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Nitrato complexes of the platinum group metals have been prepared by treating selected hydridic or zero oxidation state precursors with nitric acid, neat or in organic media. Products obtained in this manner include [M(NO,),(CO)(PPh,),], [.M(NOJ2(CO)2(PPh3),1 (M = Ru or Os), [M’(NO,),(PPh,),], and [M’(NO,),(NO)(PPh,),] (M’ = Rh or Ir). The species [M(N03),(CO)(PPh,)2] undergo carbonylation to yield the dicarbonyls [M(N0,)2(CO)2(PPh3)2] and alcoholysis followed by P-elimination to form the hydrides [MH(NO,)(CO)(PPh,),]. The latter products are readily carbonylated to afford the species [MH(NO,)(CO),(PPh,),]. The new complexes have been characterized and their stereochemistry has been assigned by reference to spectroscopic data. The complex “Rh(N03)(NO)2(0PPh3)2” has been reformulated as [Rh(N03)2(NO)(PPh,)2]. However, one product obtained on treating [RuH,(CO)(PPh,),] with nitric acid has been tentatively identified as a triphenylphosphine oxide derivative [Ru(N0,),(NO)(OPPh3)(PPh,)]. The ability of [RU(NO,)~(CO)(PP~,)~] to catalyze the dehydrogenation of primary and secondary alcohols is noted.