M. Basato, F. Benetollo, G. Facchin
Jan 15, 2004
Citations
0
Influential Citations
34
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract 2-(Azidomethyl)phenyl isocyanide, 2-(CH 2 N 3 )C 6 H 4 NC (AziNC), coordinates to some cationic Pt(II) and Pd(II) species to afford isocyanide complexes of the type trans -[MCl(AziNC)(PPh 3 ) 2 ][BF 4 ] (M=Pt, l ; Pd, 2 ). AziNC is coordinated also in some neutral Pt(II) and Pd(II) species such as [MCl 2 (AziNC) 2 ] (M=Pt, 3 ; Pd, 4 ) derived from the reactions of 2 equiv. of AziNC with [PtCl 2 (COD)] and [PdCl 2 (MeCN) 2 ], respectively. Complexes 1 and 2 react with 1 equiv. of PPh 3 affording the heterocyclic carbene complexes trans -[MCl{ (H)}(PPh 3 ) 2 ][BF 4 ] (M=Pt, 5 ; Pd, 6 ). Complexes 3 and 4 react with 1 equiv. of PPh 3 displacing the isocyanide with the formation of the complexes cis -[MCl 2 (AziNC)(PPh 3 )] (M=Pt, 7 ; Pd, 8 ). These latter ones react with 2 equiv. of PPh 3 affording as the final products the cationic carbene species trans -[MCl{ (H)}(PPh 3 ) 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)°. The C(1)–N(1) and C(1)–N(2) bond distances in the latter of 1.32(2) and 1.30(2) A, respectively, are short for a single bond and indicate extensive π-bonding between the nitrogen atoms and the carbene carbon.