Abstract
The complexes [OsH2Cl2(PR3)3](PR3= PMePh2, PEt2Ph, PEtPh2, or PPhPrn2) have been prepared by the amalgamated-zinc reduction, under dihydrogen, of mer-[OsCl3(PR3)3]. The compounds mer-[OsXY(L)(PR3)3](X = H or D; Y = Cl or Br; L = CO or N2; PR3= PMe2Ph or PEt2Ph) result from mer-[OsY2(L)(PR3)3] by sodium borohydride or lithium aluminium deuteride reduction. The 1H n.m.r. and i.r. spectra of these compounds are recorded and used to assign the configuration of the monohydrido-complexes. The dihydro-complexes react with carbon monoxide, tertiary phosphines and carbon tetrachloride–dichlorine with loss of dihydrogen. With one mole of anhydrous HCl the dihydrido-complexes give the unstable compounds [OsHCl3(PR3)3](PR3= PMePh2 or PEt2Ph) which readily give fac-[OsCl3(PR3)3] and ½H2 when heated. Dinitrogen does not react with [OsH2Cl2(PMePh2)3]. The compound mer-[OsHCl(N2)(PEt2Ph)3] reacts with anhydrous HCl in toluene to give [OsCl2(N2)(PEt2Ph)3] and dihydrogen.
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