuya Kamimura; Hidemitsu Uno; Yuichi Shimazaki; Yoshinori Naruta; Fumito Tani, Cyclic nickel and free-base porphyrin dimers (Ni-2-CPDpy and H-4-CPDpy) include fullerene C-70 both in solution and in the crystals. Based on the C-13 NMR spectra in solution, the included C(70 molecu)le inside the cavity of Ni-2-CPDpy shows both end-on and side-on orientations, whereas the C-70 molecule within H-4-CPDPy has only a side-on orientation toward the porphyrin rings. X-ray crystallography revealed both "end-on" and "side-on" orientations of C-70 in the crystal structure of the inclusion complex of Ni-2-CPDPy and C-70. This is the first example of an X-ray crystallographic determination for an end-on orientation of C-70 cocrystallized with porphyrins. On the other hand, only a side-on orientation of C-70 was observed in the crystal structure of the complex of H-4-CPDPy and C-70. Further, a zigzag array of C-70 molecules through van der Waals contacts with each other is formed along the monoclinic b axis in the latter crystal., CHEMICAL SOC JAPAN
Bulletin of the Chemical Society of Japan, 2011年, ［査読有り］

Unprecedented formation of binuclear copper(II) complex with a perylene derived ligand by the oxidative reaction
J. Hagiwara; Y. Shimazaki; G. Saito, A new perylene-pendent tridentate ligand, N-(3-perylenylmethyl)-N,N-bis(2-pyridylmethyl) amine (perbpa) 1 and its Cu(II) complex, [Cu(perbpa)Cl-2] (2) were prepared and structurally characterized by the X-ray diffraction method. In the packing structure of ligand 1, perylene groups were aggregated to form a pi-pi stacked layer of dimerized pelylene moieties similar to the packing of pristine perylene. This result suggests both that the p-p interactions among the perylene moieties predominate for the arrangement of perbpa molecules in the crystal and that this ligand is a good candidate for constructing electron conducting path. A complex 2 was prepared from the ligand 1 and a copper(II) chloride dehydrate. Complex 2 had a mononuclear and 5-coordinate distorted square pyramidal structure with a perbpa and two coordinated chloride ions. The chemical oxidation of 2 by iodine resulted in the unprecedented binuclear Cu(II) species, [Cu-2(mu-Cl)(2)(perbpa)(2)](I-3)(2), 3.(I-3)(2). An X-ray crystal structure analysis of 3.(I-3)(2) revealed the binuclear structure bridged by the chloride ions. A temperature dependent magnetic susceptibility measurement of 3 showed a weak ferromagnetic exchange interaction with S = 1 ground state, g = 2.12 and J = +1.17 cm(-1), based on H = -2JS(1) . S-2. The UV-Vis absorption and the EPR spectra of 3 showed that the perylene groups are not oxidized. These results indicate a couple of Cu(II) constructed S = 1 ground state with intermolecular ferromagnetic interaction. The electrochemical study suggested that the crystallization of 3 center dot(I3) 2 was initiated by the oxidation of the N,N-bis-(2-pyridylmethyl) amino (bpa) groups of 2 by I-2. (C) 2010 Elsevier B.V. All rights reserved., ELSEVIER SCIENCE SA
Inorg. Chim. Acta, 2010年, ［査読有り］

Ligand Radical Localization in a Nonsymmetric One-Electron Oxidized Ni(II) Bis-phenoxide Complex
T. Storr; P. Verma; Y. Shimazaki; E. C. Wasinger; T. D. P. Stack, WILEY-BLACKWELL
Chem. Eur. J., 2010年, ［査読有り］

Supramolecular Structures and Photoelectronic Properties of the Inclusion Complex of a Cyclic Free-Base Porphyrin Dimer and C60
H. Nobukuni; Y. Shimazaki; H. Uno; Y. Naruta; K. Ohkubo; T. Kojima; S. Fukuzumi; S. Seki; H. Sakai; T. Hasobe and F. Tani, A cyclic free-base porphyrin dimer H-4-CPDPy (CPD = cyclic porphyrin dimer) linked by butadiyne moieties bearing 4-pyridyl groups self-assembles to form a novel porphyrin nanotube in the crystalline state. The cyclic molecules link together through non-classical C-H center dot center dot center dot N hydrogen bonds and pi-pi interactions of the pyridyl groups along the crystallographic a axis. H-4-CPDPy includes a C-60 molecule in its cavity in solution. In the crystal structure of the inclusion complex (C-60 subset of H-4-CPDPy), the dimer "bites" a C-60 molecule by tilting the porphyrin rings with respect to each other, and there are strong pi-pi interactions between the porphyrin rings and C-60. The included C-60 molecules form a zigzag chain along the crystallographic b axis through van der Waals contacts with each other. Femtosecond laser flash photolysis of C-60 subset of H-4-CPDPy in the solid state with photoexcitation at 420 nm shows the formation of a completely charge-separated state {H-4-CPDPy center dot+ + C-60(center dot-)}, which decays with a lifetime of 470 Ps to the ground state. The charge-carrier mobility of the single crystal of C-60 subset of H-4-CPDPy was determined by flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements. C-60 subset of H-4-CPDPy has an anisotropic charge mobility (Sigma mu=0.16 and 0.13 cm(2)V(-1) s(-1)) along the zigzag chain of C-60 (which runs at 45 degrees and parallel to the crystallographic b axis). To construct a photoelectro-chemical cell, C-60 subset of H-4-CPDPy was deposited onto nanostructured SnO2 films on a transparent electrode. The solar cell exhibited photovoltaic activity with an incident photon to current conversion efficiency of 17%., WILEY-BLACKWELL
Chem. Eur. J., 2010年, ［査読有り］

Metal Complexes involving indole rings: Structure and effects of metal-indole interaction
Yuichi Shimazaki; Tatsuo Yajima; Masako Takani; Osamu Yamauchi., Indole is an electron-rich aromatic compound with characteristic properties and is widely distributed in natural products and in proteins as the important constituent of essential amino acid tryptophan. it is known to form a hydrophobic environment in proteins and to be involved in enzymatic reactions. In addition to the redox activities and various weak interactions, it shows versatile metal binding abilities through the nitrogen and carbon atoms. This review focuses on the properties of the indole ring in and around the coordination sphere and the structures and bonding modes of Cu(I), Cu(II), Pd(II), and Pt(II) complexes of indole-containing ligands. Reactivities of indole-containing Cu(I) complexes with dioxygen, indole-radical formation by oxidation of Pd(II) and Pt(II) Complexes, and the effects of the proximal indole ring on the reactivity of the Cu(I) center are also reviewed. (C) 2008 Elsevier B.V. All rights reserved., ELSEVIER SCIENCE SA
Coord. Chem. Rev., 2009年, ［査読有り］, ［招待有り］

Synthesis and Characterization of platinum(II) complexes of 2N10-donor ligands with a pendent indole ring
Yuichi Shimazaki; Tatsuo Yajima; Yasuo Nakabayashi; Yoshinori Naruta; Osamu Yamauchi., The Pt(II) complexes of 2N1O-donor ligands containing a pendent indole, 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl) benzylamino] ethylindole (Htbu-iepp), and 1-methyl-3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl) benzylamino] ethylindole (Htbu-miepp) (H denotes an ionizable hydrogen), were synthesized, and the structure of [Pt(tbu-iepp) Cl] (1) was determined by X-ray analysis. Complex 1 prepared in CH(3)CN was revealed to have the C2 atom of the indole ring bound to Pt(II) with the Pt(II)-C2 distance of 1.981(3) angstrom. On the other hand, [Pt(tbu-miepp) Cl] (2) was concluded to have a phenolate coordination instead of the C2 atom of the indole ring by (1)H NMR spectra. Reaction of 1 with 1 equiv. of Ce(IV) in DMF gave the corresponding one-electron oxidized species, which exhibited an ESR signal at g = 2.004 and an absorption peak at 567 nm, indicating the formation of the Pt(II)-indole-pi-cation radical species. The half-life, t(1/2), of the radical species at -60 degrees C was calculated to be 43 s (k(obs) = 1.6 x 10(-2) s(-1)). (C) 2008 Elsevier B. V. All rights reserved., ELSEVIER SCIENCE SA
Inorg. Chim. Acta, 2009年, ［査読有り］

