Reaction of ruthenium(II) and osmium(II) hydrides with anhydrous HF

Abstract

The reactions of anhydrous HF with the ruthenium(II) and osmium(II) hydride complexes [MH₂(CO)_x(PPh₃)_y] (M = Ru or Os; x = y = 2; x = 1, y = 3) have been studied. For [OC-6-13][MH₂(CO)₂(PPh₃)₂], elimination of dihydrogen affords the previously described [OC-6-13][MF₂(CO)₂(PPh₃)₂]. For [OC-6-13][MH₂(CO)(PPh₃)₃], elimination of dihydrogen is accompanied by loss of one phosphine ligand and aggregation to give the novel, triply fluoride-bridged, dinuclear, [M₂(µ-F)₃(CO)₂(PPh₃)₄][HF₂]; anion exchange with Na[BPh₄] afford air-stable products. These complexes have been characterised by mass spectrometry, NMR, IR and metal-edge extended X-ray absorption fine structure spectroscopies which confirm their dinuclear structures.