کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1327241 | 977470 | 2005 | 9 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Catalytic hydrogenolysis of alkyl halides by sulfido-bridged molybdenum clusters: A density functional study Catalytic hydrogenolysis of alkyl halides by sulfido-bridged molybdenum clusters: A density functional study](/preview/png/1327241.png)
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.
Density functional theory has been used to explore the cleavage of H2 at a molybdenum cluster, CpMo(μ-SH)(μ-S)(μ-S2CH2)MoCp. The addition occurs across a single Mo–S bond, and strong Mo–S π bonding in the ground state leads to a very high barrier (ΔE‡ = +43 kcal mol−1). Once formed, hydride migration over the cluster is a facile process (ΔE‡ = +13 kcal mol−1).Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 690, Issue 23, 15 November 2005, Pages 5206–5214