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Synthesis, crystal structure and some reactions of the ruthenacarborane complex [Ru(CO)2(MeCCPh)(η5-7,8-C2B9H11],

1998; Elsevier BV; Volume: 562; Issue: 1 Linguagem: Inglês

10.1016/s0022-328x(98)00363-5

1872-8561

John C. Jeffery, Paul A. Jelliss, Elefteria Psillakis, Gillian E.A. Rudd, F. Gordon A. Stone,

Radiopharmaceutical Chemistry and Applications

The alkyne complex [Ru(CO)2(MeCCPh)(η5-7,8-C2B9H11] (3c) has been prepared and its structure determined by X-ray crystallography. The ruthenium is co-ordinated on one side by the nido-7,8-C2B9H11 fragment in a pentahapto manner, and on the other by the two CO molecules and the alkyne [Ru–Cav.=2.305, C–C=1.228(3) Å. Treatment of 3c with PEt3 and Ph2PCH2PPh2 in CH2Cl2 affords the ylid complexes [Ru{C(Me)C(Ph)PEt3}(CO)2(η5-7,8-C2B9H11)] (4b) and [Ru{C(Me)C(Ph)P(Ph)2CH2PPh2}(CO)2(η5-7,8-C2B9H11)] (4c), respectively. The structure of 4b was established by an X-ray diffraction study which revealed that the PEt3 molecule was attached to the carbon atom of the CPh group. In contrast, reactions between 3c and the donor molecules AsPh3, SbPh3 and Ph2P(S)CH2P(S)Ph2 resulted in displacement of the alkyne and formation of the complexes [Ru(CO)2(L)(η5-7,8-C2B9H11)] (5a, L=AsPh3; 5b, L=SbPh3; 5c, L=Ph2P(S)CH2P(S)Ph2). Treatment of 4c with the Ru(CO)2(η5-7,8-C2B9H11) fragment yielded the diruthenium complex [Ru2(μ-Ph2PCH2PPh2)(CO)4(η5-7,8-C2B9H11)2] (6). The structure, based on the linking of two Ru(CO)2(η5-7,8-C2B9H11) groups by the ligand Ph2PCH2PPh2, was determined by X-ray crystallography. NMR data for the new complexes are reported.