Structural comparison of alkylated derivatives of (bmmp-dmed)Ni and (bmmp-dmed)Zn

被引：13

作者：

Grapperhaus, CA ^{[1
]}

Mullins, CS ^{[1
]}

Mashuta, MS ^{[1
]}

机构：

[1] Univ Louisville, Dept Chem, Louisville, KY 40292 USA

来源：

INORGANICA CHIMICA ACTA | 2005年 / 358卷 / 03期

基金：

美国国家科学基金会;

关键词：

nickel; zinc; S-alkylation; ligand centered reactivity;

D O I：

10.1016/j.ica.2004.09.035

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The sulfur-alkylation of the nickel (1) and zinc (2) complexes of the dithiolate N2S2 ligand N,N'-bis-2-methyl-mercaptopropyl- N,N'-dimethylethylenediamine, H-2(bmmp-dmed), have been investigated. Reactions with iodomethane yield [(Me-bmmp-dmed)Ni]PF6 (3), [(Me-2-bmmp-dmed)NiI2] (4), and [(Me-2-bmmp-dmed)ZnI](2)[ZnI4] (5). Addition of iodoacetamide yields [(AA(2)-bmmp-dmed)Ni]I-2 (6) and [(AA(2)-bmmp-dmed)Zn]I-2 (7). Each of the metal-thioether products (3-7) have been characterized spectroscopically and by X-ray crystallography. Structural data is compared with that of the previously reported thiolato precursors 1 and 2. Sulfur-alkylation of 1 results in small relative changes in the nickel-sulfur bond distance, whereas for 2, the zinc-sulfur bond distance increases significantly, but is not cleaved. The difference between nickel and zinc is attributed to the release of a pi*-bonding interaction between the metal and sulfur upon alkylation that compensates for the decreased a-donor ability of the thioether in the case of nickel. but not for zinc. (C) 2004 Elsevier B.V. All rights reserved.

引用

页码：623 / 632

页数：10

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