Zinc(II)-phenoxyl radical complexes: Dependence on complexation properties of Zn-phenolate species
Yuichi Shimazaki; Tatsuo Yajima; Tadashi Shiraiwa; Osamu Yamauchi., Zinc(II) complexes of N(3)O-donor tripodal ligands, 2,4-di(tert-butyl)-6-{[bis(2-pyridyl) methyl] aminomethyl} phenol (HtbuL), 2,4-di(tert-butyl)-6-{[ (6-methyl-2-pyridyl) methyl]-(2-pyridyl) methylaminomethyl} phenol (HtbuLMepy), and 2,4-di(tert-butyl)-6-{[bis(6-methyl-2-pyridyl) methyl] aminomethyl} phenol (HtbuL(Mepy)(2)), [Zn(tbuL)Cl] center dot CH(3)OH (1), [Zn(tbuLMepy)Cl] (2), and [Zn(tbuL(Mepy)(2))Cl] (3), respectively, were prepared and structurally characterized by the X-ray diffraction method. All the complexes were found to have a mononuclear structure with a coordinated phenolate moiety, the geometry of the Zn(II) center being 5-coordinate trigonal-bipyramidal. The Zn(II) binding ability of the ligands with and without 6-methyl-2-pyridylmethyl moieties was evaluated for similar ligands, which lacked the t-butyl groups at the 2-and 4-positions of the phenol moiety, by the stability constants determined by potentiometric titration at 25 degrees C (I = 0.1 M (KNO(3))). The stability of the complexes was found to be in the order L > LMepy > L(Mepy)(2), reflecting the steric hindrance of the 6-methyl group of the pyridine ring. Complexes 1, 2, and 3 were converted to the phenoxyl radicals upon oxidation with Ce(IV), giving a phenoxyl radical pi-pi* transition band at 394-407 nm. ESR and resonance Raman spectra established that the radical species had a Zn(II)-phenoxyl radical bond. The cyclic voltammograms showed similar quasi-reversible redox waves with E(1/2) = 0.68, 0.67, and 0.63 V (versus Ag/AgCl) for 1, 2, and 3, respectively, corresponding to the formation of the phenoxyl radical, which displayed a first-order decay. The half-lives, 58.6, 25.8, and 15.6 min at -40 degrees C for 1, 2, and 3, respectively, follow the order of the stability constants of the complexes, indicating that the metal(II) -phenoxyl radical stability is in close relationship with the complexation properties of the present series of N(3)O-donor ligands. (C) 2008 Elsevier B. V. All rights reserved., ELSEVIER SCIENCE SA
Inorg. Chim. Acta, 2009年, ［査読有り］

Metal complexes of amino acids and amino acid side chain groups. Structure and properties.
Yuichi Shimazaki; Masako Takani; Osamu Yamauchi, alpha-Amino acid residues exhibit various functions in biological systems. The side chain groups are very important for formation of the metal center and its catalytic action in proteins. They are involved in metal binding, molecular recognition by weak interactions, enzyme catalysis, and formation of the molecular environment. This perspective focuses on recent studies on characterization of metal-amino acid complexes involving imidazole, phenol, indole, or alkyl groups, their reactivities, and some selected metal-side chain group interactions., ROYAL SOC CHEMISTRY
Dalton Trans.(perspective), 2009年, ［査読有り］, ［招待有り］

Detailed Evaluation of the Geometric and Electronic Structures of One-electron Oxidized Group 10 (Ni, Pd, and Pt) Metal(II)-(Disalicylidene)diamine Complexes
Yuichi Shimazaki; T. Daniel P. Stack; Tim Storr, The geometric and electronic structures of a series of one-electron oxidized group 10 metal salens (Ni, Pd, Pt) have been investigated in solution and in the solid state. Ni (1) and Pd (2) complexes of the tetradentate salen ligand N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine (H(2)Salen) have been examined along with the Pt (3) complex of the salen ligand N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediamine (H(2)Salen). All three oxidized compounds exist as ligand radical species in solution and in the solid state. The solid state structures of [1](+) and [3](+) exhibit a symmetric coordination sphere contraction relative to the neutral forms. By contrast, the coordination sphere of the Pd derivative [2](+) exhibits a pronounced asymmetry in the solid state. In solution, the oxidized derivatives display intense low-energy NIR transitions consistent with their classification as ligand radical compounds. Interestingly, the degree of communication between the phenolate moieties depends strongly on the central metal ion, within the Ni, Pd, and Pt series. Electrochemical measurements and UV-vis-NIR spectroscopy, in conjunction with density functional theory calculations provide insights into the degree of delocalization of the one-electron hole in these systems. The Pd complex [2](+) is the least delocalized and is best described as a borderline Class II/III intervalence complex based on the Robin-Day classification system. The Ni [1](+) and Pt [3](+) analogues are Class III (fully delocalized) intervalence compounds. Delocalization is dependent on the electronic coupling between the redox-active phenolate ligands, mediated by overlap between the formally filled metal d(xz) orbital and the appropriate ligand molecular orbital. The degree of coupling increases in the order Pd < Ni < Pt for the one-electron oxidized group 10 metal salens., AMER CHEMICAL SOC
Inorg. Chem., 2009年, ［査読有り］

Anisotropic High Electron Mobility and Photodynamics of a Self-Assembled Porphyrin Nanotube including C60 Molecules
Hirofumi Nobukuni; Fumito Tani; Yuichi Shimazaki; Yoshinori Naruta; Kei Ohkubo; Tatsuaki Nakanishi; Takahiko Kojima; Shunichi Fukuzumi; Shu Seki, A cyclic porphyrin dimer (Ni-2-CPDpy) linked by butadiyne moieties bearing 4-pyridyl groups includes a C-60 molecule inside its cavity in solution to give a 1:1 inclusion complex (C-60 subset of Ni-2-CPDPy). The charge-transfer (CT) band is observed at 645 nm in the UV-vis absorption spectrum of the solution of C-60 subset of Ni-2-CPDPPy. In the cyclic voltammogram of C-60 subset of Ni-2-CPDPy, a small anodic shift of the porphyrin oxidation potential and a small cathodic shift of the fullerene reduction potential compared with their original redox potentials are indicative of CT interaction from the porphyrin to C-60. In the crystal structure of C-60 subset of Ni-2-CPDPy a porphyrin nanotube is formed by the self-assembly of Ni-2-CPDPy . Ni-2-CPDPy molecules link together through nonclassical C-H center dot center dot center dot N hydrogen bonds and pi-pi interactions of the pyridyl groups along the crystallographic b axis. The included C-60 molecules are linearly arranged in the nanotube to afford a supramolecular peapod. The charge-carrier mobility of the single crystal of C-60 subset of Ni-2-CPDPy was determined by flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements. It has an anisotropic high electron mobility (Sigma mu = 0.72 cm(2) V-1 s(-1)) along the linear army of C-60 (crystallographic b axis). Femtosecond laser flash photolysis of C-60 subset of Ni2CPDPy in the solid state with photoexcitation at the Soret band of the porphyrin shows the formation of a triplet exciplex (3){Ni-x-CPDPy center dot center dot center dot C-60}*, which decays with a lifetime of 34 ps to the ground state without observation of a complete charge-separated state., AMER CHEMICAL SOC
J. Phys. Chem. C, 2009年, ［査読有り］

CH•••Metal(II) axial interaction in planar complexes (metal = Cu, Pd) and implications for possible environmental effects of alkyl groups at biological copper site
Osamu Yamauchi; Tatsuo Yajima; Rie Fujii; Yuichi Shimazaki; Masanobu Yabusaki; Masako Takani; Minoru Tashiro; Takeshi Motoyama; Mitsuhiro Kakuto; Yasuo Nakabayashi, Intramolecular M(II)center dot center dot center dot H-C interactions (M(II)=Cu(II), Pd(II)) involving a side chain alkyl group of planar d(8) and d(9) metal complexes of the N-alkyl (R) derivatives of N,N-bis(2-pyridylmethyl)amine with an N3Cl donor set were established by structural and spectroscopic methods. The methyl group from the branched alkyl group (R = 2,2-dimethylpropyl and 2-methylbutyl) axially interacts with the metal ion with the M center dot center dot center dot C and M center dot center dot center dot H distances of 3.056(3)-3.352(9) and 2.317(1)-2.606(1) angstrom, respectively, and the M-H-C angles of 122.4-162.3 degrees. The Cu(II) complexes showing the interaction have a higher redox potential as compared with those without it, and the H-1 NMR signals of the interacting methyl group in Pd(II) complexes shifted downfield relative to the ligand signals. Dependence of the downshift values on the dielectric constants of the solvents used indicated that the M(II)center dot center dot center dot H-C interaction is mainly electrostatic in nature and may be regarded as a weak hydrogen bond. Implications for possible environmental effects of the leucine alkyl group at the type I Cu site of fungal laccase are also discussed. (C) 2007 Elsevier Inc. All rights reserved., ELSEVIER SCIENCE INC
J. InorgBio. Chem., 2008年, ［査読有り］

