Isomerisation following the platination of [7,8-Ph2-9,11-I2-7,8-nido-C2B9H7]2-

被引：7
作者：
Ellis, D [1 ]
Garrioch, RM [1 ]
Rosair, GM [1 ]
Welch, AJ [1 ]
机构：
[1] Heriot Watt Univ, Dept Chem, Sch Engn & Phys Sci, Edinburgh EH14 4AS, Midlothian, Scotland
来源：
POLYHEDRON | 2006年 / 25卷 / 04期
关键词：
metallacarborane; synthesis; NMR spectroscopy; X-ray crystallography; isomerisation mechanisms;
D O I：
10.1016/j.poly.2005.10.006
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The synthesis, by electrophilic substitution, and characterisation of two new B-substituted nido diphenylcarboranes is described. [HNMe3][7,8-Ph-2-9-1-7,8-nido-C2B9H9] (1) and [HNMe3][7,8-Ph-2-9,11-I-2-7,8-nido-C2B9H8] (2) were characterised spectroscopically with the structure of the latter additionally confirmed by a crystallographic study. [7,8-Ph-2-9,11-I-2-7,8-nido-C2B9H8](2-) was treated with a source of {Pt(PMe2Ph)(2)}(2+) and three new platinacarboranes isolated. All were characterised by a combination of H-1, B-11 and P-31 NMR spectroscopies and by single crystal X-ray diffraction, and all were found to have undergone a 1,2 -> 1,7 cage C atom isomerisation, relative to the presumed first product of the metallation. The major product 3 is 1,8-Ph-2-2,2-(PMe2Ph)(2)-6,7-I-2-2,1,8-CIOSO-PtC2B9H7 with both (iodide) substituted boron vertices in the upper part of the icosahedron. The minor products 4 and 5 are, respectively, 1,8-Ph-2-2,2-(PMe2Ph)(2)-6,12-I-2-2,1,8-closo-PtC2B9H7 and 1,8-Ph-2-2,2-(PMe2Ph)(2)-10,12-I-2-2,1,8-closo-PtC2B9H7, having one and two substituted boron vertices in the lower pentagonal belt. These structural results allow speculation on the mechanism of isomerisation of crowded platinacarboranes. (c) 2005 Elsevier Ltd. All rights reserved.
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页码：915 / 922
页数：8
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