title: Side-on bound complexes of phenyl- and methyl-diazene.
abstract: 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.
authors.affiliation: School of Chemistry, University of New South Wales, NSW 2052, Australia. l.field@unsw.edu.au
authors.forename: Leslie D
authors.initials: LD
authors.lastname: Field
authors.forename: Hsiu L
authors.initials: HL
authors.lastname: Li
authors.forename: Scott J
authors.initials: SJ
authors.lastname: Dalgarno
authors.forename: Ruaraidh D
authors.initials: RD
authors.lastname: McIntosh
mesh_terms: D018360:Crystallography, X-Ray; D007094:Imides / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular
chemical_list: D007094:Imides; D007097:Imines; C038868:methyl diazene; C011981:phenyldiazene