Cluster Growth Reactions with Selenido‐Carbonyl Clusters − Synthesis, Characterisation and Theoretical Study of the Dimetallic closo Clusters [WRu 3 (μ 4 ‐Se) 2 (μ‐CO) 4 (CO) 6 (L) 2 ] (L = Phosphane) and of the Donor‐Acceptor Adduct [(CO) 5 W(μ 4 ‐Se)Ru 3 (μ 3 ‐Se)(CO) 7 {P(CH 2 Ph)Ph 2 } 2 ]

The open‐triangular, nido clusters of the type [Ru 3 (μ 3 ‐Se) 2 (CO) 7 (L) 2 ] (L = PPh 3 , PPh 2 (OMe), PPh 2 (Me), P( p ‐MeO‐C 6 H 4 ) 3 ] react at room temperature with [W(CO) 3 (MeCN) 3 ] to give the dimetallic closo clusters [WRu 3 (μ 4 ‐Se) 2 (μ‐CO) 4 (CO) 6 (L) 2 ]. When L is P(CH 2 Ph)Ph 2 the donor‐acceptor adduct [(CO) 5 W(μ 4 ‐Se)Ru 3 (μ 3 ‐Se)(CO) 7 {P(CH 2 Ph)Ph 2 } 2 ] is obtained where the nido cluster [Ru 3 (μ 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 [WRu 3 (μ 4 ‐Se) 2 (μ‐CO) 4 (CO) 6 (PH 3 ) 2 ] and [(CO) 5 W(μ 4 ‐Se)Ru 3 (μ 3 ‐Se)(CO) 7 (PH 3 ) 2 ], showed that the computed total energy of the latter is 1.1 eV lower than that of the former. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)