Novel ketene formation by reactions of acid chlorides with low-valent platinum complexes

Article abstract of DOI:10.1016/0022-328X(91)83163-X

Pt(CO)n(PPh3)4-n (n = 0-2) reacts with Ph2CHCOCl under CO to afford diphenylketene and trans-PtHCl(PPh3)2.For this reaction, the rate law is zero order in the platinum complex, first order in Ph2CHCOCl, and first order in free PPh3.A primary isotope effect (k_H/k_D = 4.5) was observed in the reaction of Ph2CDCOCl.A mechanism is proposed which involves the rate-determining enolization of Ph2CHCOCl by PPh3 followed by fast abstraction of HCl by a platinum(0) complex.