一（丙二腈二硫醇根）钼（IV）和双（μ-硫代）桥联二钼（V）配合物，其中 Mo=S 部分。

Mono(maleonitriledithiolene)molybdenum(IV) and bis(μ-sulfido)-bridged dimolybdenum(V) complexes with Mo=S moiety.

机构信息

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.

出版信息

Chem Biodivers. 2012 Sep;9(9):1867-79. doi: 10.1002/cbdv.201100450.

DOI:10.1002/cbdv.201100450

Abstract

Mono(maleonitriledithiolene)sulfidomolybdenum(IV) complex, MoS(S(4))(mnt) (2; mnt=maleonitriledithiolene) was synthesized by the substitution reaction of a tetrasulfido ligand of the known MoS(S(4))(2) (1) upon reaction with one or even excess equivalent of Na(2)(mnt) in aqueous MeCN solution in air. Surprisingly, 2 undergoes dimerization on treatment with alkyl halide such as MeI and PhCH(2)Br to form bis(μ-sulfido)dimolybdenum(V) species, {MoS(mnt)}(2)(μ-S)(2) (3). These complexes have been characterized by IR, UV/VIS spectroscopy, cyclic voltammetry, elemental analysis, and by X-ray crystal-structure analysis. Differences in the relative stability and electrochemical behavior of 1, 2, and 3 have been correlated with theoretical calculations at DFT level.

摘要

单（马来二腈二硫醇根合）硫化钼（IV）配合物，[MoS(S(4))(mnt)]^(2-)（2；mnt=马来二腈二硫醇根合）是通过在空气中的水溶液 MeCN 溶液中，用 1 （已知[MoS(S(4))(2)]^(2-)的四硫配体与 1 当量甚至过量的 Na(2)(mnt)反应，取代反应合成的。令人惊讶的是，2 在与烷基卤化物（如 MeI 和 PhCH(2)Br）处理时会发生二聚化，形成双（μ-硫代）二钼（V）物种，[{MoS(mnt)}(2)(μ-S)(2)]^(2-)（3）。这些配合物通过 IR、UV/VIS 光谱、循环伏安法、元素分析和 X 射线晶体结构分析进行了表征。通过理论计算在 DFT 水平上，研究了 1、2 和 3 的相对稳定性和电化学行为的差异。