Oxidation of a dimeric nickel thiolate complex with O-2

被引：46

作者：

Mirza, SA ^{[1
]}

Day, RO ^{[1
]}

Maroney, MJ ^{[1
]}

机构：

[1] UNIV MASSACHUSETTS,DEPT CHEM,AMHERST,MA 01003

来源：

INORGANIC CHEMISTRY | 1996年 / 35卷 / 07期

关键词：

D O I：

10.1021/ic950736a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of dimeric bis{[mu-(2-mercaptoethyl)(2-mercaptoethyl)methylaminato(2-)] nickel(II)}, 1, with either O-2 or H2O2 leads to the formation of a dimeric product, bis{[mu-(2-mercaptoethyl)(2-sulfinatoethyl)methylaminato (2-)]nickel(II)}, 2. The reaction is first-order in [Ni] and proceeds at a very slow rate at 40 degrees C (t(1/2) = 7.8 days; k = 1.0(1) x 10(-6) s(-1)) under 1 atm of O-2. Crystals of 2 form in the orthorhombic space group Pbca with cell dimensions a = 14.271(2) Angstrom, b = 20.424(3) Angstrom, c = 11.766(2) Angstrom, V = 3429.4(9) Angstrom(3), and Z = 8. A single-crystal X-ray diffraction study of these crystals reveals a dimeric structure that is quite similar to 1, where the terminal thiolates have been oxidized to sulfinate ligands in 2. Compound 1 has several structural features in common with the dimeric mu-dithiolato Ni,Fe site found in the active site of Desulfovibrio gigas hydrogenase. The structural similarities and the potential relevance of the oxidation reaction are discussed.

引用

页码：1992 / 1995

页数：4

共 16 条

[1] STUDY OF SULFINATE AND SULFENATE COMPLEXES DERIVED FROM THE OXYGENATION OF THIOLATE SULFUR IN [1,5-BIS(2-MERCAPTO-2 METHYLPROPYL)-1,5-DIAZACYCLOOCTANATO(2-)]NICKEL(II) [J].