Insertion of a phospholide unit into a metal-metal bond: Synthesis and X-ray structure of [Ru3(CO)9(μ:η1:η5-PC4H2Me2)(η1-C6H5)]

The reaction of [Ru-3(CO)(12)] with 3,4-dimethyl-1-phenylphosphole under mild conditions affords three derivatives which were identified by means of spectroscopic methods as the substitution compounds [Ru-3(CO)(12) (x)(PhPC4H2Me2)(x)] (x = 1, 2, 3) in which the phosphole ligand acts as a tertiary phosphine bonded through the phosphorus atom. Thermolysis of the monosubstituted [Ru-3(CO)(11)(PhPC4H2Me2)] in cyclohexane affords two new clusters, characterised as [Ru-3(CO)(9)(mu(3):eta(2):eta(2):eta(2)-PhPC4H2Me2)] and [Ru-3(CO)(9)(mu:eta(1):eta(5)-PC4H2Me2)(eta(1)-C6H5)], where the phosphole ring behaves as a six-and seven-electron donor ligand respectively. The reaction with [Os3H2(CO)(10)] gives the new species [Os-3(mu-H)(CO)(9)(mu(3):eta(1):eta(1):eta(2)-PhPC4H3Me2)] in which the ligand behaves as a five-electron donor. (C) 2012 Elsevier B. V. All rights reserved.