TY - JOUR
T1 - Ruthenium complexes of substituted hydrazine
T2 - New solution- and solid-state binding modes
AU - Dabb, Serin L.
AU - Messerle, Barbara A.
AU - Otting, Gottfried
AU - Wagler, Jörg
AU - Willis, Anthony
PY - 2008/11/10
Y1 - 2008/11/10
N2 - The methylhydrazine complex [Ru(NH2NHMe)(PyP) 2]Cl(BPh4) (PyP = 1-[2-(diphenylphosphino)ethyl]pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(μ-Cl)(PyP)2]2(BPh4)2. The methylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (η2-) when the complex is in the solid state and end-on (η1-) when the complex is in solution. The solid-state structure of [Ru(PyP)2-(NH2NHMe)]Cl(BPh4) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with 15N at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH2 group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP) 2(η1-NH2NRR′)]OSO2CF 3 (in which R = H, R′ = Ph, R = R′ = Me and NRR′ = NC5H10) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(μ-Cl)(PyP)2] 2-(OSO2CF3)2 in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.
AB - The methylhydrazine complex [Ru(NH2NHMe)(PyP) 2]Cl(BPh4) (PyP = 1-[2-(diphenylphosphino)ethyl]pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(μ-Cl)(PyP)2]2(BPh4)2. The methylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (η2-) when the complex is in the solid state and end-on (η1-) when the complex is in solution. The solid-state structure of [Ru(PyP)2-(NH2NHMe)]Cl(BPh4) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with 15N at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH2 group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP) 2(η1-NH2NRR′)]OSO2CF 3 (in which R = H, R′ = Ph, R = R′ = Me and NRR′ = NC5H10) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(μ-Cl)(PyP)2] 2-(OSO2CF3)2 in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.
UR - http://www.scopus.com/inward/record.url?scp=55449091168&partnerID=8YFLogxK
U2 - 10.1002/chem.200801061
DO - 10.1002/chem.200801061
M3 - Article
C2 - 18803189
AN - SCOPUS:55449091168
SN - 0947-6539
VL - 14
SP - 10058
EP - 10065
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 32
ER -