Abstract
The title compounds (L = phosphine oxide, pyridine N-oxides)have been isolated and characterized, and their ClCH 2CN so1utions studied by variabletemperature 1H, 19F and 31PNMR. A detailedinvestigation on Et 4N[WO 2F 3(OPMe 3)] showsthat the F atom trans to an oxo ligand, as well as the OPMe 3 ligand trans to the other oxo ligand in thecis-dioxostructure A, are rapidly dissociated on the NMRtimescale, while the apical F atoms trans to each otherare not, which illustrates the trans-labilizing effect ofthe oxo ligands. Upon ageing new species are formed in the solutions, including WO 2F 2[OPMe 3 2,[WO 2F 3(CICH 2CN)],WO 2F 2(ClCH 2CN) 2, F- and OPMe 3 An equilibrium situation is reached after 4 days' heating at 80°C. The neutral WO 2F 2(OPMe 3) 2is then largely predominant. Material balance calculationsindicate that polynuclear species are also likely to be present.
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