Synthesis and structural studies of new ruthenium cluster carbonyl derivatives from (PhP)5 and [Ru3(CO)12] and [Ru3(CO)10(NCMe)2]

Abstract

Reaction of the cyclopolyphosphane (PhP)₅ with [Ru₃(CO)₁₂] in p-xylene at 135 °C for 19 h afforded the new clusters [Ru₄(CO)₁₀(µ₃-(PPh)₂){µ₄-(PPh)₂}]1 and [Ru₄(CO)₈(µ-PHPh)₂(µ₄-PPh)}µ₄-(PPh)₂}]2. Treatment of (PhP)₅ with the activated triruthenium cluster [Ru₃(CO)₁₀(NCMe)₂] at room temperature overnight gave [Ru₃(CO)₁₀{(PhP)₅}]3. The structures of the three clusters have been established by single-crystal X-ray analysis. In 1 the four ruthenium atoms have a skew, chain structure while in 2 the four ruthenium atoms adopt a rectangular geometry. Novel phosphido or phosphinidene groups are present in both clusters. In the case of 3 the cyclophosphane (PhP)₅ remains intact and acts as a bidentate ligand, occupying the equatorial sites of the ruthenium triangular plane, through the two P atoms in the 1,3 positions.