Synthesis and characterisation of pseudocloso iridium and ruthenium diphenyl carbaboranes. Molecular structures of 1,2-Ph2-3-(η-C6H6)-3,1,2-pseudocloso-RuC2B9H9and 1,2-Ph2-3-(cym)-3,1,2-pseudocloso-RuC2B9H9(cym =p-cymene) and individual gauge for localised orbitals calculations on carbametallaboranes

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Abstract
The syntheses and characterisations of 1,2-Ph2-3-(η-C5Me5)-3,1,2-pseudocloso-IrC2B9H91, 1,2-Ph2-3-(η-C6H6)-3,1,2-pseudocloso-RuC2B9H92, 1,2-Ph2-3-(cym)-3,1,2-pseudocloso-RuC2B9H9(cym =p-cymene)3 and 1,2-Ph2-3-(η-C6Me6)-3,1,2-pseudocloso-RuC2B9H94 are reported from the reactions between Tl2[7,8-Ph2-nido-7,8-C2B9H9] 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-RhC2B9H11, and allow a tentative assignment of those of 1,2-Ph2-3-(η-C5Me5)-3,1,2-pseudocloso-RhC2B9H9.

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