The Staudinger reaction of platinum(II)- and palladium(II)-coordinated 2-(azidomethyl)phenyl isocyanide.: X-ray structure of trans-[PtCl{CN(H)C6H4-2-CH2N(H)} (PPh3)2][BF4] • CDCl3 • H2O

2-(Azidomethyl)phenyl isocyanide, 2-(CH2N3)C(6)H(4)NdropC (AziNC), coordinates to some cationic Pt(II) and Pd(II) species to afford isocyanide complexes of the type trans-[MCl(AziNC(PPh3)(2)][BF4] (M = Pt, 1; Pd, 2). AziNC is coordinated also in some neutral Pt(II) and Pd(II) species such as [MCl2(AziNC)(2)] (M = Pt, 3; Pd, 4) derived from the reactions of 2 equiv. of AziNC with [PtCl2(COD)] and [PdCl2(MeCN)(2)], respectively. Complexes 1 and 2 react with 1 equiv. of PPh3 affording the heterocyclic carbene complexes trans-[MCl{CN(H)C6H4-2-CH2N(H)}(PPh3)(2)][BF4] (M = Pt, 5; Pd, 6). Complexes 3 and 4 react with 1 equiv. of PPh3 displacing the isocyanide with the formation of the complexes cis-[MCl2(AziNC(PPh3)](M = Pt, 7; Pd, 8). These latter ones react with 2 equiv. of PPh3 affording as the final products the cationic carbene species trans-[MCl{CN(H)C6H4-2-CH2N(H)}(PPh3)(2)][Cl] (M = Pt, 9; Pd, 10). Complex 5 was also characterized by single crystal X-ray diffraction. The carbene complex is square-planar and the angle formed between the platinum square plane and the heterocyclic carbene ligand is 87.9(2)degrees. The C(1)-N(1) and C(1)-N(2) bond distances in the latter of 1.32(2) and 1.30(2) Angstrom, respectively, are short for a single bond and indicate extensive pi-bonding between the nitrogen atoms and the carbene carbon. (C) 2003 Elsevier B.V. All rights reserved.