Influence of ancillary ligands in the coordination mode of P and As carbonyl stabilized ylides on Pt(II) systems. X-ray structure of trans-[Pt(PPh3)2(CF3){OC(OCH 3)=C(H)(PPh3)}][BF4]·0.5CH 2Cl2

Article abstract of DOI:10.1016/s0020-1693(96)05358-3

The carbonyl stabilized P and As ylides Ph₃PCHCOR (R = CH₃, Ph, OCH₃) and Ph₃AsCHCOR (R = CH₃, Ph, OCH₃) have been reacted with some platinum(II) complexes bearing ancillary ligands with different steric hindrance, in order to determine the factors that influence the C-versus O-coordination mode of the ylides. Thus, the reactions of [(dppe)PtCl₂] and [(dppv)PtCl₂] with Ph₃PCHCOR (R = CH₃, Ph) give the O-coordinated complexes, while with Ph₃PCHCOOCH₃ they give the corresponding C-coordinated derivatives. The reactions of trans-[(PPh₃)₂(CF₃)Pt(solv)]⁺BF ₄^- yield the O-coordinated compounds and the reactions with [Pt(C₃H₅)Cl]₄ give selectively the C-coordinated derivatives as well as the reactions with the dimer [PtCl{P(Bu¹)₂C(Me)₂CH₂}] ₂. The derivative trans-[Pt(PPh₃)₂(CF₃){OC(OCH ₃)=C(H)(PPh₃)}][BF₄] crystallizes in the triclinic space group P1? (No. 2), a = 10.385(4), b = 14.844(5), c = 18.511(6) ?, α = 96.46(2), β = 99.79(2), γ = 97.00(2)°, V = 2765(1) ?³, Z = 2. The values of coordination distances and of the Pt-O-C angle appear influenced by steric factors.