Ruthenium complexes of substituted hydrazine: New solution- and solid-state binding modes

Serin L. Dabb; Barbara A. Messerle; Gottfried Otting; Jörg Wagler; Anthony Willis

doi:10.1002/chem.200801061

Ruthenium complexes of substituted hydrazine: New solution- and solid-state binding modes

Serin L. Dabb, Barbara A. Messerle, Gottfried Otting, Jörg Wagler, Anthony Willis

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	10058-10065
Number of pages	8
Journal	Chemistry - A European Journal
Volume	14
Issue number	32
DOIs	https://doi.org/10.1002/chem.200801061
Publication status	Published - 10 Nov 2008

Access to Document

10.1002/chem.200801061

Cite this

@article{b70f3f7f155b47b6bb0d508781976d14,

title = "Ruthenium complexes of substituted hydrazine: New solution- and solid-state binding modes",

abstract = "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.",

keywords = "Coordination modes, Hydrazine, NMR spectroscopy, Ruthenium, X-ray diffraction",

author = "Dabb, {Serin L.} and Messerle, {Barbara A.} and Gottfried Otting and J{\"o}rg Wagler and Anthony Willis",

year = "2008",

month = nov,

day = "10",

doi = "10.1002/chem.200801061",

language = "English",

volume = "14",

pages = "10058--10065",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag GmbH",

number = "32",

}

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.

KW - Coordination modes

KW - Hydrazine

KW - NMR spectroscopy

KW - Ruthenium

KW - X-ray diffraction

UR - http://www.scopus.com/inward/record.url?scp=55449091168&partnerID=8YFLogxK

U2 - 10.1002/chem.200801061

DO - 10.1002/chem.200801061

M3 - Article

SN - 0947-6539

VL - 14

SP - 10058

EP - 10065

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 32

ER -

Ruthenium complexes of substituted hydrazine: New solution- and solid-state binding modes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this