ON THE ELECTRONIC HYPERSURFACE OF THE METHYLENEPHOSPHENIUM CATION

Schoeller W, STRUTWOLF J. ON THE ELECTRONIC HYPERSURFACE OF THE METHYLENEPHOSPHENIUM CATION. THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE. 1994;111:127-137.The electronic hypersurface of the methylenephosphenium cation is explored on the basis of ab initio calculations of double-zeta quality. The findings are compared with corresponding investigations on the nitrogen analogue (iminomethylene cation), methylenesilylene and methylenecarbene. For the phosphorus case, PCH2 is the most stable species on the potential energy surface, while for the nitrogen case the acetylenic structure, HNCH+ (C(infinity v) symmetry) is the most stable species. For the substituted cases a bridged geometry comes to the fore for PCHR+ (R = NH2, PH2, C6H5). These substituents strongly pronounce cation stability for PCHR+, as evaluated by corresponding group transfer reactions