A simple preparation of d-alloisoleucine via acetylation and separation of the ammonium salts
Tatsuo Yajima; Takao Horikawa; Nobuhiro Takeda; Eri Takemura; Hiroaki Hattori; Yuichi Shimazaki; Tadashi Shiraiwa, D-Alloisoleucine was obtained from L-isoleucine by acetylation and epimerization by acetic anhydride followed by separation of the diastereoisomeric ammonium salts using the solubility difference. The structure-solubility relationship of diastereoisomeric salts was explained by X-ray crystal structure analysis. (C) 2008 Elsevier Ltd. All rights reserved., PERGAMON-ELSEVIER SCIENCE LTD
Tetrahedron Assymetry, 2008年, ［査読有り］

Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper-Bis-phenoxide Complexes
Tim Storr; Pratik Verma; Russell C. Pratt; Eric. C. Wasinger; Yuichi Shimazaki; T. Daniel P. Stack, The geometric and electronic structure of an oxidized Cu complex ([CuSal](+); Sal = N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal](+) (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal](+), affording exclusively a Cu(III) species in the solid state (4-300 K). Variable-temperature solution studies suggest that [CuSal](+) exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal(center dot)](+) (S = 1) and the high-valent metal form [Cu(III)Sal](+) (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine-bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSal(red)](+) (Sal red = N,N-bis(3,5-di-tert-butylhydroxybenzyl)-1,2-cyclohexane-(1 R,2R)-diamine) exists as a temperature-invariant Cu(II)-ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu-bis-phenoxide complexes., AMER CHEMICAL SOC
J. Am. Chem. Soc., 2008年, ［査読有り］

- Stacking assisted binding of aromatic amino acids by copper(II)-aromatic diimine complexes. Effects of ring substituents on ternary complex stability
Tatsuo Yajima; Reiko Takamido; Yuichi Shimazaki; Akira Odani; Yasuo Nakabayashi; Osamu Yamauchi, Ternary Cu(II) complexes containing an aromatic diimine (DA = di(2-pyridylmethyl)amine (dpa), 4,4'-disubstituted 2,2'-bipyridine (Y(2)bpy; Y = H (bpy), Me, Cl, N(Et)(2), CONH2 or COOEt) or 2,2'-bipyrimidine) and an aromatic amino acid (AA = L-phenylalanine (Phe), p-substituted phenylalanine (XPhe; X = NH2, NO2, F, Cl or Br), L-tyrosine (Tyr), L-tryptophan (Trp) or L-alanine (Ala)) were characterized by X-ray diffraction, spectroscopic and potentiometric measurements. The structures of [Cu(dpa)(Trp)]ClO4 center dot 2H(2)O and [Cu((CONH2)(2)bpy)(Phe)]ClO4 center dot H2O in the solid state were revealed to have intramolecular pi-pi interactions between the Cu(II)-coordinated aromatic ring moiety, Cu(DA) (M pi), and the side chain aromatic ring of the AA (L pi). The intensities of M pi-L pi interactions were evaluated by the stability constants of the ternary Cu(II) complexes determined at 25 degrees C and I = 0.1 M (KNO3), which revealed that the stability enhancement of the Cu(DA)(AA) systems due to the interactions is in the order (CONH2)(2)bpy < bpy < Me(2)bpy < (Et2N)(2)bpy with respect to DA. The results indicate that the electron density of coordinated aromatic diimines influences the intensities of the stacking interactions in the Cu(DA)(AA) systems. The M pi-L pi interactions are also influenced by the substituents, X, of L pi and are in linear relationship with their Hammett sigma(p) values with the exception of X = Cl and Br., ROYAL SOC CHEMISTRY
Dalton Trans., 2007年, ［査読有り］

Syntheses and Electronic Structures of One-Electron-Oxidized Group 10 Metal(II)-(Disalicylidene)diamine Complexes (Metal = Ni, Pd, Pt)
Yuichi Shimazaki; Tatsuo Yajima; Fumito Tani; Satoru Karasawa; Koichi Fukui; Yoshinori Naruta; Osamu Yamauchi, Group 10 metal(II) complexes of H(2)tbu-salen (H(2)tbu-salen = N,N'-bis(3',5'-di-tert-butylsalicylidene)ethylenediamine) and H(2)tbu-salcn (H(2)tbu-salcn = N,N'-bis(3',5'-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) containing two 2,4-di(tert-butyl)phenol moieties, [Ni(tbu-salen)] (1a), [Ni(tbu-salcn)] (1b), [Pd(tbu-salen)] (2a), [Pd(tbu-salcn)] (2b), and [Pt(tbu-salen)] (3), were prepared and structurally characterized by X-ray diffraction, and the electronic structures of their one-electron-oxidized species were established by spectroscopic and electrochemical methods. All the complexes have a mononuclear structure with two phenolate oxygens coordinated in a very similar square-planar geometry. These complexes exhibited similar absorption spectra in CH2Cl2, indicating that they all have a similar structure in solution. Cyclic voltammograms of the complexes showed a quasi-reversible redox wave at E-1/2 = 0.82-1.05 V (vs Ag/AgCl), corresponding to formation of the relatively stable one-electron-oxidized species. The electrochemically oxidized or Ce(IV)-oxidized species of 1a, 2a, and 3 displayed a first-order decay with a half-life of 83, 20, and 148 min at -20 degrees C, respectively. Ni(II) complexes 1a and 1b were converted to the phenoxyl radicals upon one-electron oxidation in CH2Cl2 above -80 degrees C and to the Ni(III)-phenolate species below -120 degrees C. The temperature-dependent conversion was reversible with the Ni(III)-phenolate ground state and was found to be a valence tautomerism governed by the solvent. One-electron-oxidized 1b was isolated as [Ni(tbu-salcn)]NO3 (4) having the Ni(II)-phenoxyl radical ground state. One-electron-oxidized species of the Pd(II) complexes 2a and 2b were different from those of the Ni(II) complexes, the Pd(II)-phenoxyl radical species being the ground state in CH2Cl2 in the range 5-300 K. The one-electron-oxidized form of 2b, [Pd(tbu-salcn)]NO3 (5), which was isolated as a dark green powder, was found to be a Pd(II)-phenoxyl radical complex. On the other hand, the ESR spectrum of the one-electron-oxidized species of Pt(II) complex 3 exhibited a temperature-independent large g anisotropy in CH2Cl2 below -80 degrees C, while its resonance Raman spectrum at -60 degrees C displayed nu(8a) of the phenoxyl radical band at 1600 cm(-1). These results indicated that the ground state of the Pt(II)-phenoxyl radical species has a large distribution of the radical electron spin at the Pt center. One-electron oxidation of 3 gave [Pt(tbu-salen)]NO3 (6) as a solid, where the oxidation state of the Pt center was determined to be ca. +2.5 from the XPS and XANES measurements., AMER CHEMICAL SOC
J. Am. Chem. Soc., 2007年, ［査読有り］

Synthesis and characterization of imidazolate-bridged polynuclear copper complexes
Takumi Higa; Masaki Moriya; Yuichi Shimazaki; Tatsuo Yajima; Fumito Tani; Satoru Karasawa; Motohiro Nakano; Yoshinori Naruta; Osamu Yamauchi, Copper(II) complexes of N4-donor ligands containing imidazole moieties, 4-[bis(1-methylimidazole-2-yl-methyl)aminomethyl]imidazole (Him-im(2)) and 4-[bis(1-methylimidazole-2-yl-methyl)aminoethyl]imidazole (Hhis-im2), were prepared, and [Cu(Him-im(2))Cl]ClO4 (1) and [Cu(Hhis-im(2))Cl]ClO4 (2) were structurally characterized by the X-ray diffraction method. Complexes 1 and 2 have a mononuclear structure with a coordinated chloride ion. The geometry of the Cu(II) center in 1 was found to be 5-coordinate trigonal-bipyramidal, whereas that of 2 was square-pyramidal. Complexes 1 and 2 showed different absorption and EPR spectra in MeOH, indicating that these compounds in solution maintain the structures revealed in the solid state. On the other hand, the reaction of Him-im(2) with Cu(ClO4)(2) center dot 6H(2)O under basic conditions gave a tetranuclear Cu(II) complex, [Cu-4(im-im(2))(4)](ClO4)(4) (3), whereas using the ligand Hhis-im(2) gave two kinds of polynuclear complexes [Cu-4(his-im(2))(4)](ClO4)(4) (4) and [Cu-6(his-im(2))(6)](ClO4)(6) (5) exhibiting discretely different structures. X-ray crystal structure analysis of the polynuclear complexes revealed their cyclic structures bridged by the imidazolate moiety. The geometry difference of the Cu(II) centers between 1 and 2 is thus concluded to determine the structures of tetranuclear complexes 3 and 4, respectively. Temperature dependent magnetic susceptibility measurements of complexes 3, 4, and 5 have shown an antiferromagnetic exchange interaction with a coupling constant of J=-32.5, -27.1 and -22.8 cm(-1), respectively. (c) 2007 Elsevier B.V. All rights reserved., ELSEVIER SCIENCE SA
Inorg. Chim. Acta, 2007年

