Oxygen/Sulfur Substitution Reactions of Tetraoxometalates Effected by Electrophilic Carbon and Silicon Reagents
作者:David V. Partyka、R. H. Holm
DOI:10.1021/ic040097g
日期:2004.12.1
Dithiolene chelate rings are readily introduced upon reaction with 1,2-C(6)H(4)(SSiMe(3))(2), leading to the square pyramidal trioxo complexes [MO(3)(bdt)](2)(-), a previously unknown dithiolene molecular type. Further ring insertion occurs upon reaction of [WO(3)(bdt)](2)(-) with 1,2-C(6)H(4)(SSiMe(3))(2), giving [WO(2)(bdt)(2)](2)(-). Related reactions occur with [ReO(4)](1)(-). Treatment with 1 equiv
在乙腈中研究了[MO(4)](2)(-)(M = Mo,W)与某些碳和硅亲电试剂的反应,以产生可能用于合成黄嘌呤位点类似物的物质氧化还原酶家族。[MoO(4)](2)(-)的甲硅烷基化提供[MoO(3)(OSiPh(3))](1)(-),将其与Ph(3)SiSH转换为[MoO(2)S (OSiPh(3))](1)(-)。与(Ph(3)C)(PF(6))/ HS(-)反应生成四面体单硫键物质[MO(3)S](2)(-),以前仅从水性体系[MO(4) )](2)(-)/ H(2)S。与1,2-C(6)H(4)(SSiMe(3))(2)反应后很容易引入二硫代螯合环,从而导致方形金字塔三氧杂合物[MO(3)(bdt)](2) (-),一种以前未知的二硫烯分子类型。当[WO(3)(bdt)](2)(-)与1,2-C(6)H(4)(SSiMe(3))(2)反应时,会进一步发生环插入,给出[WO(2)(