Bis(phosphine) Pd-azido complexes containing heterocycles such as tetrazolyl, pyrazinyl, and thienyl groups reacted with aryl isocyanides to give the corresponding Pd-carbodiimido or -imidoyl carbodiimido complexes. These products were formed by the insertion of the isocyanides into the Pd-N (azido) or the Pd-C (heterocycles) bond. (C) 2007 Elsevier B.V. All rights reserved.