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.
Published Version
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