Abstract
The reaction between [5-I-7,8-Ph 2-7,8- nido-C 2B 9H 8] 2− and NiCl 2(dppe) affords 1,2-Ph 2-4,4-dppe-12-I-4,1,2- closo-NiC 2B 9H 8 ( 1) and 1,8-Ph 2-2,2-dppe-10-I-2,1,8- closo-NiC 2B 9H 8 ( 2). Reaction between the same carborane ligand and cis-PtCl 2(PMe 2Ph) 2 yields three species, 1,8-Ph 2-2,2-(PMe 2Ph) 2-10-I-2,1,8- closo-PtC 2B 9H 8 ( 3), 1,8-Ph 2-2,2-(PMe 2Ph) 2-12-I-2,1,8- closo-PtC 2B 9H 8 ( 4), and 1,8-Ph 2-2,2-(PMe 2Ph) 2-7-I-2,1,8- closo-PtC 2B 9H 8 ( 5). Compounds 1– 5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC 2B 9 architecture of 1 constitutes a “1,2 → 1,2” cage C atom isomerisation, and the 2,1,8-MC 2B 9 architectures of 2– 5 a 1,2 → 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph 2-3,3-L 2-9-I-3,1,2- closo-MC 2B 9H 8 [M = Ni, L 2 = dppe; M = Pt, L 2 = (PMe 2Ph) 2]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed.
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