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Formation of (σ‐Alkenyl)‐ and (μ‐Vinylidene)palladium and ‐platinum Complexes by Oxidative Addition of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabuta‐1,3‐diene − The Molecular Structure of an Unusual Asymmetric (μ‐Vinylidene)Pd−Pd Complex
Author(s) -
Knorr Michael,
Schmitt Gérard,
Kubicki Marek M.,
Vigier Estelle
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200390073
Subject(s) - chemistry , palladium , oxidative addition , platinum , medicinal chemistry , toluene , diene , stereochemistry , crystal structure , ligand (biochemistry) , crystallography , catalysis , organic chemistry , receptor , natural rubber , biochemistry
4,4‐Dichloro‐1,1‐diphenyl‐2‐azabuta‐1,3‐diene ( 1 ) oxidatively adds to [Pd(PPh 3 ) 4 ] and [Pt(C 2 H 4 )(PPh 3 ) 2 ] giving rise to the σ‐alkenyl complexes trans ‐[MCl{[C(Cl)=C(H)−N=CPh 2 ]}(PPh 3 ) 2 ] ( 2a : M = Pd; 2b : M = Pt). When 1 is treated with [Pd(PPh 3 ) 4 ] in a 1:2 ratio in refluxing toluene, the dimetallic μ‐vinylidene complex [(PPh 3 )ClPd{μ‐[C=C(H)−N=CPh 2 ]}PdCl(PPh 3 ) 2 ] ( 3 ) is formed. In this fluxional compound, a PPh 3 ligands migrates in a reversible manner between the two Pd centers. Substitution of the PPh 3 ligands of 3 by 2 equiv. of Ph 2 PCH 2 PPh 2 affords the A‐frame complex [ClPd(μ‐dppm) 2 {μ‐[C=C(H)−N=CPh 2 ]}PdCl] ( 4 ). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)