Vibrational and nuclear magnetic resonance spectra of some complexes of trihalogeno(trihalogenophosphine)platinate(II), and their methanolysis reactions

Abstract

Tetrabutylammonium salts of the anions [PtX₃(PY₃)]^–(X = Cl, Br, or I; Y = F or Cl) and [PtBr₃(PBr₃)]^– have been isolated and their Raman and infrared spectra studied in detail. Fluorine-19, ³¹P, and ¹⁹F-{¹⁹⁵Pt} n.m.r. spectra have been recorded as have ³¹P n.m.r. spectra of [PtBr₃L]^–(L = PBrCl₂ or PBr₂Cl) prepared in situ. The anions [PtX₃{P(OMe)₃}]^–(X = Cl, Br, or I) have been obtained by methanolysis of their PCl₃ or PBr₃ equivalents. N.m.r. parameters of these complexes and the methanolysis intermediates [PtX₃{PY_n(OMe)_3–n}]^–(n=1 or 2) are reported. Trends in ₃₁P co-ordination shifts, ¹⁹⁵Pt–³¹P coupling constants, and ¹⁹⁵Pt chemical shifts are discussed.