Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 107. Reactions of diphenylphosphine with molybdenumtungsten dimetal complexes; crystal structures of [MoW(µ-PPh2){µ-C(OH)C(C6H4Me-4)}-(CO)(η7-C7H7)(η5-C2B9H11)]and[MoW(µ-PPh2)(CO)3(η5-C9H7){η5-C2B9H8(CH2C6-H4Me-4

Treatment of the compounds [MoW(µ-CC6H4Me-4)(CO)2(η7-C7H7)(η5-C2B9H10R)](R = H or Me) in CH2Cl2with PHPh2 affords the complexes [MoW(µ-PPh2){µ-C(OH)C(C6H4Me-4)}(CO)(η7-C7H7)-(η5-C2B9H10R)]. The structure of the species with R = H was established by X-ray diffraction. The Mo–W bond [2.713(1)A] is spanned by the PPh2 group [Mo–P 2.439(3), W–P 2.360(3)A], and in a transverse manner by the alkyne. However, the latter is twisted so that the C(OH) atom lies appreciably closer to the tungsten [µ-C–W 2.067(8)A] than the molybdenum [µ-C–Mo 2.352(8)A], whereas the C(C6H4Me-4) atom is essentially symmetrically bridging [µ-C–Mo 2.224(9), µ-C–W 2.251(8)A]. The molybdenum atom carries the η7-C7H7 group (C–Mo av. 2.27 A), and the tungsten atom is η5 co-ordinated by the C2B9H11 cage and a CO group. The reaction between [MoW(µ-CC6H4Me-4)(CO)3(η5-C9H7)(η5-C2B9H9Me2)] and PHPh2in CH2Cl2 gives the complex [MoW(µ-CC6H4Me-4)(CO)2(PHPh2)(η5-C9H7)(η5-C2B9H9Me2)]. The latter on heating in toluene at 70 °C yields the compound [MoW(µ-PPh2)(CO)3(η5-C9H7){η5-C2B9H8(CH2C6H4Me-4)Me2}], the structure of which was established by X-ray diffraction. The Mo–W bond [2.708(1)A] is bridged by the PPh2 group [Mo–P 2.357(2), W–P 2.456(2)A]. The tungsten atom is ligated by two CO groups, and η5 co-ordinated by the C2B9 cage. In the open face of the latter a BH group in the α position to a CMe fragment forms a B–H⇀Mo exopolyhedral bond, while the boron atom β to the CMe groups in the pentagonal ring carries a CH2C6H4Me-4 substituent. The molybdenum atom is ligated by a CO molecule and the indenyl group. The n.m.r. data (1H, 13C-{1H}, 11B-{1H}, and 31P-{1H}) for the new compounds are reported and discussed.

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