1148133-05-4Relevant articles and documents
Interaction of organoplatinum(II) complexes with monovalent coinage metal triflates
Moret, Marc-Etienne,Chen, Peter
, p. 5675 - 5690 (2009/09/08)
The organoplatinum(II) complexes [(NN)PtMe2] and [(NN)PtPh 2] (NN ) ArNC(Me)C(Me)NAr, Ar = 2,6-dichlorophenyl) can act as donor ligands for copper(I) and silver(I) triflates, affording a series of homo- and heteroleptic complexes which were characterized by X-ray diffraction. [(NN)PtMe2] binds to the coinage metals through short, ligand-unsupported d-d10 contacts that are best described as Pt→M dative bonds (M ) Cu, Ag), in which the dz2 orbital of the square-planar Pt(II) center donates electron density to the Lewis-acidic metal. Spectroscopic studies in solution and DFT calculations corroborate this description. [(NN)PtPh2] binds preferentially by η1 or η2 complexation of the ipso carbon atoms of the phenyl groups to the coinage metal, affording homoleptic complexes {[(NN)PtPh2]2M}+{TfO}- in the solid state. The 1:1 adducts of formula {[(NN)PtPh2]M(OTf)}n (M ) Cu, n ) 1; M ) Ag, n ) 2) are observed in solution, and a 1:2 adduct of formula {[(NN)PtPh2]Ag2(OTf)2(C 6H6)}n was characterized in the solid state, showing that unsupported Pt→M bonds are also accessible for [(NN)PtPh 2]. The thermolyses of the complexes [(NN)PtMe2]MOTf in benzene affords moderate yields of [(NN)PtPh2] through an oxidatively induced double C-H activation process.
