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

Paul T. Brain, Michael Bühl, Jill Cowie, Zoë G. Lewis, Alan J. Welch

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)231-237
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number2
DOIs
Publication statusPublished - 1996

ASJC Scopus subject areas

  • Chemistry(all)

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