Electron-deficient triruthenium and triosmium clusters from the reaction of the cluster anions [HM3(CO)(11)](-) (M = Ru, Os) with tricyclohexylphosphine in methanol
Author(s)
Godefroy, Isabelle
Ferrand, Vincent
Neels, Antonia
Kahlal, Samia
Saillard, Jean-Yves
Garland, Maria Teresa
Date issued
1999
In
Journal of Organometallic Chemistry
Vol
1-2
No
579
From page
285
To page
297
Subjects
cluster trinuclear unsaturated phosphine hydrido METAL-CARBONYL CLUSTERS MOLECULAR-ORBITAL CALCULATIONS X-RAY STRUCTURES CRYSTAL-STRUCTURE SUBSTITUTED DERIVATIVES TRIANGULAR PLATINUM TRINUCLEAR CLUSTER TRANSITION-METALS PHOSPHINE-LIGANDS MIXED-VALENCE
Abstract
The reaction of Na[HRu3(CO)(11)] with an excess of tricyclohexylphosphine in methanol gives the neutral complex H2Ru3(CO)(6)(PCy3)(3) which is the first 44 e(-) triruthenium cluster reported. This highly electron-deficient species reacts with carbon monoxide to give the saturated 48 e(-) cluster Ru-3(CO)(9)(PCy3)(3). The electronic structure of the novel 44 e- cluster was established by EHT and DFT molecular orbital calculations of isoelectronic model compounds. The analogous reaction of [N(PPh3)(2)][HOs3(CO)(11)] with PCy3 in methanol affords the 46 e(-) cluster H2Os3(CO)(7)(PCy3)(3), the first trisubstituted derivative of H2Os3(CO)(10). In all cases methanol acts as source of protons for the formation of the hydride clusters. (C) 1999 Elsevier Science S.A. All rights reserved.
Publication type
journal article