Theoretical evaluation of kinetic stereoelectronic effects on hydride transfer
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.