The side-on bound metal complex of diazene cis-[Fe(NH[double bond]NH)(dmpe)(2)] was synthesised by reaction of [Fe(dmpe)(2)Cl(2)] with hydrazine in the presence of potassium graphite and characterised by (15)N NMR spectroscopy and X-ray crystallography.

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The treatment of the hydrazine complex cis-[Fe(N(2)H(4))(dmpe)(2)](2+) with base afforded the diazene complex cis-[Fe(N(2)H(2))(dmpe)(2)]. This reaction is reversed by the treatment of the diazene complex with a mild acid, while treatment of the hydrazine complex with a mixture of KOBu(t) and Bu(t)Li afforded the dinitrogen complex [Fe(N(2))(dmpe)(2)].

Treatment of trans-[FeCl(2)(dmpe)(2)] with phenylhydrazine and 1 equiv of base afforded the side-on bound phenylhydrazido complex cis-[Fe(η(2)-NH(2)NPh)(dmpe)(2)](+). Further deprotonation of the phenylhydrazido complex afforded the side-on bound phenyldiazene complex cis-[Fe(η(2)-HN═NPh)(dmpe)(2)] as a mixture of diastereomers. Treatment of cis-[RuCl(2)(dmpe)(2)] with phenylhydrazine or methylhydrazine afforded the end-on bound phenylhydrazine or methylhydrazine complexes cis-[RuCl(η(1)-NH(2)NHR)(dmpe)(2)](+) (R = Ph, Me). Treatment of the substituted hydrazine complexes with base afforded the side-on bound phenylhydrazido complex cis-[Ru(η(2)-NH(2)NPh)(dmpe)(2)](+) as well as the phenyldiazene and methyldiazene complexes cis-[Ru(η(2)-HN═NR)(dmpe)(2)] (R = Ph, Me). cis-[RuCl(η(1)-NH(2)NHR)(dmpe)(2)](+) (R = Ph, Me), cis-[M(η(2)-NH(2)NPh)(dmpe)(2)](+) (M = Fe, Ru) and cis-[Ru(η(2)-HN═NPh)(dmpe)(2)] were characterized structurally by X-ray crystallography. cis-[Ru(η(2)-HN═NPh)(dmpe)(2)] is the first side-on bound phenyldiazene complex to be structurally characterized. In the structure of cis-[Ru(η(2)-HN═NPh)(dmpe)(2)], the geometry of the coordinated diazene fragment is significantly nonplanar (CNNH angle 137°) suggesting that the complex is probably better described as a Ru(II) metallodiaziridine than a Ru(0) diazene π-complex.

A reinvestigation of the treatment of [Fe(N2)(PP)2] (PP = depe, dmpe) with acid revealed no ammonium formation. Instead, rapid protonation at the metal center to give hydride complexes was observed. Treatment of [Fe(N2)(dmpe)2] with methylating agents such as methyl triflate or methyl tosylate resulted in methylation of the metal center to afford [FeMe(N2)(dmpe)2](+). Treatment of [Fe(N2)(dmpe)2] with trimethylsilyl triflate, however, resulted in reaction at dinitrogen affording NH4(+) on subsequent treatment with acid. The side-on bound hydrazine complex [Fe(N2H4)(dmpe)2](2+) and bis(ammonia) complex [Fe(NH3)2(dmpe)2](2+) were identified by (15)N NMR spectroscopy as other species formed in the reaction mixture.