Isomerization energies and surface electrostatic potential analyses on nitriles and isocyanides.

Isocyanide-nitrile rearrangement has long been a continuing and interesting topic. A series of nitriles and isocyanides with the substituents of R = -AlH2, -BeH, -BH2, -C≡CH, -CF3, -CH3, -Cl, -C≡N, -COOH, -F, -H, Li, -MgH, -Na, -NH2, -NO2, -OH, -PH2, -SH, -SiH3, and -CH = CH2 were investigated systematically based on full optimization at B3LYP-D3(BJ)/def2-QZVP level, and the isomerization energies from R-C≡N to:C = N-R were estimated. The substituent effect and bonding characters were analyzed by surface ESP colored van der Waals surfaces in conjunction with the global and local electrostatic extrema.