Formation and Characterization of Co(III)-Semiquinonate Phenoxyl Radical Species
Yuichi Shimazaki; Ryota Kabe; Stefan Huth; Fumito Tani; Yoshinori Naruta; Osamu Yamauchi, Co(III) complexes of N3O-donor tripodal ligands, 2,4-di(tert-butyl)-6-{[bis(2-pyridyl)methyl]aminomethyl}phenolate (tbuL), 2,4-di(tert-butyl)-6-{[bis(6-methyl-2-pyridyl)methyl]aminomethyl}phenolate (tbuL(Mepy)(2)), were prepared, and precursor Co(II) complexes, [Co(tbuL)Cl] (1) and [Co(tbuL(Mepy)(2))Cl] (2), and ternary Co(III) complexes, [Co(tbuL)(acac)]ClO4 (3), [Co(tbuL)(tbu-cat)] (4), and [Co(tbuL(Mepy)(2))(tbu-SQ)]ClO4 (5), where acac, tbu-cat, and tbu-SQ refer to pentane-2,4-dionate, 3,5-di(tert-butyl)catecholate, and 3,5-di(tert-butyl)semiquinonate, respectively, were structurally characterized by the X-ray diffraction method. Complexes 3 and 5 have a mononuclear structure with a fac-N3O3 donor set, while 4 has a mer-N3O3 structure. The cyclic voltammogram (CV) of complex 3 exhibited one reversible redox wave centered at 0.93 V (vs Ag/AgCl) in CH3CN. Complex 5 was converted to a phenoxyl radical species upon oxidation with Ce(IV), showing a characteristic pi-pi* transition band at 412 nm. The ESR spectrum at low temperature and the resonance Raman spectrum of 3 established that the radical species has a Co(III)-phenoxyl radical bond. On the other hand, the CVs showed two oxidation processes at E-1/2 = 0.01 and E-pa = 0.92 V for 4 and E-1/2a = 0.05 and E-1/2b = 0.69 V for 5. The rest potential of 4 (-0.11 V) was lower than the E-1/2 value, whereas that of 5 (0.18 V) was higher, indicating that the first redox wave of 4 and 5 is assigned to the tbu-cat and the tbu-SQ redox process, respectively. One-electron oxidized 4 showed absorption, resonance Raman, and ESR spectra which are similar to those of 5, suggesting formation of a stable Co(III)-semiquinonate species, which has the same oxidation level of 5. The resonance Raman spectrum of two-electron oxidized 4 showed the nu(8a) bands of the semiquinonate and phenoxyl radical, which were absent in the spectrum of one-electron oxidized 5. Since both oxidized species were ESR inactive at 5 K, the former was concluded to be a biradical species containing semiquinonate and phenoxyl radicals coupled antiferromagnetically and the latter to a species with a coordinated quinone., AMER CHEMICAL SOC
Inorg. Chem., 2007年, ［査読有り］

A Nanotube of Cyclic Porphyrin Dimer Connected by Nonclassical Hydrogen Bonds and Its Inclusion of C60 in a Linear Arrangement
Hirofumi Nobukuni; Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 2007年, ［査読有り］

Synthesis Crystal Structures and Single Small Molecule Encapsulation Properties of Cavitand-Porphyrin
Jun Nakazawa; Maki Mizuki; Jun Hagiwara; Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta, New capsule-shaped hosts "cavitand-linked porphyrin" metal complexes (Mcp: M = H-2, Ni, Zn, and Pd) have been synthesized to mimic the substrate binding functions of metalloenzymes such as cytochrome P-450(cam).Crystal structures of cavitand 1(.)MeOH(.)CHCl(3), [Zntpp(MeOH)], [Nicp](.)MeOH(.)2CHCl(3)(.)3H(2)O, [Zncp(MeOH)](.)2CHCl(3)(.) 3H(2)O, and [Pdcp](.)MeOH(.)2CHCl(3).3H(2)O have been determined. One methanol molecule, originating from crystallization solvent is encapsulated in each host cavity, and coordinates to Zn in Zncp but not in Ni- and Pdcp. Encapsulation of various small hydrocarbon molecules in CDCl3 Solutions of Mcps have been evaluated by determining binding constants and thermodynamic parameters obtained from H-1 NMR titrations. All Mcps encapsulate hydrocarbons smaller than propane under atmospheric pressure. The guest size selectivity is primarily influenced by cavity size, and partly by metal insertion. The metal ion radius does not affect guest size selectivity. Encapsulation of coordinating guest molecules (MeOH, EtOH, MeCN, and H2O) in Mcps has also been investigated. Only Zncp favors coordination of non-hydrocarbon guests such as MeOH. We concluded that accommodation of different size guests by Mcps depends upon guest sizes and coordination of functional groups depends upon both the identity of the porphyrin's metal ion and guest sizes., CHEMICAL SOC JAPAN
Bull. Chem. Soc. Jpn., 2006年, ［査読有り］

Encapsulation of Small Molecules by a Cavitand Porphyrin Self-Assenbled via Quadruple Hydrogen Bonds
Jun Nakazawa; Maki Mizuki; Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta, A new and stable quadruple hydrogen-bonded capsule, tetracarboxylcavitand.meso-tetra(2-pyridyl) porphyrin (1, 2) has been synthesized and spectroscopically characterized. 1, 2 can encapsulate small molecules of various size from methane to cyclopentane. The guest and host exchange rates were evaluated by EXSY., AMER CHEMICAL SOC
Org. Lett., 2006年, ［査読有り］

Selective formation of a stable -peroxo ferric heme-CuII complex from the corresponding -oxo FeIII-CuII species with hydrogen peroxide
Takefumi Chishiro; Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta, An oxo-bridged ferric heme-copper(II) complex, obtained by thermal transformation of the corresponding peroxo-bridged complex, was reacted with an equimolar amount of H2O2 to regenerate the p-peroxo, complex by a ligand exchange from oxo to peroxo, without the formation of a ferryl-oxo species or heme degradation as are observed in general ferric heme-H2O2 reactions., ROYAL SOC CHEMISTRY
Chem. Commun., 2005年02月, ［査読有り］

Size-Selective and Reversible Encapsulation of Single Small Hydrocarbon Molecules by a Cavitand-Porphyrin Species
Jun Nakazawa; Jun Hagiwara; Maki Mizuki; Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 2005年, ［査読有り］

Cyclopalladation of the Indole Ring in Palladium(II) Complexes of 2N1O Donor Ligands and Its Dependence on the O-Donor Properites
Yuichi Shimazaki; Minoru Tashiro; Takeshi Motoyama; Satoshi Iwatsuki; Tatsuo Yajima; Yasuo Nakabayashi; Yoshinori Naruta; Osamu Yamauchi, Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and H-1 NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pK(a) value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4., AMER CHEMICAL SOC
Inorg. Chem., 2005年, ［査読有り］

Characterization of Dinuclear MnV=O Complex and Its Efficient O2 Evolution in the Presence of Water
Yuichi Shimazaki; Taro Nagano; Hironori Takesue; Bao-Hui Ye; Fumito Tani; Yoshinori Naruta, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 2004年, ［査読有り］

Reactivity of the Indole Ring in Palladium(II) Complexes of 2N1O-Donor Ligands: Cyclopalladation and -Cation Radical Formation
Takeshi Motoyama; Yuichi Shimazaki; Tatsuo Yajima; Yasuo Nakabayashi; Yoshinori Naruta; Osamu Yamauchi, The Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-iepp), 1-methyl-3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-miepp), 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]methylindole (Htbu-impp), and 3- (N-2-pyridylmethyl-N-4-hydroxybenzylamino)ethylindole (Hp-iepp) (H denotes a dissociable proton), were synthesized, and the structures of [Pd(tbu-iepp)Cl] (1a), [Pd(tbu-iepp-c)Cl] (1b), [Pd(tbu-miepp)Ci] (3), and [Pd(p-iepp-c)Cl] (4) (tbu-iepp-c and p-iepp-c denote tbu-iepp and p-iepp bound to Pd(II) through a carbon atom, respectively) were determined by X-ray analysis. Complexes la prepared in CH2Cl2/CH3CN and 3 prepared in CH3CN have a pyridine nitrogen, an amine nitrogen, a phenolate oxygen, and a chloride ion in the coordination plane. Complex 1b prepared in CH3CN has the same composition as 1 a and was revealed to have the C2 atom of the indole ring bound to Pd(II) with the Pd(II)-C2 distance of 1.973(2) Angstrom. The same Pd(II)-indole C2 bonding was revealed for 4. Interconversion between 1a and 1b was observed for their solutions, the equilibrium being dependent on the solvent used. Reaction of 1b and 4 with 1 equiv of Ce(IV) in DMF gave the corresponding one-electron-oxidized species, which exhibited an ESR signal at g = 2.004 and an absorption peak at similar to550 nm, indicating the formation of the Pd(II)-indole pi-cation radical species. The half-lite, t(1/2), of the indole radical species at room temperature was calculated to be 20 s (k(obs) = 3.5 x 10(-2) s(-1)) for 1b. The cyclic voltammogram for 1b in DMF gave two irreversible oxidation peaks at E-pa = 0.68 and 0.80 V (vs Ag/AgCl), which were ascribed to the oxidation processes of the coordinated indole and phenolate moieties, respectively., AMER CHEMICAL SOC
J. Am. Chem. Soc., 2004年, ［査読有り］

