Abstract
A kinetic study is reported for the reactions of secondary aromatic amines p-YC 6H 4NHR (Y = MeO, Me, H; R = Me, Et) with the isocyanide complexes cis-[PdCl 2( p-XC 6H 4NC)(PPh 3)] (X = Me, H, Cl) leading to the carbene derivatives cis-[PdCl 2 {C(NH- p-C 6H 4X)NR- p-C 6H 4Y} (PPh 3)] in 1,2-dichloroethane at 25°C. A stepwise mechanism is proposed which involves a direct nucleophilic attack of the entering amine on the isocyanide carbon followed by proton transfers to the final carbene complexes. These take place both intramolecularly in a four-membered cyclic transition state and by the agency of one further amine molecule serving as a proton acceptor-donor in a six-membered transition state. Competition experiments with primary amines and trends in rate parameters are discussed to support the mechanism.
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