Base-induced dehydrogenation of ruthenium hydrazine complexes.

Treatment of [RuCl(PP(3)(iPr))](+)Cl(-) (PP(3)(iPr) = P(CH(2)CH(2)P(i)Pr(2))(3)) with hydrazine, phenylhydrazine, and methylhydrazine afforded side-on bound hydrazine complexes [RuCl(η(2)-H(2)N-NH(2))(η(3)-PP(3)(iPr))](+), [RuCl(η(2)-H(2)N-NHPh)(η(3)-PP(3)(iPr))](+), and [RuCl(η(2)-H(2)N-NHMe)(η(3)-PP(3)(iPr))](+). The analogous reactions of [RuCl(2)(PP(3)(Ph))] (PP(3)(Ph) = P(CH(2)CH(2)PPh(2))(3)) with hydrazine, phenylhydrazine, and methylhydrazine afforded end-on bound hydrazine complexes [RuCl(η(1)-H(2)N-NH(2))(PP(3)(Ph))](+), [RuCl(η(1)-H(2)N-NHPh)(PP(3)(Ph))](+), and [RuCl(η(1)-H(2)N-NHMe)(PP(3)(Ph))](+). Treatment of parent hydrazine complex [RuCl(N(2)H(4))(PP(3)(iPr))](+) with strong base afforded the dinitrogen and dihydride complexes [Ru(N(2))(PP(3)(iPr))] and [RuH(2)(PP(3)(iPr))]. Treatment of phenylhydrazine complex [RuCl(NH(2)NHPh)(PP(3)(iPr))](+) with strong base afforded the hydrido ruthenaindazole complex [RuH(η(2)-NH═NC(6)H(4))(η(3)-PP(3)(iPr))] while similar treatment of methylhydrazine complex [RuCl(NH(2)NHMe)(PP(3)(iPr))](+) afforded the hydrido methylenehydrazide complex [RuH(NHN═CH(2))(PP(3)(iPr))]. Treatment of the hydrazine complexes [RuCl(NH(2)NHR)(PP(3)(Ph))](+) (R = H, Ph, Me) with strong base afforded the dinitrogen complex [Ru(N(2))(PP(3)(Ph))].