STRUCTURAL VARIATIONS IN HEXANUCLEAR RUTHENIUM CLUSTERS WITH THIOUREATO LIGANDS - SYNTHESES AND MOLECULAR-STRUCTURES OF S)(MU(3),ETA(2)-SCNHPHNPH)(MU(3),ETA(2)-NPHCNHPH)] AND [(MU-H)(6)RU-6(CO)(14)(MU(3),ETA(2)-SCNHPHNPH)(2)]

Under thermal conditions, the trinuclear ruthenium cluster [(mu-H)RU(3 )(CO)(9)(mu(3),eta(2)-SCNHPhNPh)] (1) was found to undergo metal frame work condensation to hexanuclear ruthenium clusters. The hexanuclear c luster 14)(mu(2)-CO)(2)(mu(4)-S)(mu(3),eta(2)-SCNHPhNPh)] (2), shown b y X-ray crystallography to contain a hexagonal boat arrangement of the six metal atoms, was isolated along with the hexagonal sofalike clust er (2)H)Ru-6(CO)(16)(mu(5)-S)(mu(3),mu(2)-SCNHPhNPh)] (3), reported pr eviously. Crystals of 2 are triclinic, space group P (1) over bar, wit h a = 12,141(3) Angstrom, b = 12.449(4) Angstrom, c = 19.712(6) Angstr om, alpha = 90.22(3)degrees, beta = 99.50(2)degrees, gamma = 111.61(2) degrees, and Z = 2. Compound 3 was found to take up molecular hydrogen under mild conditions to give (mu(2)-H)(6)Ru(CO)(14)(mu(3),eta(2)-SCN HPhNPh)(2)] (4), the X-ray structure analysis of which reveals a hexag onal raft arrangement of the Ru-6 skeleton. Crystals of 4 are triclini c, space group P (1) over bar, with a 9.799(1) Angstrom, b = 12.594(2) Angstrom, c = 14.466(1) Angstrom, alpha = 112.45(1)degrees, beta = 92 .71(1)degrees, gamma = 102.05(1)degrees, and Z = 1.