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

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.