Synthesis and Structure of Pd and Pt Complexes with Doubly Stabilized Phosphorus Ylides

The doubly stabilized P‐ylide ligands Ph 3 P=C(CO 2 Me)C(=S)N(H)Ph ( L1 ), Ph 3 P=C(CN)C(=S)N(H)Ph ( L2 ), and Ph 3 P=C(CN)–[( E )‐C(CO 2 Me)=CH(CO 2 Me)] ( L3 ) have been prepared and fully characterized. The X‐ray structures of L1 and L2 are reported. The reactivity of L1 , L2 , and L3 towards cationic Pd II and Pt II precursors with two vacant coordination sites has been studied. Adducts of general formula [M(CX)( L n )]ClO 4 , [M(CX)( L n ) 2 ]ClO 4 , and [M(μ‐ L n )(CX)] 2 (ClO 4 ) 2 (CX = ancillary ligands) were obtained. The ylides L n coordinate to the metal center through their heteroatoms (O, N, S), while the C bonding of L n has not been observed in any of the cases studied. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)