二硫代氨基甲酸盐配合物的金属-硫键中多次氮宾插入反应：硫代酰胺和两性离子四酰胺配合物的合成。

Multiple nitrene insertions into metal-sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes.

作者信息

Hogarth Graeme, Holman K Travis, Pateman Andrew, Sella Andrea, Steed Jonathan W, Richards Idris

机构信息

Department of Chemistry, University College London, 20 Gordon Street, London, UK WC1H 0AJ.

出版信息

Dalton Trans. 2005 Aug 21(16):2688-95. doi: 10.1039/b503004h. Epub 2005 Jul 7.

DOI:10.1039/b503004h

PMID:16075107

Abstract

The iodine(III) reagent, PhI[double bond, length as m-dash]NTs, acts as a source of the nitrene fragment NTs, which undergoes facile insertion into the metal-sulfur bonds of a range of dithiocarbamate complexes. Addition of two equivalents of PhI=NTs to [M(S(2)CNR2)2] affords sulfido-amido complexes [M{SC(NR2)SNTs}2](M=Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR2)SNTs}2](M=Co, Ni, Cu). Crystallographic studies have been carried out on both types of complex allowing possible resonance hydrids of the new ligand types to be assessed.

摘要

碘（III）试剂PhI=NTS作为氮宾片段NTS的来源，它能轻易插入一系列二硫代氨基甲酸盐配合物的金属-硫键中。向[M(S₂CNR₂)₂]中加入两当量的PhI=NTS，可得到硫代酰胺配合物[M{SC(NR₂)SNTs}₂](M = Ni, Cu)，该配合物能进一步插入两个氮宾片段，生成两性离子四酰胺配合物[M{TsNSC(NR₂)SNTs}₂](M = Co, Ni, Cu)。已对这两种配合物进行了晶体学研究，从而能够评估新配体类型可能的共振杂化物。