2006 Fiscal Year Final Research Report Summary
Synthesis and Control of Functions of Metal Complexes Having Oxygen Active Species
| Project/Area Number |
16350030
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Inorganic chemistry
|
|---|
| Research Institution | Kanazawa University |
|---|
Principal Investigator |
SUZUKI Masatatsu Graduate School of Natural Science and Technology, Professor, 自然科学研究科, 教授 (20091390)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
FUJINAMI Shuhei Graduate School of Natural Science and Technology, Associate Professor, 自然科学研究科, 助教授 (10115272)
FURUTACHI Hideki Graduate School of Natural Science and Technology, Assistant Professor, 自然科学研究科, 助手 (40332663)
|
|---|
| Project Period (FY) |
2004 – 2006
|
| Keywords | Synthetic Chemistry / Bioinorganic Chemistry / Peroxo-dicopper(II) / Oxygen active species / Oxidation reactions / C-H bond activation / Peroxo-diiron(III) / Crystal structures |
|---|
| Research Abstract |
The purpose of this project is the development of the peroxo-dicopper(II) and diiron(III) complexes as functional models for tyrosinase and toluene monooxygenase.
We have succeeded in synthesis of (μη^2:η^2-peroxo)Cu(II)_2 complexes, [Cu_2(O_2)(R-L)]^<2+> (oxy-R-1: R = H, MeO, t-Bu, and NO_2), where R-L = 1,3-Bis[bis(6-methyl-2pyridylmethyl)aminomethy1]-5-R-benzene, which can perform not only hydroxylation of the m-xylyl linker of R-L, but also epoxidation of styrene via an electrophilic addition of the peroxide to the C=C bond, the latter of which is the first example of the epoxidation of styrene by a discrete (μη^2:η^2-peroxo)Cu(II)_2 species. In addition, oxy-H-1 can oxidize various aliphatic C-H bonds via H-atom abstraction. A linear correlation between log k (the second order rate constants of oxidation) and the bond dissociation energies of the C-H bonds was observed. The results provide new insights into the reactivity of (μη^2:η^2 peroxo) Cu(II)_2 complexes.
(μ-Peroxo)diiron(III) Complex: A Functional Model for Toluene Monooxygenase. We have succeeded in synthesis of two types of peroxodiiron(III) complexes, [Fe2(L^<Ph4>)(RCO_2)(O_2)]^<2+> (R = Ph_3C (oxy-1) and Ph (oxy-2)), the former leads to regioselective hydroxylation of a phenyl group of L^<Ph4> and the latter exhibits reversible deoxygenation (L^<Ph4> = N, N, N',N'-tetrakis[(1-methyl-2-pheny1-4-imidazolyl)methy1]-1,3-diamino-2-propanolate). This is the first example of the peroxodiiron(III) complex which is capable of arene hydroxylation. The reactions mimic toluene monooxygenase and hemerythrin reactivity, respectively. They provide new insights into the reactivity of the peroxodiiron(III) complexes having a nitrogen-rich coordination environment like alkane arhydroxylase and hemerythrin.
|
Research Products
(25 results)
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
[Book] 金属錯体最前線2006
Author(s)
鈴木正樹, 山下正廣, 北川進等
Total Pages
4
Publisher
化学同人
Description
「研究成果報告書概要(和文)」より
-
[Book] 生物無機化学2005
Author(s)
鈴木正樹, 増田秀樹, 福住俊一等
Total Pages
47
Publisher
三共出版
Description
「研究成果報告書概要(和文)」より
-
