Cowley Andrew R, Dilworth Jonathan R, Donnelly Paul S
Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, U.K.
Inorg Chem. 2003 Feb 24;42(4):929-31. doi: 10.1021/ic025995w.
A new method for the synthesis of low to intermediate oxidation state rhenium complexes containing a bifunctional ligand has been developed. Reaction of ReO(4) with substituted phenylhydrazines and triphenylphosphine in acetonitrile in the presence of HCl allows the isolation of [ReCl(2)(NNC(6)H(4)-4-R)(NCCH(3))(PPh(3))(2)] (where R = OCH(3), Cl, or CO(2)CH(3)). The substituted hydrazine acts as both a reductant and source of a monodentate diazenide ligand. The compounds have all been characterized in the solid state by X-ray crystallography and in the solution state by NMR, electrospray mass spectrometry, and HPLC. Cyclic voltammetry measurements show that the mono-diazenide complexes undergo a reversible oxidation.
已开发出一种合成含双功能配体的低至中等氧化态铼配合物的新方法。在HCl存在下,[ReO(4)]⁻与取代苯肼和三苯基膦在乙腈中反应,可分离得到[ReCl(2)(NNC(6)H(4)-4-R)(NCCH(3))(PPh(3))(2)](其中R = OCH(3)、Cl或CO(2)CH(3))。取代肼既作为还原剂又作为单齿重氮化物配体的来源。这些化合物均已通过X射线晶体学在固态下以及通过NMR、电喷雾质谱和HPLC在溶液状态下进行了表征。循环伏安法测量表明,单重氮化物配合物发生可逆氧化。