Theoretical evaluation of kinetic stereoelectronic effects on hydride transfer

Ann E. Pain; Ian H. Williams

doi:10.1039/C39880001367

Theoretical evaluation of kinetic stereoelectronic effects on hydride transfer

Ann E. Pain, Ian H. Williams

Department of Chemistry

University of Bristol

Research output: Contribution to journal › Article › peer-review

Abstract

Ab initio calculations for hydride transfer from HNCH₂ to HCNH⁺ with full optimisation at the MP2/6-311G** level predict that orientation of nitrogen lone pairs antiperiplanar to the transition-state C ⋯ H bonds lowers the reaction barrier by 22 kJ mol^-1, but that a quasi-cyclic transition structure with synperiplanar lone pairs is even more favourable, being lower in energy by another 46 kJ mol^-1.

Original language	English
Pages (from-to)	1367-1368
Number of pages	2
Journal	Journal of the Chemical Society, Chemical Communications
Volume	1988
Issue number	20
DOIs	https://doi.org/10.1039/C39880001367
Publication status	Published - 1 Jan 1988

ASJC Scopus subject areas

Molecular Medicine

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abstract = "Ab initio calculations for hydride transfer from HNCH2 to HCNH+ with full optimisation at the MP2/6-311G** level predict that orientation of nitrogen lone pairs antiperiplanar to the transition-state C ⋯ H bonds lowers the reaction barrier by 22 kJ mol-1, but that a quasi-cyclic transition structure with synperiplanar lone pairs is even more favourable, being lower in energy by another 46 kJ mol-1.",

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AB - Ab initio calculations for hydride transfer from HNCH2 to HCNH+ with full optimisation at the MP2/6-311G** level predict that orientation of nitrogen lone pairs antiperiplanar to the transition-state C ⋯ H bonds lowers the reaction barrier by 22 kJ mol-1, but that a quasi-cyclic transition structure with synperiplanar lone pairs is even more favourable, being lower in energy by another 46 kJ mol-1.

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Theoretical evaluation of kinetic stereoelectronic effects on hydride transfer

Abstract

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