Nickel(II)-Phenoxyl Radical Complexes: Structure-Radical Stability Relationship
Yuichi Shimazaki; Stefan Huth; Satoru Karasawa; Shun Hirota; Yoshinori Naruta; Osamu Yamauchi, Nickel(II) complexes of N3O-donor tripodal ligands, 2,4-di-tert-butyl-6-{([bis(2-pyridyl)methyl]amino)methyl}phenol (HtbuL), 2,4-di-tert-butyl-6-{([ (6-methyl-2-pyridyl)methyl](2-pyridylmethyl)amino)methyl}phenol (HtbuLMepy), and 2,4-di-tert-butyl-6-{([bis(6-methyl-2-pyridyl)methyl]amino)methyl } }phenol (HtbuL(Mepy)(2)), were prepared, and [Ni(tbuL)-Cl(H2O)] (1), (Ni(tbuLMepy)Cl] (2), and [Ni(tbuL(Mepy)(2))Cl] (3) were structurally characterized by the X-ray diffraction method. Complexes 1 and 3 have a mononuclear structure with a coordinated phenolate moiety, while 2 has a dinuclear structure bridged by two chloride ions. The geometry of the Ni(II) center was found to be octahedral for 1 and 2 and 5-coordinate trigonal bipyramidal for 3. Complexes 1-3 exhibited similar absorption spectra in CH3CN, indicating that they all have a mononuclear structure in solution. They were converted to the phenoxyl radicals upon oxidation with Ce(IV), giving a phenoxyl radical, pi-pi* transition band at 394-407 nm. ESR spectra at low temperature and resonance Raman spectra established that the radical species has a Ni(II)-phenoxyl radical bond. The cyclic voltammograms showed a quasi-reversible redox wave at E-1/2 = 0.46-0.56 V (vs Ag/AgCl) corresponding to the formation of the phenoxyl radical, which displayed a first-order decay with a half-life of 45 min at room temperature for 1 and 26 and 5.9 min at -20 degreesC for 2 and 3, respectively. The radical stability increased with the donor ability of the N ligands., AMER CHEMICAL SOC
Inorg. Chem., 2004年, ［査読有り］

Intramolecular Rearrangement for Regioselective Complexation Delived from Intramolecular CH/ Interaction in a Hydrophobic Ruthenium Coordination Sphere
Takahiko Kojima; Sousi Miyazaki; Ken-ichi Hayashi; Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta; Yoshihisa Maeda, A Ru-11 complex with a hydrophobic cavity formed from two 1-naphthoylamide groups was prepared. Its reactions with beta-diketones gave beta-diketonato complexes in which hydrophobic pi-pi or CH/pi interactions were confirmed by NMR spectroscopy and X-ray crystallography. In the case of the asymmetric beta-diketone benzoylace-tone, an isomer with a CH/pi interaction was afforded as the sole product owing to thermodynamic control. The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-beta-diketonato coordination bonds (activation energy 52 kJmol(-1)). This indicates that CH/pi interactions can be more favored thermodynamically than pi-pi interactions in a suitable hydrophobic environment., WILEY-V C H VERLAG GMBH
Chem. Eur. J., 2004年, ［査読有り］

An Active-Site Model of Prostaglandin H Synthase: Iron “Twin Coronet” Porphyrin with an Aryloxyl Radical and Its Catalytic Oxygenation of 1,4-Diene
Eiki Matsui; Yoshinori Naruta; Fumito Tani; Yuichi Shimazaki, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 2003年

Isolation and Crystal Structure of a Peroxo-Bridged Heme-Copper Complex
Takefumi Chishiro; Yuichi Shimazaki; Fumito Tani; Yoshimitzu Tachi; Yoshinori Naruta; Satoru Karasawa; Shinya Hayami; Yonezo Maeda, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 2003年, ［査読有り］

One-electron Oxidized Nickel(II)-Di(salicylidene)diamine Complexes: Temperature Dependent Tautomerism between Ni(III)-Phenolate and Ni(II)-Phenoxyl Radical States
Yuichi Shimazaki; Fumito Tani; Koichi Fukui; Yoshinori Naruta; Osamu Yamauchi, AMER CHEMICAL SOC
J. Am. Chem. Soc., 2003年, ［査読有り］

Studies on galactose oxidase active site model complexes:effects of ring substituents on Cu(II)-phenoxyl radical formation
Yuichi Shimazaki; Stefan Huth; Shun Hirota; Osamu Yamauchi, Copper(II) complexes of new N3O- and N2O2-donor tripodal ligands bearing one or two o-substituted phenol moieties have been synthesized as models for the galactose oxidase active site. The complexes of 2-[N-(1-methyl-2'-imidazolylmethyl)-N-(6"-methyl-2"-pyridylmethyl)-aminomethyl)]-4-methyl-6-methylthiophenol (MeSL), [Cu(MeSL)Cl], and N-(6-methyl-2-pyridylmethyl)-N,N-bis(2'-hydroxy-3',5'-di-tert-butylbenzyl)amine (t-buL2mepy), [Cu(t-bul2mepy(H2O)], have been revealed by X-ray structural analysis to have a square-pyramidal structure with one and two phenolate oxygens in the basal plane, respectively. [Cu(MeSL)Cl] was converted into a Cu(II)-o-methylthiophenoxyl radical species by electrochemical or Ce(IV) oxidation. An o-methoxyphenoxyl radical in a similar complex was considerably more stable than the 2.4-di(tert-butyl)phenoxyl radical, While t-buL2mepy reacted with Cu(ClO4)(2) to give [Cu(t-buL2mepy)(H2O)] without disproportionation. an N2O2-donor ligand containing an o-methoxyphenol, a 2,4-di(tert-butyl)phenol. and an N-methylimidazole moiety gave a phenoxyl radical complex exhibiting the characteristic absorption peak at 478 nm as a reddish powder by the reaction with Cu(ClO4)(2) as a result of spontaneous disproportionation. It exhibited a quasi-reversible redox wave at E-1,E-2 = 0.34 V (vs. Ag/AgCl) in CH3CN, which is lower than the potentials of the copper complexes of various N3O-donor ligands. and oxidized ethanol to acetaldehyde with a low turnover number. (C) 2002 Published by Elsevier Science B.V., ELSEVIER SCIENCE SA
Inorg. Chim. Acta, 2002年, ［査読有り］

Conformational preference of the side chain aromatic ring in Cu(II) and Pd(II) complexes of 2N1O-donor ligands
Tatsuo Yajima; Yuichi Shimazaki; Naoya Ishigami; Akira Odani; Osamu Yamauchi, Synthetic, structural, and spectroscopic studies were performed on the copper(H) and palladium(II) complexes of various 2N1O-donor tripod-like ligands containing a pyridine or a dimethylamine nitrogen, a tertiary amine nitrogen, and a phenolate oxygen as donor atoms and a pendent indole ring. [Pd(impp)Cl].3H(2)O.CH3CN (impp = N-2-pyridylmethyl-N-2-hydroxybenzyl-3-aminomethylindole) and two other Pd(II) complexes and a Cu(II) complex were isolated as crystals and structurally characterized by the X-ray diffraction method. The indole moiety of the Pd(II) complexes was found to be located close to the pyridine ring or the dimethylamino group and away from the phenolate moiety. H-1 NMR spectra of the Pd(II) complexes in CD3CN exhibited large upfield shifts of the pyridine and dimethylamino proton signals due to the pendent indole ring, supporting that the complexes in solution have a stacked structure similar to that found in the solid state. These findings indicated that the aromatic ring stacking interactions or CH-pi interactions exist between the indole and the pyridine rings or the methyl groups, respectively. [Cu-2(impp)(2)](ClO4)(2).H2O was revealed to have a dimeric structure with the indole moiety close to both the Cu(II) center and the pyridine ring, which suggests the possibility that the Cu(II) ion may undergo metal-aromatic ring interactions. (C) 2002 Published by Elsevier Science B.V., ELSEVIER SCIENCE SA
Inorg. Chim. Acta, 2002年, ［査読有り］

