Fluorophosphine complexes of ruthenium and osmium. Part 2. Reactions of dihydrido-complexes with protic species
Abstract
The complexes [MH2(PF3)2(PPh3)2](M = Ru or Os) react with HCl gas to give [MCl2(PF3)2(PPh3)2] or the intermediate [MCI(H)(PF3)2(PPh3)2](only for M = Os) depending on the conditions. The complex [RuH2(PF3)2-(PPh3)2] and HBr gives [RuBr2(PF3)2(PPh3)2]: [RuCl(H)(PF3)2(PPh3)2] is obtained by treatment of [RuH(PF3)2-(PPh3)2][BF4]{formed by HBF4 addition to [RuH2(PF3)2(PPh3)2]} with [NEt4]Cl or by the reaction between [Ru(PF3)3(PPh3)2] and ButCl. The complexes [RuH2(L)(PPh3)3][L = PF3 or PF2(NMe2)] react with trifluoroacetic acid to form [Ru(O2CCF3)2L(PPh3)2], while [RuH2L2(PPh3)2] give [RuH(O2CCF3)(PF3)2(PPh3)2] and [Ru(O2CCF3)2{PF2(NMe2)}2(PPh3)] respectively; [RuH2(PF3)2(PPh3)2] or [RuH(O2CCF3)(PF3)2(PPh3)2] react with CF3CO2H under more vigorous conditions to yield a complex containing the PF2(O2CCF3) ligand. Fluorine-19 and 31P n m r. spectra of all these complexes enable their stereochemistry to be established, and in the trifluoro-acetate-derivativ es provide evidence for an intramolecular exchange process between uni-and bi-dentate trifluoro acetate ligands.
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