The bimetallic Ru(2)Pt complex [(Cp*Ru)(2)(mu(2)-NHPh)(mu(2)-H)(mu(3)-C)PtMe(PMe(3))(2)][OTf] (3; Cp* = eta(5)-C(5)Me(5)) containing a planar three-coordinate carbido ligand has been prepared in 93% yield by thermal isomerization of the bridging methylene precursor [(Cp*Ru)(2)Me(mu(3)-NPh)(mu(2)-CH(2))Pt(PMe(3))(2)][OTf] (2) via cleavage of the methylene C-H bonds. Exposure of the carbido complex 3 to carbon monoxide (1 atm) induced coupling of the carbido ligand with the nearby methyl and hydride ligands to produce the diruthenium ethylidene complex [(Cp*Ru)(2)(mu(2)-CHMe)(mu(2)-NHPh)(CO)(2)][OTf] (4) and the known triplatinum complex [Pt(CO)(PMe(3))](3). The crystal structures of 2, 3, and 4 (BPh(4) salt) are reported.
The diruthenium mu2-imido mu2-methylene complex [(Cp*Ru)2(mu2-NPh)(mu2-CH2)] serves as a bifunctional scaffold for cluster synthesis, producing a mu3-imido Ru2Pt cluster [(Cp*Ru)2(mu3-NPh)(mu2-CH2)Pt(PMe3)2] on treatment with [Pt(eta2-C2H4)(PMe3)2] and a mu3-methylidyne Ru4Pd2 cluster [(Cp*Ru)2(mu2-NPh)(mu3-CH)PdCl]2 with [PdMeCl(cod)].
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