Synthesis and Characterization of the Dicobalt Bisporphyrin Complex Linked by 1, 2-phenylene Bridged
Yuichi Shimazaki; Hironori Takesue; Takefumi Chishiro; Fumito Tani; Yoshinori Naruta, The structure of a 1,2-phenylene linked dicobalt tetraarylporphyrin dimer was determined by X-ray crystallography and its dioxygen adduct was characterized by absorption and ESR spectroscopies. Since the porphyrin dimer has a long metal-metal distance and a rigid framework against inward bending, the cobalt centers were not bridged by the coordinated dioxygen., CHEMICAL SOC JAPAN
Chem. Lett., 2001年, ［査読有り］

Effects of a Side Chain Aromatic Ring on the Reactivity of Copper(I) complexes with Dioxygen
Yuichi Shimazaki; Takeo Nogami; Fumito Tani; Akira Odani; Osamu Yamauchi, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 2001年, ［査読有り］

2-(Imidazol-1-yl)-4-methylphenol
Yoshinori Naruta; Yoshimitzu Tachi; Takefumi Chishiro; Yuichi Shimazaki; Fumito Tani, The title compound, C10H10N2O, was synthesized to investigate the structure of the Tyr-His residue in the active site of cytochrome c oxidase (CcO). The dihedral angle between the cresol and imidazole moieties is 42.21 (4)degrees, which is similar to that of the tyrosine-linked histidine in bovine heart CcO. In the title compound, the R and S enantiomers of axial chirality are connected by an O-H . . .N hydrogen bond., MUNKSGAARD INT PUBL LTD
Acta Crystallogr., Sect E, 2001年, ［査読有り］

Chemical Approach to the Cu(II)-Phenoxyl Radical Site in Galactose Oxidase: Dependence of the Radical Stability on N-Donor Properties
Yuichi Shimazaki; Stefan Huth; Shun Hirota; Osamu Yamauchi, Copper(II) complexes of several new N3O-type tripodal ligands, 2,4-di(t-butyl)-6-{[bis(2-pyridyl)methyl] amino-methyl}phenol (HtbuL), 2,4-di(t-butyl)-6-{[ (6-methyl-2-pyridyl)methyl](2-pyridylmethyl)aminomethyl}phenol (HtbuL(Mepy)), 2,4-di(t-butyl)-6-{bis[ (6-methyl-2-pyridyl)methyl]aminomethyl}phenol (HtbuL(Mepy)(2)), and 2,4-di(t-butyl)-6-{[ (1-methyl-2-imidazolyl)methyl] [ (6-methyl-2-pyridyl)methyl]aminomethyl}phenol (HtbuL(im)(Mepy)), were prepared.They were structurally characterized by the X-ray crystallographic method to have a square-pyramidal structure with a weakly coordinating group at an apical position. The phenol moiety of [CuCl(tbuL(Mepy))] (2), [CuCl(tbuL(Mepy)(2))] (3), and [CuCl(tbuL(im)(Mepy))] (4) was revealed to be coordinated equatorially; it was converted to the phenoxyl radical upon oxidation with Ce(IV), giving a new absorption peak at 405-420 nm. ESR measurements at low temperatures and resonance Raman spectra established that the radical species has a Cu(II)-phenoxyl radical bond. The cyclic voltammograms exhibited a quasi-reversible redox wave at E-1/2 = 0.56-0.61 V (vs. Ag/AgCl) corresponding to the formation of the phenoxyl radical, which displayed a first order decay with a half life of 65 and 62 min at -20 degrees C for 2 and 4, respectively, while that for 3 was only 9.0 min at -40 degrees C. The radical stability increased with the donor ability of the equatorial N ligands., CHEMICAL SOC JAPAN
Bull. Chem. Soc. Jpn., 2000年, ［査読有り］

A Structure Model for Galactose Oxidase Active Site and Counteranion-Dependent Phenoxyl Radical Formation by Disproportionation
Yuichi Shimazaki; Stefan Huth; Akira Odani; Osamu Yamauchi, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 2000年, ［査読有り］

Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu,Zn-SOD　　　　　　　　　　　　　　　
Hideki Ohtsu; Yuichi Shimazaki; Akira Odani; Osamu Yamauchi; Wasuke Mori; Shinobu Itoh; Shunichi Fukuzumi
J. Am. Chem. Soc., 2000年, ［査読有り］

Chemical Approach to the Cu(II)-Phenoxyl Radical Site in A novel imidazolate-bridged copper-zinc heterodinuclear complex as a Cu,Zn-SOD active site model
Hideki Ohtsu; Yuichi Shimazaki; Akira Odani; Osamu Yamauchi, A novel imidazolate-bridged Cu(II)-Zn(II) heterodinuclear complex of an imidazole derivative containing two metal-binding groups has been synthesized, and its structure and properties have been clarified., ROYAL SOC CHEMISTRY
Chem. Commun., 1999年12月, ［査読有り］

Copper(I) Complexes with a Prooxymal Aromatic Ring: Novel Copper-Indole Bonding
Yuichi Shimazaki; Hiroshi Yokoyama; Osamu Yamauchi, WILEY-V C H VERLAG GMBH
Angew. Chem. Int. Ed., 1999年, ［査読有り］

One-electron oxidized Cu(II)-di(phenolate) complexes; Relationship between electronic structures and reactivities
Yuichi Shimazaki
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY, 2014年08月

環状ポルフィリン二量体のフラーレンC₇₀包接挙動
上村拓也; 信国浩文; 宇野英満; 島崎優一; 成田吉徳; 谷文都
基礎有機化学討論会要旨集, 2011年09月07日

フラーレン類を包接した環状ポルフィリン二量体の超分子構造とその光・電子物性
信国浩文; 谷文都; 島崎優一; 成田吉徳; 大久保敬; 中西達昭; 小島隆彦; 福住俊一; 関修平; 宇野英満
基礎有機化学討論会要旨集, 2009年09月18日

INOR 757-Investigation of the locus of oxidation and spectroscopic features of oxidized copper and nickel bis-phenoxide complexes
Tim Storr; Erik C. Wasinger; Russell Pratt; Yuichi Shimazaki; T. Daniel P. Stack
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2008年08月

〔主要な業績〕大学生 これから学ぶ化学　　　　　　　　　　　　　　　
速水真也・黒岩敬太・島崎優一・大久保貴志・折山 剛・西野 宏・須藤 篤, 共著
培風館, 2023年05月19日
9784563046422

錯体化合物事典　　　　　　　　　　　　　　　
島崎優一, 分担執筆
朝倉書店, 2019年09月10日
9784254141054

Recent Advances in the Field of Phenoxyl Radical–Metal Complexes in The Chemistry of Metal Phenolates (Volume 2)　　　　　　　　　　　　　　　
Yuichi Shimazaki, 共著
John Wiley & Sons, Ltd, 2016年09月19日

The Chemistry of Metal-Phenolates　　　　　　　　　　　　　　　
Yuichi Shimazaki; Ed. J. Zabicky, 単著
John Wiley & Sons, Ltd, 2014年04月04日
9780470973585

Electrochemistry　　　　　　　　　　　　　　　
単著
INTECH, 2013年02月

ベーシックマスター 無機化学　　　　　　　　　　　　　　　
増田秀樹・長嶋雲兵 共編, 共著
オーム社, 2010年10月15日
9784274209215

Reaction of Cu(II)-phenolate with O2: Formation of Cu(II)-phenoxyl radical via the Cu(I)-phenoxyl radical species　　　　　　　　　　　　　　　
Yuichi ShImazaki
The 17th European Biological Inorganic Chemistry Conference (EuroBIC-17), 2024年08月27日
20240825, 20240929

p-ジメチルアミノフェノラート配位子を有するコバルト錯体の原子価異性　　　　　　　　　　　　　　　
金城星彦; 島崎優一
錯体化学会第74回討論会, 2024年09月20日
20240918, 20240920

The role of a side-chain indole group for formation of Cu(II)-phenoxyl radical by Cu(II)-phenolate and O2　　　　　　　　　　　　　　　
Hoshihiko Kaneshiro; Yuichi Shimazaki
The 17th European Biological Inorganic Chemistry Conference (EuroBIC-17), 2024年08月26日
20240825, 20240829

大気下における銅(II) -フェノキシルラジカル錯体を用いた第一級アルコールの触媒的酸化　　　　　　　　　　　　　　　
吉井 万里奈; 島崎 優一
日本化学会 第104回春季年会, 2024年03月20日
20240318, 20240321

酸素分子によるCu(II)-フェノラート錯体からCu(II)-フェノキシルラジカル錯体への変換反応における側鎖インドール基の効果　　　　　　　　　　　　　　　
金城星彦; 矢島辰雄; 島崎優一
日本化学会 第104回春季年会, 2024年03月19日
20240318, 20240321

