Five-coordinate bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(tertiary phosphine)palladium(II) and -platinum(II) complexes. X-ray crystal and molecular structures and fluxional motions in solution.

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Five-coordinate complexes [M(hfac)2L] (M=Pd, Pt; hfac=1,1,1,5,5,5-hexafluoro-2,4-pentanedionate anion) were produced by the reactions of [M(hfac)2] with equimolar amounts of tertiary phosphines, phosphites, and triphenylarsine. They were characterized by 1H, 13C, 19F, and 31P NMR spectra in solution and several complexes containing bulky phosphines as L were isolated, and structures of [Pd(hfac)2{P(o-tolyl)3}] and [Pt(hfac)2{P(cyclohexyl)3}] were determined by X-ray analysis. Both complexes have very distorted square-pyramidal structures, one of the two hfac anions in either of them spanning the apical and basal coordination sites. NMR spectra at various temperatures disclosed the fluxional behaviors of these complexes which retain the solid-state structures at such low temperatures as −60 °C. Two kinds of twist mechanisms were proposed.
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