title: Ruthenium complexes of substituted hydrazine: new solution- and solid-state binding modes.
abstract: The methylhydrazine complex [Ru(NH(2)NHMe)(PyP)(2)]Cl(BPh(4)) (PyP=1-[2-(diphenylphosphino)ethyl]pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(BPh(4))(2). The methylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (eta(2)-) when the complex is in the solid state and end-on (eta(1)-) when the complex is in solution. The solid-state structure of [Ru(PyP)(2)(NH(2)NHMe)]Cl(BPh(4)) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with (15)N at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH(2) group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP)(2)(eta(1)-NH(2)NRR')]OSO(2)CF(3) (in which R=H, R'=Ph, R=R'=Me and NRR'=NC(5)H(10)) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(OSO(2)CF(3))(2) in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.
authors.affiliation: School of Chemistry, The University of New South Wales, Sydney, NSW, Australia.
authors.forename: Serin L
authors.initials: SL
authors.lastname: Dabb
authors.forename: Barbara A
authors.initials: BA
authors.lastname: Messerle
authors.forename: Gottfried
authors.initials: G
authors.lastname: Otting
authors.forename: Jörg
authors.initials: J
authors.lastname: Wagler
authors.forename: Anthony
authors.initials: A
authors.lastname: Willis
mesh_terms: D018360:Crystallography, X-Ray; D006834:Hydrazines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry
chemical_list: D006834:Hydrazines; D009942:Organometallic Compounds; D012996:Solutions; C029424:hydrazine; D012428:Ruthenium