Polyhedral metallathiaborane chemistry: Synthesis and characterisation of metallathiaboranes based on the twelve-vertex icosahedral closo-{MSB10H10} unit, where M is Rh or Ir
摘要:
The reaction of [nido-7-SB10H12] With [RhCl(PPh3)(3)] ill the presence of N,N,N'N'-tetramethylnaphthalene-1,8-diamine (tmnd) in CH2Cl2 gives twelve-vertex [2,2-(PPh3)(2)-2-H-closo-2,1-RhSB10H10] (1) and eleven-vertex [8,8-(PPh3)(2)-nido-8,7-RhSB9H10] (2), as major products, plus the dimeric species [{(PPh3)-closo-RhSB10H10)(2)] (3) as a minor product. Reaction of 1 with PMe2Ph in CH2Cl2 results in phosphine exchange and hydride substitution, affording the chloro analogue of 1, [2,2-(PMe2Ph)(2)-2-Cl-closo-2,1-RhSB10H10] (4). By contrast, reaction between [IrCI(PPh3)(3)] and [nido-7-SB10H12] in CH2C12 With timid affords only one product, twelve-vertex (2,2(PPh3)(2)-2-H-(closo-2,1-IrSB10H10] (5). [RuCl2(eta(5)-C5Me5)](2) with [nido-7-SB10H12] under the same conditions gives twelve-vertex [2-(eta(5)- C5Me5)-closo-2,1-RhSB10H10] (6). All the compounds are characterised by NMR spectroscopy, and by mass spectrometry, and the molecular structure of [2,2-(PMe2Ph)(2)-2-Cl-closo-2,1-RhSB10H10] (4) was established by single-crystal X-ray diffraction analysis. This last rhodathiaborane 4 is fluxional in solution through a process that involves a reversible partial rotation of the {RhCl(PMe2Ph)(2)} unit above the {SB4} pentagonal face of the {SB10H10} fragment. (C) 2007 Elsevier B.V. All rights reserved.