SYNTHESIS AND STRUCTURAL STUDIES OF NEW RUTHENIUM CLUSTER CARBONYL DERIVATIVES DERIVED FROM (PHP)(5) AND [RU-3(CO)(12)] AND [RU-3(CO)(10)(NCME)(2)]

Reaction of the cyclopolyphosphane (PhP)(5) with [Ru-3(CO)(12)] in p-xylene at 135 degrees C for 19 h afforded the new clusters [RU(4)(CO)(10)(mu(3)-PPh)(2){mu(4)-(PPh)(2)}] 1 and [RU(4)(CO)(8)(mu-PHPh)(2)(mu(4)-PPh){mu(4)-(PPh)(2)}] 2. Treatment of (PhP)(5) with the activated triruthenium cluster [Ru-3(CO)(10)(NCMe)(2)] at room temperature overnight gave [Ru-3(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), 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.