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Chemistry of Polynuclear Metal Complexes with Bridging Carbene or Carbyne Ligands. Part 88. Carbaboranetungsteniridium Compounds; Crystal Structure of the Complex 5-C2B9H9Me2)>

DOI: 10.1039/DT9890001845

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1845 - 1854 (1989)

Update date:2022-08-11

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Authors:

Jeffery, John C.Jeffery, John C.

Ruiz, Miguel A.Ruiz, Miguel A.

Sgerwood, PaulSgerwood, Paul

Stone, F. Gordon A.Stone, F. Gordon A.

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Article abstract of DOI:10.1039/DT9890001845

The reaction between the compounds (cod = cyclo-octa-1,5-diene) and CR)(CO)2(η5-C2B9H9Me2)> (R = C6H4Me-4) in thf (tetrahydrofuran) at room temperature affords the complex 5-C2B9H9Me2)>.The triphenylphosphine groups in the latter can be displaced with PEt3, P(OPh)3, or P(OMe)3 to give the compounds 5-C2B9H9Me2)> .In solution several of these products exist as isomeric mixtures.An X-ray diffraction study was carried out on an isomer of 5-C2B9H9Me2)>.The W-Ir bond <2.590(1) Angstroem> is spanned by the p-tolylmethylidyne group <μ-C-W 2.06(1), μ-C-Ir 1.95(1) Angstroem>.The nido-icosahedral fragment C2B9H9Me2 is η5-co-ordinated to the tungsten, but the central boron CCBBB in the pentagonal face of the ligand is attached to the iridium via a two-electron three-centre B-H<*>Ir bond.The tungsten atom also carries two terminal CO groups, and the two PEt3 ligands are bonded to the iridium.The co-ordination environment of the iridium is such that the plane defined by the atoms IrP2 is perpendicular to that containing the atoms W, μ-C, and B-H<*>Ir, and the midpoint of the cage C-C bond.The reaction between 5-C2B9H9Me2)> and P(OMe)3 also affords the compounds 5-C2B9H8Me2)(CO)32> and 5-CH(R)(C2B9H7Me2)>(CO)24>.Similarly PMe3 displaces the PPh3 groups in the precursor to give 5-C2B9H8Me2)(CO)2(PMe3)3> and 5-CH(R)(C2B9H7Me2)>(CO)2(PMe3)4>.The reactions between 2(cod)> (L2 = Ph2PCH2CH2PPh2 or 2,2'-bipyridine) and CR)(CO)2(η5-C2B9H9Me2)> yield tungsten-iridium complexes 5-C2B9H8Me2)(CO)3L2> with terminal Ir-H bonds, and ? B-Ir linkages to the carbaborane group ligating the tungsten.N.m.r. data (1H, 13C-<1H>, 31P-<1H>, and 11B-<1H>) for the new compounds are reported and discussed.

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Product name:cyclo-octa-1,5-diene

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