CLUSTER CHEMISTRY .84. REACTIONS OF RU5(MU-5-C2PPH2)(MU-PPH2)(CO)13 WITH ALKENES - ATTACK AT THE C2PPH2 LIGAND WITHOUT CLEAVAGE OF THE C-P BOND - X-RAY STRUCTURES OF RU5(MU-5-C)(MU-PPH2)(MU-RC3H3PPH2)(CO)11 (R = ME, PH) AND RU5(MU-5-C)(MU-PPH2)(MU-PHC3H3PPH2)(CO)11-N(P(OME)3) (N = 0, 1)

Reactions of terminal alkenes (CH2=CHR; R = Me, Ph) with Ru5(mu-C2PPh2)(mu-PPh2)(CO)13 resulted in addition of the alkene to C(alpha) of the Ph2PC2 ligand and the cleavage of the C(alpha)-C(beta) bond to give complexes containing the mu-eta3,P-(CHRCHCH)PPh2 ligand attached to a square pyramidal Ru5C core. Both complexes were characterized by single crystal X-ray studies. Addition of P(OMe)3 to the styrene derivative resulted in Ru-Ru bond cleavage and CO substitution reactions. The product from the former reaction contains a basket-like (or wing-tip-bridged butterfly) Ru5 Cluster retaining the central carbido C atom. When this is heated, it is converted into a square pyramidal Ru5C cluster, with migration of the tertiary phosphine ligand. The structures of both of the complexes Ru5(mu5-C)(mu-PPh2)(mu-PhC3H3PPh2)(CO)10{P(OMe)3} and Ru5(mu5-C)(mu-PPh2)(mu-PhC3H3PPh2)(CO)11{P(OMe)3} have been determined by X-ray diffraction studies. Probable routes to these clusters are discussed.