銅−フェノラート錯体のおはなし　　　　　　　　　　　　　　　
島崎優一
錯体化学若⼿の会・関東⽀部勉強会, 2023年12月02日, ［招待有り］
20231202, 20231202

p-ジメチルアミノフェノラートを配位子とする八面体型Co錯体の電子状態　　　　　　　　　　　　　　　
金城星彦; 島崎優一
錯体化学会 第73回討論会, 2023年09月21日
20230921, 20230923

Cu(II)-フェノラート錯体の空気酸化により生成するCu(II)-フェノキシルラジカル錯体におけるπ - π スタッキング相互作用の影響　　　　　　　　　　　　　　　
金城星彦; 島崎優一
第２回 生命金属科学シンポジウム, 2023年05月20日
20230520, 20230521

〔主要な業績〕Formation of Copper(II)-Phenoxyl Radical Complexes from Copper(II)-Phenolates by O2:Characterization of Copper(I)-Phenoxyl Radical Intermediates　　　　　　　　　　　　　　　
10th Asian Biological Inorganic Chemistry,Conference, 2022年11月30日, ［招待有り］
20221126, 20221203

フェノキシルラジカルが配位したコバルト(II), 銅(I)錯体の性質　　　　　　　　　　　　　　　
島 悠⼈・鈴⽊ 崇・〇島崎 優⼀
錯体化学会第72回討論会, 2022年09月26日
20220926, 20220928

各種高原子価金属錯体の詳細な電子状態と反応性の相関　　　　　　　　　　　　　　　
島崎優一 ・大下宏美・鈴木 崇・星野哲久・芥川智行・谷 文都
物質・デバイス領域共同研究拠点 キックオフシンポジウム, 2022年08月08日, 大阪大学産業科学研究所, ［招待有り］
20220808

Ni(II)-フェノラート錯体及びNi(II)-フェノール錯体と酸素分子との反応によるNi(II)-フェノキシルラジカル錯体の生成とプロトンの効果　　　　　　　　　　　　　　　
鈴木 崇・島崎 優一
日本化学会第101回春季年会, 2021年03月

Formation of CuII-phenoxyl Radical by Reaction of O2 with the CuII-Phenolate Complex via the CuI-Phenoxyl Radical Species　　　　　　　　　　　　　　　
Takashi Suzuki; Yuichi SHIMAZAKI
錯体化学会第70回討論会, 2020年09月28日, ［招待有り］
20200928, 20200930

Formation of NiII-phenoxyl radical species by O2 from the NiII-(phenol)(phenolate) complexes and their mechanisms　　　　　　　　　　　　　　　
鈴木崇、島崎優一
錯体化学会第７０回討論会, 2020年09月30日

分子内酸化還元による銅(I)-フェノキシルラジカル錯体の生成と性質　　　　　　　　　　　　　　　
島悠人; 鈴木崇; 島崎優一
錯体化学会第70回討論会, 2020年09月30日

Oxidation Chemistry of Nickel(II)-di(phenolate) Complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
PACIFICHEM 2015, 2015年12月14日, ［招待有り］

Oxidation Chemistry of ,Nickel(II)-di(phenolate) Complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
PACIFICHEM 2015, 2015年12月14日, ［招待有り］

Characterization of One-Electron Oxidized Metal(II) Salen-type Complexes: Electronic Structure and Reactivity Relationship　　　　　　　　　　　　　　　
Y. Shimazaki
Third International Symposium on the Photofunctional Chemistry of Complex Systems, 2015年12月12日

Characterization of One-Electron Oxidized Metal(II) Salen-type Complexes:,Electronic Structure and Reactivity Relationship　　　　　　　　　　　　　　　
Y. Shimazaki
Third International Symposium,on the Photofunctional Chemistry of Complex Systems, 2015年12月12日

金属−フェノラート錯体を酸化してみると…　　　　　　　　　　　　　　　
島崎優一
第28回 生物無機化学夏季セミナー, 2015年08月28日, ［招待有り］

Electronic Structures of One-Electron Oxidized Nickel(III)-Phenolate Complexes　　　　　　　　　　　　　　　
Y. Shimazaki
EuCheMS – 2015 – Inorganic Chemistry Conference, 2015年06月28日

Oxidation Chemistry of Metal(II)-diphenolato complexes with Salen-Type Ligands; Electronic Structure and Reactivity Relationship　　　　　　　　　　　　　　　
Y. Shimazaki
The 3rd International Conference on Material Sciences & Engineering, 2014年10月06日, ［招待有り］

One-electron oxidized Cu(II)-di(phenolate) complexes; Relationship between electronic structures and reactivities　　　　　　　　　　　　　　　
Y. SHIMAZAKI
the European Biological Inorganic Chemistry Conference, 2014年08月24日

ELECTRONIC STRUCTURES OF ONE-ELECTRON OXIDIZED NICKEL(III)-PHENOLATE COMPLEXES　　　　　　　　　　　　　　　
Y. SHIMAZAKI
41st International Conference on Coordination Chemistry, 2014年07月21日

One-electron oxidized Cu(II)-salen type complexes; Relationship between electronic structures and reactivities　　　　　　　　　　　　　　　
Y. Shimazaki
The 13th Challenges in Inorganic and Materials Chemistry (ISACS13), 2014年07月01日

Characterization and Reactivity of one-electron oxidized Cu(II)-salen-type complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
The 11th European Biological Inorganic Chemistry Conference, 2012年09月12日

Electronic Structures and Reactivities of Oxidized Metal(II)-salen-type Complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
Challenges in Inorganic and Materials Chemistry 8 (ISACS8), 2012年07月19日

Concentration dependent Pd(II)-C bond formation　　　　　　　　　　　　　　　
Satoshi Iwatsuki; Yuichi Shimazaki
the 11th International Symposium on Applied Bioinorganic Chemistry, 2011年12月05日

Pd(II)-C bond formation mechanism in various Pd complexes containing an indole moiety　　　　　　　　　　　　　　　
Yuichi Shimazaki; Takuya Suzuki; Satoshi Iwatsuki; Tatsuo Yajima
5th EuCheMS NLigands Conference, 2011年09月05日

Pd(II)-C bond formation mechanism in various Pd complexes,containing an indole moiety　　　　　　　　　　　　　　　
Yuichi Shimazaki; Takuya Suzuki; Satoshi Iwatsuki; Tatsuo Yajima
5th EuCheMS NLigands Conference, 2011年09月05日

Electronic Structures of Oxidized Metal(II)-salen Type Complexes Dependence with the Diamine Backbone　　　　　　　　　　　　　　　
Yuichi Shimazaki
ICBIC15, 2011年08月11日, ［招待有り］

Concentration-dependent Pd(II)-C bond formation in complexes with a 2N-donor ligand containing an indole moiety　　　　　　　　　　　　　　　
Yuichi Shimazaki
18th International SPACC Symposium, 2011年08月06日, The Society of Pure and Applied Coordination Chemistry And Department of Chemistry, Simon Fraser University, ［招待有り］

Influence of chelate effect on the electronic structure of oxidized metal(II)-di(salicylidene)diamine complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
1st EuCheMS Inorganic Chemistry Conference, 2011年04月13日

Characterization and electronic structures of oxidized metal(II)-salen-type complexes　　　　　　　　　　　　　　　
PACIFICHEM 2010, 2010年12月16日, ［招待有り］

金属(II)salen錯体の一電子酸化体の電子構造　　　　　　　　　　　　　　　
島崎 優一
第４回日本化学会関東支部大会, 2010年08月30日, 日本化学会関東支部, ［招待有り］

Characterization of one-electron oxidized metal-salen type complexes (metal = Cu, Ni, Pd, and Pt)　　　　　　　　　　　　　　　
39th International conference on Coordination Chemistry, 2010年07月27日

Electronic structures and reactivities of oxidized metal(II)-salen-type complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
Faraday Discussion 148: Spectroscopy Theory and mechanism in Bioinorganic chemistry, 2010年07月06日, Royal society of chemistry

Snthesis and characterization of Pd-indole complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki; Takuya Suzuki; Tatsuo Yajima; Tadashi Shiraiwa
10th European Biological Inorganic Chemistry Conference, 2010年06月24日

Correlation of Electronic Structure and Reactivity- The Case of Oxidized Metal Salens　　　　　　　　　　　　　　　
Osaka City University International Symposium on the Foundation of Environmentaal Research, 2010年03月10日, Osaka City University, ［招待有り］

Characterizations and electronic structures of oxidized metal(II)-salen complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
Gordon Research Conference, Metals in Biology, 2010年02月01日

