Ruthenium complexes of substituted hydrazine: new solution- and solid-state binding modes |
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Authors: | Dabb Serin L Messerle Barbara A Otting Gottfried Wagler Jörg Willis Anthony |
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Institution: | School of Chemistry, The University of New South Wales, Sydney, NSW, Australia. |
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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. |
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Keywords: | coordination modes hydrazine NMR spectroscopy ruthenium X‐ray diffraction |
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