A Theoretical Insight into the Mechanism of the Silver-Catalysed Transsiliranation Reaction

• Published in: European Journal of Organic Chemistry Vol. 2010; no. 7; pp. 1231 - 1234
• Main Authors: Mayoral, José Antonio, Rodríguez-Rodríguez, Sergio, Salvatella, Luis
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-03-2010; WILEY‐VCH Verlag; Wiley-VCH
• Subjects: Chemistry; Density functional calculations; Exact sciences and technology; Heterocyclic compounds; Kinetics and mechanisms; Miscellaneous; Organic chemistry; Organometalloidal and organometallic compounds; Preparations and properties; Reaction mechanisms; Reactivity and mechanisms; Si derivatives; Silanes; Silver; Small ring systems; Silanes; Catalytic reaction; Silicon heterocycle; Molecular structure; Organic silylene; Prediction; Theoretical study; Organic silane; Transition metal; NMR spectrometry; Density functional calculations; Experimental study; Infrared spectrometry; Silver; Small ring systems; Alkene; Reaction mechanism; Density functional method; Reaction mechanisms; Ethylenic compound
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200901315

DFT calculations on a silver‐catalysed transsiliranation reaction (silylene transfer from a silirane to an alkene) have shown the key role of a silylenesilver ion in the catalyticcycle. Although the corresponding triflate‐bound species has previously been detected by NMR and IR spectroscopy, no significant silylene‐transfer activity is predicted for such a nonionised structure. Several experimental results can be explained by this new reaction mechanism.
DFT calculations on a silver‐catalysed transsiliranation reaction (silylene transfer from a silirane to an alkene) have shown the key role of a silylenesilver ion in thecatalytic cycle. Although the triflate‐bound species has previously been observed, no significant silylene‐transfer activity is predicted for such nonionised structures.