Abstract
Reactions of the open Ru 5C 2 cluster complex, Ru 5(μ 5-C 2)(μ-SMe) 2(μ-PPh 2) 2(CO) 11, ( 1), with hydrogen or olefins afforded electron-rich vinylidene complexes Ru 5(μ 3-CCHR)(μ 3-SMe) 2(μ-PPh 2) 2(CO) 10 [ 2; R H and 3; R CHCHF′ (R′ H, Me, Ph and CO 2Et)]. X-ray structural determinations have been carried out on 2 and 3 (R′ H, Me and Ph). These complexes contain an Ru 5 core consisting of three edge-sharing triangles; the vinylidene ligand, which spans one of the Ru 3 faces, is fluxional, with concomitant changes occurring in the orientations of the SMe, PPh 2 and CO groups. The clusters have 80 cluster valence electrons, the Ru-Ru separations being elongated (av. 3.03 Å) as a result of occupation of Ru-Ru anti-bonding orbitals.
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