P. Giannoccaro et al., CARBAMOYL COMPLEXES AS A SOURCE OF ISOCYANATES OR CARBAMYL CHLORIDES, Journal of organometallic chemistry, 476(1), 1994, pp. 13-18
Isocyanates or carbamyl chlorides have been prepared by reaction of ca
rbamoyl complexes of nickel and palladium with CuCl2. Isocyanates are
selectively produced from the carbamoyl complexes of primary amines, [
LNiCl(CONHR)], (L = 2,6-bis(diphenyl-phosphinomethyl) pyridine; R = C6
H5, P-CH3C6H4, or P-ClC6H4)) and [Pd(PPh3)2Cl(CONHCH2COOCH3)], whereas
carbamoyl complexes of secondary amines, such as [Pd(PPh3)2Cl(CO(CH2)
4CH2)], afford carbamyl chloride. As expected, the reaction of the res
ulting isocyanates or carbamyl chlorides in situ with alcohols or amin
es produces carbamates or N,N'-substituted ureas, respectively.