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

Abstract Further studies of the attack of bidentate tertiary phosphines, such as dppm and dppe, and the related diarsine dpam, on Ru 3 (μ-H){μ 3 -C 2 CHR(OH)}(CO) 9 (R = H, Me) are described, together with the X-ray determined structures of [Ru 3 (μ 3 -C 2 CH 2 PPh 2 CH 2 CH 2 PPh 2 )(CO) 9 ]BF 4 ( 6 ) and Ru 3 (μ-H){μ 3 -C 2 CHMePPh 2 CH PPh 2 }(CO) 9 ( 7 ) (containing diphospha heterocycles), Ru 3 (μ-H){μ 3 -CH 2 (OH)C 2 PPh 2 CH 2 PPh 2 }(CO) 8 ( 8 ) (containing a phosphonium-alkynyl ligand also coordinated to a cluster Ru atom) and Ru 3 (μ-H)(μ 3 -CC CHAsPh 2 CH 2 AsPh 2 )(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.