Inorganic Chemistry, Vol.52, No.3, 1570-1583, 2013
Base-Induced Dehydrogenation of Ruthenium Hydrazine Complexes
Treatment of [RuCl(PP3iPr)]Cl-+(-) (PP3iPr = P((CH2CH2PPr2)-Pr-i)(3)) with hydrazine, phenylhydrazine, and methylhydrazine afforded side-on bound hydrazine complexes [RuCl(eta(2)-H2N-NH2)(eta(3)-PP3iPr)](+), [RuCl(eta(2)-H2N-NHPh)(eta(3-PP3iPr))] and [RuCl(eta(2)-H2N-NHMe)(eta(3)-PP3iPr)](+). The analogous reactions of [RuCl2( pp(3)(Ph))] (pp(3)(ph) = p- (CH2CH2PPh2)3) with hydrazine, phenylhydrazine, and methylhydrazine afforded end-on bound hydrazine complexes [RuCl(eta(1)-H2N-NH2)(PP3Ph)](+), [RuCl(eta(1)-H2N-NHPh)-(PP3Ph)](+), and [RuCl(eta(1)-H2N-NHMe)(PP3Ph)](+). Treatment of parent hydrazine complex [RuCl(N2H4)(PP3iPr)](+) with strong base afforded the dinitrogen and dihydride complexes [Ru(N-2)(PP3iPr)] and [RuH2(PP3iPr)]. Treatment of phenylhydrazine complex [RuCl(NH2NHPh)(PP3iPr)](+) with strong base afforded the hydrido nithenaindazole complex [RuH(eta(2)-NH==NC6H4)(eta(3)-PP3iPr)] while similar treatment of methylhydrazine complex [RuCl(NH2NHMe)(PP3iPr)](+) afforded the hydrido methylenehydrazide complex [RuH(NHN=CH2)(PP3iPr)]. Treatment of the hydrazine complexes [RuCl(NH2NHR)(PP3Ph)](+) (R = H, Ph, Me) with strong base afforded the dinitrogen complex [Ru(N-2)(PP3Ph)].