Single and double nucleophilic attack on cluster-bonded allenylidenes: Synthesis of phosphorus heterocycles

Further studies of the attack of bidentate tertiary phosphines, such as dppm and dppe, and the related diarsine dpam, on Ru3(μ-H){μ3-C2CHR(OH)}(CO)9 (R = H, Me) are described, together with the X-ray determined structures of [Ru3(μ3-C2CH2PPh2CH2CH2PPh2)(CO)9]BF4 (6) and Ru3(μ-H){μ3-C2CHMePPh2CHdouble bond; length as m-dashPPh2}(CO)9 (7) (containing diphospha heterocycles), Ru3(μ-H){μ3-CH2(OH)C2PPh2CH2PPh2}(CO)8 (8) (containing a phosphonium-alkynyl ligand also coordinated to a cluster Ru atom) and Ru3(μ-H)(μ3-CCdouble bond; length as m-dashCHAsPh2CH2AsPh2)(CO)9 (9) (containing an arsino-allenylidene ligand). These complexes are formed by nucleophilic attack of the Group 15 ligand on an alkynyl or allenylidene ligand on the cluster.