Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph2-7,8-nido-C2B9H8]2−
- 作者：Robertson ; Susan ; Garrioch ; Rhona M. ; Ellis ; David ; McGrath ; Thomas D. ; Hodson ; Bruce E. ; Rosair ; Georgina M. ; et. al.
- 关键词：Metallacarborane ; Synthesis ; NMR spectroscopy ; X-ray crystallography ; Isomerisation mechanisms ; Vertex labelling
- 刊名：Inorganica Chimica Acta
- 出版年：2005
- 期刊代码：40_00201693
- 类别：ch
- 出版时间：March 15, 2005
- 卷：358
- 期：5
- 页码：1485-1493
- 文件大小：416 K
摘要
The reaction between [5-I-7,8-Ph2-7,8-nido-C2B9H8]2芒芒芒 and NiCl2(dppe) affords 1,2-Ph2-4,4-dppe-12-I-4,1,2-closo-NiC2B9H8 (1) and 1,8-Ph2-2,2-dppe-10-I-2,1,8-closo-NiC2B9H8 (2). Reaction between the same carborane ligand and cis-PtCl2(PMe2Ph)2 yields three species, 1,8-Ph2-2,2-(PMe2Ph)2-10-I-2,1,8-closo-PtC2B9H8 (3), 1,8-Ph2-2,2-(PMe2Ph)2-12-I-2,1,8-closo-PtC2B9H8 (4), and 1,8-Ph2-2,2-(PMe2Ph)2-7-I-2,1,8-closo-PtC2B9H8 (5). Compounds 1芒芒芒5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC2B9 architecture of 1 constitutes a 芒芒芒1,2芒芒芒1,2芒芒芒 cage C atom isomerisation, and the 2,1,8-MC2B9 architectures of 2芒芒芒5 a 1,2芒芒芒1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph2-3,3-L2-9-I-3,1,2-closo-MC2B9H8 [M=Ni, L2