Stoichiometric and Catalytic Conversion of 1-Adamantyl Azide to 1-Adamantyl Isocyanate by [Cr(CO)(3)Cp](2) and Reaction with Mo(CO)(3)((PPr3)-Pr-i)(2) To Form Mo(kappa(2)-(Pr3P)-Pr-i = NN = NAd)(CO)(3)((PPr3)-Pr-i)

摘要

The reaction of 1-adamantyl azide (N(3)Ad.) with [Cr(CO)(3)CP](2) under Ar results in conversion of N(3)Ad to 1-adamantyl isocyanate (OCNAd) and [Cr(CO)(2)Cp](2). Two reaction intermediates were detected: Cr-3(2)(CO)(5)Cp-2 and an electron spin resonance active complex proposed to he center dot Cr(CO)(2)(O=C=NAd)Cp. Under a CO atmosphere, Cr-3(2)(CO)(5)Cp-2 regenerates [Cr(CO)(3)Cp](2) and approximately five turnovers can be achieved. Hydrogenation of N(3)Ad by HMo(CO)(3)Cp yields H(2)NAd, N-2, and [Mo(CO)(3)CP](2). N(3)Adreacts with Mo(CO)(3)((PPr3)-Pr-i) to form Mo(N(3)Ad)(CO)(3)((PPr3)-Pr-i)(2), which slowly isomerizes to Mo(kappa(2)-(i)Pr(3)PN(3)Ad)(CO)(3)((PPr3)-Pr-i), the structure of which is reported.