Catalytic hydrogenolysis of alkyl halides by sulfido-bridged molybdenum clusters: A density functional study

Conference item

Density functional theory has been used to explore the mechanism of cleavage of H2 at a sulfido-bridged molybdenum cluster, CpMo(μ-SH)(μ-S)(μ-S2CH2)MoCp. The addition occurs across a single Mo-S bond, and the disruption of the strong Mo-S π bonding in the ground state leads to a very high-lying transition state (+43 kcal mol-1). Once formed, the adsorbed hydrogen migrates over the cluster via a series of hops from metal to sulphur, formally corresponding to a switch from hydridic to protic character. The low barrier (+15 kcal mol-1) for migration leads to facile hydrogenolysis of coordinated substrates. © 2005 Elsevier B.V. All rights reserved.

Authors: McGrady, J; Gracia, J

• Publication status: Published
• Host title: JOURNAL OF ORGANOMETALLIC CHEMISTRY
• Volume: 690
• Issue: 23
• Pages: 5206-5214
• Publication date: 2005-11-15
• DOI: 10.1016/j.jorganchem.2005.04.004
• ISSN: 0022-328X
• Keywords: sulfide clusters; hydrogen activation; density functional theory