| Summary: | A range of low-valent osmium and ruthenium fluoride complexes of the type [OC-6-13][MF2(CO)2(L)2], L = tertiary phosphine, arsine or nitrogen donor ligand, have been prepared and fully charcacterized by a combination of mass spectrometry, infrared spectroscopy, 19F, and 31P{1H} (where appropriate) NMR spectroscopies. The compounds [OC-6-13][RuF2(CO)2(PEtPh2)2], [OC-6-13][OsF2(CO)2(PPh3)2] and [OC-6-13][OsF2(CO)2(PCy3)2] have been further characterized by single crystal X-ray diffraction, the last two representing the first crystallographic analyses of osmium(II) fluoride complexes. The photolysis and thermolysis of [RuF2(CO)2(PMe3)2] have been shown to give several novel complexes including [RuF2(CO)(PMe3)3] which is a rare example of fluoride ligand trans to tertiary phosphine. Reactions of some of the prepared complexes with a variety of reagents have given rise to a number of low-valent cationic fluoride complexes as well as novel alkyl and carboxylato species. Fluorination of the ruthenium carbonyl [Ru3(CO)12] with elemental fluorine has given rise to a plethora of products which have been characterized by 19F NMR spectroscopy. Hydride complexes of the type [MH2(CO)2(PPh3)2] and [MH2(CO)(PPh3)3] have been allowed to react with anhydrous hydrofluoric acid and have been shown to give the complexes [MF2(CO)2(PPh3)2] and [M2(?-F)3(CO)2(PPh3)4]+ respectively, where M = osmium or ruthenium. X-ray crystal structure determinations for the complexes [OC-6- 75][Os(CH3)2(CO)2(PPh3)2], [OC-6-13][Os(CH3)2(CO)2(PCy3)2], [OC-6-13]-[Ru(OC(O)CF3)2(CO)2(PCy3)2] and [Ru(?2-CO3-OO)(CO)(PMe3)3] are described.
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