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Synthesis and characterisation of pseudocloso iridium and ruthenium diphenyl carbaboranes. Molecular structures of

DOI: 10.1039/DT9960000231

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 231 - 237 (1996)

Update date:2022-08-04

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Authors:

Brain, Paul T.Brain, Paul T.

Buehl, MichaelBuehl, Michael

Cowie, JillCowie, Jill

Lewis, Zoe G.Lewis, Zoe G.

Welch, Alan J.Welch, Alan J.

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Article abstract of DOI:10.1039/DT9960000231

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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Product name:[(C6H5)2(CH3C6H4CH(CH3)2)RuC2B9H9]

Cas No:174744-51-5

174744-51-5

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