Characterization of One-Electron Oxidized Cu(II)-salen Type Complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki; Kazuaki Tsukidate; Tim Storr; T. Daniel; P. Stack
10th International Symposium on Applied Bioinorganic Chemistry (ISABC 10), 2009年09月28日, ［招待有り］

マンガン錯体による水の酸化と酸素発生　　　　　　　　　　　　　　　
島崎 優一
応用物理学会春期年会, 2009年03月, 応用物理学会, ［招待有り］

Characterization of metal complexes containing indole rings as versatile C-donor ligands　　　　　　　　　　　　　　　
Yuichi Shimazaki
Gordon Research Conference, Metals in Biology., 2009年01月28日

金属(II)-salen錯体の一電子酸化体の同定と反応性（金属＝銅、ニッケル、パラジウム、白金）　　　　　　　　　　　　　　　
島崎 優一
有機合成化学協会第45回化学関連支部合同九州大会, 2008年07月04日, ［招待有り］

Synthesis and Characterization of Metal Complexes Containing Biological Molecules　　　　　　　　　　　　　　　
Yuichi Shimazaki
Lecture in Stanford University, 2008年03月, ［招待有り］

Characterization of One-Electron Oxidized Metal-Salen Type Complexes (Metal = Cu, Ni, Pd, Pt)　　　　　　　　　　　　　　　
Yuichi Shimazaki
Zing Conference, 2008年

Synthesis and Characterization of Imidazolate-Bridged Polynuclear Copper Complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki
4th Europian Association for Chemystry and Molecular Science Conference, 2008年

Oxidation Behavior of Metal-Phenolate Complexes with N3O-donor Tripodal Ligands and Characterization of Their Phenoxyl Radical Species　　　　　　　　　　　　　　　
Yuichi Shimazaki
9th European Biological Inorganic Chemistry Conference (EUROBIC 9), 2008年

Characterization reactivities of metal phenoxyl radical species　　　　　　　　　　　　　　　
Yuichi Shimazaki
The 13th International Conference on Bioinorganic Chemistry (ICBIC 13), 2007年, ［招待有り］

Structures and Oxidations of Metal phenolate Complexes.　　　　　　　　　　　　　　　
Yuichi Shimazaki
China-Japan Crossover Science Symposium, 2007年, ［招待有り］

A Formation and Reactivity of Indole-Binding Palladium(II) and Platinum(II) Complexes　　　　　　　　　　　　　　　
Yuichi Shimazaki; Osamu Yamauchi
The 8th European Biological Inorganic Chemistry Conference (Eurobic 8), 2006年

O2 evolution from a high-valent oxo-manganese porphyrin dimer.　　　　　　　　　　　　　　　
Yuichi Shimazaki; Fumito Tani; Yoshinori Naruta
The 37th International Conference on Coordination Chemistry (ICCC 37), 2006年

Structures and Reactivities of Metal Complexes Containing Indole Rings　　　　　　　　　　　　　　　
Yuichi Shimazaki
Japan-China Crossover Science Symposium, 2006年, ［招待有り］

O2 evolution from a high-valent oxo-manganese porphyrin dimer　　　　　　　　　　　　　　　
Yuichi Shimazaki
International Conference on Bioinorganic Chemistry of the New Age, 2006年, ［招待有り］

Characterization of a High Valent Oxo-Manganses Porphyrin Dimer : Studies Relevant to the Intermediate of a Functional Model for Oxygen Evolving Center　　　　　　　　　　　　　　　
Yuichi Shimazaki; Taro Nagano; Hironori Takesue; Bao-Hui. Ye; Fumito Tani; Yoshinori Naruta
The 36th International Conference on Coordination Chemistry (ICCC 36), 2004年

Indole radical formation in a Pd(II) complex involving a coordinated indole ring.　　　　　　　　　　　　　　　
Osamu Yamauchi; Takeshi Motoyama; Yuichi Shimazaki; Tatsuo Yajima; Yasuo Nakabayashi
The 11th International Conference on Bioinorganic Chemistry (ICBIC 11), 2003年

First isolation and crystal structure of peroxo bridged heme-copper complexes.　　　　　　　　　　　　　　　
Takefumi Chishiro; Yuichi Shimazaki; Fumito Tani; Yochimitsu Tachi; Yoshinori Naruta; Satoru Karasawa; Sinya Hayami; Yonezo Maeda
The 11th International Conference on Bioinorganic Chemistry (ICBIC 11), 2003年

O2 evolution from the high-valent oxo-manganese porphyrin dimer.　　　　　　　　　　　　　　　
Yuichi Shimazaki; Taro Nagano; Hironori Takesue; Bao-Hui. Ye; Fumito Tani; Yoshinori Naruta
The 11th International Conference on Bioinorganic Chemistry (ICBIC 11), 2003年

Characterization of a High Valent Oxo-Manganses Porphyrin Dimer : Studies Relevant to the Intermediate of a Functional Model for Oxygen Evolving Center　　　　　　　　　　　　　　　
Yuichi Shimazaki
Gordon Reserch Conference (Organic structure and property), 2002年, ［招待有り］

Phenoxyl Radical Formation in a Ni(II) Complex and the Temperature-Dependent Valence State.　　　　　　　　　　　　　　　
Yuichi Shimazaki; Osamu Yamauchi
The 6th European Biological Inorganic Chemistry Conference (Eurobic 6), 2002年

Reaction Mechanism for Water Oxidation Catalyzed by Mn-Porphyrin Dimer　　　　　　　　　　　　　　　
Yuichi Shimazaki; Hironori Takesue; Fumito Tani; Yoshinori Naruta
The 10th International Conference on Bioinorganic Chemistry (ICBIC 10), 2001年

2010年07月, イギリス化学会

2008年09月, アメリカ化学会

2006年04月, 錯体化学会

1996年04月, 日本化学会

金属イオンを用いたフェノールの酸化とその機構に関する研究　　　　　　　　　　　　　　　
2022年06月 - 2023年03月

各種高原子価金属錯体の詳細な電子状態と反応性の相関　　　　　　　　　　　　　　　
2021年04月 - 2022年03月

金属イオンを用いたフェノールの酸化とその機構に関する研究　　　　　　　　　　　　　　　
2021年04月 - 2022年03月

金属錯体の酸化状態制御と特異的反応性に関する研究　　　　　　　　　　　　　　　
2019年04月 - 2022年03月

空気酸化による金属-フェノキシルラジカル錯体の生成・性質と反応性の相関　　　　　　　　　　　　　　　
基盤研究(C)
2016年04月 - 2019年03月

ニッケル(IV)、銅(IV)錯体ならびにそれらの等酸化体の性質と反応性
基盤研究(C)
茨城大学
2013年04月01日 - 2016年03月31日

各種高原子価金属錯体の詳細な電子状態と反応性の相関
基盤研究(C)
茨城大学
2010年 - 2012年

水と酸素の相互変換分子触媒の創製
基盤研究(S)
九州大学
2005年 - 2009年

高原子価マンガン(V,V)種の合成・単離とその反応性に関する研究
若手研究(B)
九州大学
2005年 - 2007年

メタン分子の識別・捕捉と選択的酸化分子触媒創製への挑戦
萌芽研究
九州大学
2004年 - 2005年

合理的設計に基づく金属錯体の動的反応制御とテーラーメイド触媒への応用
特定領域研究
九州大学
2004年 - 2005年

新規酸素活性化分子触媒の開発と生体型燃料電池への展開
基盤研究(A)
九州大学
2002年 - 2004年

合理的設計に基づく金属錯体の動的反応制御とテーラーメイド触媒への応用
特定領域研究
九州大学
2003年 - 2003年

プロスタグランジン合成酵素:人工酵素への挑戦
萌芽研究
九州大学
2002年 - 2003年

金属錯体の合理的設計による新しい酵素分子活性化反応
特定領域研究
九州大学
1999年 - 2002年

化学合成モデルによる水の酸化酵素反応の解明
特別研究員奨励費
九州大学
2001年 - 2001年

米国アナハイム市学生親善大使への模擬授業　　　　　　　　　　　　　　　
講師
水戸市国際交流協会, 2024年06月26日

茨城県立境高校 出前授業　　　　　　　　　　　　　　　
講師
2022年10月04日

茨城県立水海道第一高等学校 出前授業　　　　　　　　　　　　　　　
講師
茨城県立水海道第一高等学校, 2014年11月06日

茨城県立牛久栄進高等学校 出前授業　　　　　　　　　　　　　　　
講師
茨城県立牛久栄進高等学校, 2014年08月04日

福島県立磐城桜ヶ丘高等学校 出前授業　　　　　　　　　　　　　　　
講師
福島県立磐城桜ヶ丘高等学校, 2014年07月16日

霞ヶ浦高等学校 出前授業　　　　　　　　　　　　　　　
講師
霞ヶ浦高等学校, 2014年07月09日