一步法合成环金属化的 Au(III) N，S-杂环卡宾：晶体结构分析。

One-step formation of cyclometallated Au(III) N,S-heterocyclic carbene: crystallographic analysis.

机构信息

Department of Chemistry, National University of Singapore, 3 Science Drive 3, Kent Ridge, Singapore117543.

出版信息

Dalton Trans. 2009 Sep 21(35):7248-52. doi: 10.1039/b909661b. Epub 2009 Jul 30.

PMID:20449169

Abstract

Gold(I) N,S-heterocyclic carbene AuBr(NSHC) (NSHC = N-allylbenzothiazolin-2-ylidene) (1) with an allyl pendant is oxidised by iodine to give [AuI2(NSHC)2]+[I3]- (2) and a cyclometallated byproduct AuBr2(-C6H4SCNCH2CHCH2Br-C,C) (3). The latter can be prepared directly from bromination of 1. Similar reaction with the crotyl (but-2-en-1-yl) derivative AuBr(NSHC) (NSHC = N-crotylbenzothiazolin-2-ylidene) (4) gives an oxidative addition product AuBr3(C6H4SCNCH2CHCHCH3) (5). X-Ray single-crystal crystallographic analysis of 3 reveals a 5-membered cyclometallated ring in a sq planar metal that gives two types of AuIII-C bonds. Similar structural analysis has also been carried out in 1, 2 and 5.

摘要

具有烯丙基侧链的金(I) N,S-杂环卡宾 AuBr(NSHC)(NSHC=N-烯丙基苯并噻唑-2-亚基)(1)被碘氧化生成[AuI2(NSHC)2]+[I3]- (2)和一个环金属化副产物 AuBr2(-C6H4SCNCH2CHCH2Br-C,C) (3)。后者可以直接通过 1 的溴化来制备。与丙烯基(丁-2-烯-1-基)衍生物 AuBr(NSHC)(NSHC=N-丙烯基苯并噻唑-2-亚基)(4)的类似反应得到一个氧化加成产物 AuBr3(C6H4SCNCH2CHCHCH3)(5)。3 的 X 射线单晶晶体结构分析揭示了一个 sq 平面金属中的 5 元环金属化环，该环形成两种类型的 AuIII-C 键。在 1、2 和 5 中也进行了类似的结构分析。