Base-Induced Dehydrogenation of Ruthenium Hydrazine Complexes

Treatment of [RuCl­(PP3iPr)]+Cl– (PP3iPr = P­(CH2CH2PiPr2)3) with hydrazine, phenylhydrazine, and methylhydrazine afforded side-on bound hydrazine complexes [RuCl­(η2-H2N-NH2)­(η3-PP3iPr)]+, [RuCl­(η2-H2N-NHPh)­(η3-PP3iPr)]+, and [RuCl­(η2-H2N-NHMe)­(η3-PP3iPr)]+. The analogous reactions of [RuCl2(PP3Ph)] (PP3Ph = P­(CH2CH2PPh2)3) with hydrazine, phenylhydrazine, and methylhydrazine afforded end-on bound hydrazine complexes [RuCl­(η1-H2N-NH2)­(PP3Ph)]+, [RuCl­(η1-H2N-NHPh)­(PP3Ph)]+, and [RuCl­(η1-H2N-NHMe)­(PP3Ph)]+. Treatment of parent hydrazine complex [RuCl­(N2H4)­(PP3 iPr)]+ with strong base afforded the dinitrogen and dihydride complexes [Ru­(N2)­(PP3 iPr)] and [RuH2(PP3iPr)]. Treatment of phenylhydrazine complex [RuCl­(NH2NHPh)­(PP3iPr)]+ with strong base afforded the hydrido ruthenaindazole complex [RuH­(η2-NHNC6H4)­(η3-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(N2)­(PP3Ph)].