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[摘要]：The methylhydrazine complex [Ru(NH2NHMe)(PyP)2]Cl(BPh4) (PyP = 1-[2-(diphenylphosphino)ethyl]pyrazole 5) was synthesized by addn. of methylhydrazine to the bimetallic complex [Ru(m-Cl)(PyP)2]2(BPh4)2 (6). The methylhydrazine ligand of the Ru complex has two different binding modes: side-on (h2-) when the complex is in the solid state 5a and end-on (h1-) when the complex is in soln. 5b. The solid-state structure of [Ru(PyP)2(NH2NHMe)]Cl(BPh4) was detd. by x-ray crystallog. 2D NMR spectroscopic expts. with 15N at natural abundance confirmed that in soln. the methylhydrazine is bound to the metal center by only the -NH2 group and the Ru complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP)2(h1-NH2NRR')]OSO2CF3 (in which R = H , R' = Ph 10 , R = R' = Me 11 and NRR' = piperidine 12) were formed in situ by the addn. of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, resp., to a soln. of the bimetallic complex [Ru(m-Cl)(PyP)2]2(OSO2CF3)2 (7) in CH2Cl2. These substituted hydrazine complexes of Ru exist in an equil. mixt. with the bimetallic starting material. |
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