Cluster growth reactions with selenido-carbonyl clusters -: Synthesis, characterisation and theoretical study of the dimetallic closo clusters [WRu3(μ4-Se)2(μ-CO)4(CO)6(L)2] (L = phosphane) and of the donor-acceptor adduct [(CO)5W(μ4-Se)Ru3(μ3-Se)(CO)7{P(CH2Ph)Ph2}2]

The open-triangular, nido clusters of the type [RU3(mu(3)-Se)(2)-(CO)(7)(L)(2)] (L = PPh3, PPh2(OMe), PPh2(Me), P(p-MeO-C6H4)(3)] react at room temperature with [W(CO)(3)(MeCN)(3)] to give the dimetallic closo clusters [WRu3(mu(4)-Se)(2)(mu-C)(4)-(CO)(6)(L)(2)] When L is P(CH2Ph)Ph-2 the donor-acceptor adduct [(CO)(5)W( mu(4)-Se)Ru-3(mu(3)-Se)(CO)(7){P(CH2Ph)Ph-2}(2)] is obtained where the nido cluster [Ru-3{mu(3)-Se)(2)(CO)(7)(L)(2)] interacts with the fragment W(CO)5 through a selenido ligand. DFT calculations, performed on the model species [WRu3(mu(4)-Se)(2)(mu-CO)(4)(CO)(6)(PH3)(2)] and [(CO)(5)W(mu(4)-Se)-Ru-3(mu(3)-Se)-(CO)(7)(PH3)(2)] showed that the computed total energy of the latter is 1.1 eV lower than that of the former. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).