Preparation, crystal structure, spectroscopic characterization, and normal coordinate analysis of trans-[PtF2(Py)(4)](BPh4)2 center dot 2H(2)O

By reaction of [Pt(Py)(4)](BPh4)(2) with XeF2 in propylencarbonate trans-[PtF2(Py)(4)](BPh4)(2) . 2H(2)O is formed and purified by recrystallization. X-ray structure determination on a single crystal has been performed (tetragonal, space group P 4/ncc, a = 18.403(3), c = 17.183(3) Angstrom). The pyridine rings are twisted propeller-like against the Pt-N-4 plane with an angle of 62.3(3)degrees. The bond lengths are Pt-N = 2.008(9), Pt-F1 = 1.938(10) and Pt-F2 = 1.943(10) Angstrom. Using the molecular parameters of the X-ray structure determination and assuming D-4 point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis. Good agreement between observed and calculated frequencies is obtained with the valence force f(d)(PtF) = 3.51 and f(d)(PtN) = 2.75 mdyn/Angstrom. The F-19 NMR spectrum of trans-[PtF2(Py)(4)](BPh4)(2) in N,N-dimethylformamide solution exhibits a pseudotriplet at -267 ppm resulting in the coupling constant (1)J((FPt)-F-19-Pt-195) of 1724 Hz. The Pt-195 NMR spectrum shows a triplet at 6265 ppm.