Synthesis, structures and electrochemical properties of hydroxyl- and pyridyl-functionalized diiron azadithiolate complexes

被引：34

作者：

Cui, Hong-Guang

Wang, Mei

Dong, Wei-Bing

Duan, Le-Le

Li, Ping

Sun, Li-Cheng

机构：

[1] Dalian Univ Technol, DUT KTH Joint Educ & Res Ctr Mol Devices, State Key Lab Fine Chem, Dalian 116012, Peoples R China

[2] Royal Inst Technol, Dept Chem, S-10044 Stockholm, Sweden

来源：

POLYHEDRON | 2007年 / 26卷 / 04期

基金：

中国国家自然科学基金;

关键词：

azapropanedithiolate; bioinorganic chemistry; diiron complex; iron-only hydrogenase; S center dot center dot center dot O intermolecular contact;

D O I：

10.1016/j.poly.2006.09.023

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The hydroxyl- and pyridyl-functionalized diiron azadithiolate complexes [[(mu-SCH2)(2)N(CH2CH2OH)}Fe-2(CO)(6)] (1) and [{(mu-SCH2)(2)N(CH2CH2OOCPy)} Fe-2(CO)(6)] (Py = pyridyl) (2) were prepared as biomimetic models of the active site of Fe-only hydrogenases. Both complexes were characterized by MS, IR, H-1 NMR spectra and elemental analysis. The molecular structures of 1 and 2 were determined by single crystal X-ray analysis. A network is constructed by intermolecular H-bonds in the crystals of 1. An S center dot center dot center dot O intermolecular contact was found in the crystals of 2, which is scarcely found for organometallic complexes. Cyclic voltammograms of 1 and 2 were studied to evaluate their redox properties. (c) 2006 Elsevier Ltd. All rights reserved.

引用

页码：904 / 910

页数：7

共 37 条

[1] BONDING BETWEEN NONBONDED SULFUR AND OXYGEN-ATOMS IN SELECTED ORGANIC-MOLECULES (A QUANTUM CHEMICAL STUDY) [J].

ANGYAN, JG ;

POIRIER, RA ;

KUCSMAN, A ;

CSIZMADIA, IG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) :2237-2245

[2] [Fe2(SR)2(μ-CO)(CNMe)6]2+ and analogues:: A new class of diiron dithiolates as structural models for the HoxAir air state of the Fe-only hydrogenase [J].

Boyke, CA ;

Rauchfuss, TB ;

Wilson, SR ;

Rohmer, MM ;

Bénard, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (46) :15151-15160

[3] Bioinorganic chemistry - Hydrogenase sophistication [J].

Cammack, R .

NATURE, 1999, 397 (6716) :214-215

[4] N-heterocyclic carbene ligands as cyanide mimics in diiron models of the all-iron hydrogenase active site [J].

Capon, JF ;

El Hassnaoui, S ;

Gloaguen, F ;

Schollhammer, P ;

Talarmin, J .

ORGANOMETALLICS, 2005, 24 (09) :2020-2022

[5] Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure/function relationships [J].

Chong, DS ;

Georgakaki, IP ;

Mejia-Rodriguez, R ;

Samabria-Chinchilla, J ;

Soriaga, MP ;

Darensbourg, MY .

DALTON TRANSACTIONS, 2003, (21) :4158-4163

[6] An insight into the protonation property of a diiron azadithiolate complex pertinent to the active site of Fe-only hydirogenases [J].

Dong, WB ;

Wang, M ;

Liu, XY ;

Jin, K ;

Li, GH ;

Wang, FJ ;

Sun, LC .

CHEMICAL COMMUNICATIONS, 2006, (03) :305-307

[7] A capable bridging ligand for Fe-only hydrogenase: Density functional calculations of a low-energy route for heterolytic cleavage and formation of dihydrogen [J].

Fan, HJ ;

Hall, MB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (16) :3828-3829

[8]

Frey M, 2002, CHEMBIOCHEM, V3, P153, DOI 10.1002/1439-7633(20020301)3:2/3<153::AID-CBIC153>3.0.CO

[9]

2-B

[10] Fundamental properties of small molecule models of Fe-only hydrogenase: computations relative to the definition of an entatic state in the active site [J].

Georgakaki, IP ;

Thomson, LM ;

Lyon, EJ ;

Hall, MB ;

Darensbourg, MY .

COORDINATION CHEMISTRY REVIEWS, 2003, 238 :255-266

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