A theoretical comparison of phosphino and amino groups in the isocyanide–cyanide rearrangement

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Abstract
Ab initio molecular orbital calculations have been used to study the isocyanide–cyanide rearrangement involving the migration of the hydrogen, amino and phosphino groups. Geometries were optimized using MP2/6-311 G(d,p) while relative energies were obtained from CISDQ/6-311 ++ G(d,p) wavefunctions. Structures and some spectroscopic properties of the equilibrium structures are predicted. Phosphinoisocyanide is found to lie 16 ± 2 kcal mol–1 above phosphinocyanide, and to rearrange to the latter with an energy barrier of 27 ± 2 kcal mol–1. Energetics (kcal mol–1) of two other rearrangements are as follows: isocyanamide (0)→ TS (37)→ cyanamide (–44) and hydrogen isocyanide (0)→ TS (30)→ hydrogen cyanide (–14). Phosphinoisocyanide exhibits kinetic and thermodynamic stability similar to hydrogen isocyanide (relative to their isomers) and should thus be detectable in both gaseous and condensed phases.

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