Journal of the Chemical Society, Dalton Transactions p. 231 - 237 (1996)
Update date:2022-08-04
Topics:
Brain, Paul T.
Buehl, Michael
Cowie, Jill
Lewis, Zoe G.
Welch, Alan J.
The syntheses and characterisations of 1,2-Ph2-3-(η-C5Me 5)-3,1,2-pseudocloso-IrC2B9H9 1, 1,2-Ph2-3-(η-C6H 6)-3,1,2-pseudocloso-RuC2B9H9 2, 1,2-Ph2-3-(cym)-3,1,2-pseudocloso-RuC2B9H 9 (cym = p-cymene) 3 and 1,2-Ph2-3-(η-C6Me 6)-3,1,2-pseudocloso-RuC2B9H9 4 are reported from the reactions between Tl2[7,8-Ph2-nido-7,8-C2B9H 9] and either [{IrCl2(C5Me5)}2] or the appropriate [{RuCl2(arene)}2] species. By 11B NMR spectroscopy all these compounds have pseudocloso geometries, in which the C(1) ... C(2) connectivity is broken and an approximately square M(3)C(1)B(6)C(2) face is generated. Crystallographic studies on 2 and 3 confirm this suggestion. It is suggested that distortion in these species arises from steric crowding between the Cphenyl substituents, forced to adopt conformations with high θ values by the presence of the η-bonded substituent at M(3). Individual gauge for localised orbitals calculations, reported for the first time on transition-metal heteroboranes, reasonably reproduce the (previously assigned) 11B NMR chemical shifts of 3-(η-C5Me5)-3,1,2-closo-RhC2B 9H11, and allow a tentative assignment of those of 1,2-Ph2-3-(η-C5Me 5)-3,1,2-pseudocloso-RhC2B9H9.
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