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Nitric oxide (NO) reactivity studies on mononuclear iron(ii) complexes supported by a tetradentate Schiff base ligand

机译:一氧化氮(NO)反应性研究由四晶席夫碱配体负载的单核铁(II)复合物

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Mononuclear high-spin [Fe ~(II) ( Gimpy )(Cl) _(2) ], ( 1 ) and low-spin [Fe ~(II) ( Gimpy )(CN) _(2) ]·3H _(2) O, ( 2 ·3H _(2) O) complexes, where; Gimpy : (1,2-bis(2-phenyl-2-(pyridin-2-yl)hydrazono)ethane), were synthesized and characterized by various analytical and spectral techniques. The NO reactivity of complex 2 ·3H _(2) O via acidified nitrite solution gave rise to a mixture of two different complexes; a ligand nitrated unsymmetrical complex [Fe( Gimpy -NO _(2) )(CN) _(2) ]·CH _(2) Cl _(2) , ( 3 ·CH _(2) Cl _(2) ) via electrophilic route as well as nitrosylation at the metal centre, formation of unstable complex [Fe( Gimpy )(NO)(CN)] ~(2+) , ( 4 ). Formation of unstable complex 4 was monitored via visual colour change from purple to brownish-red and evidence of this complex has been established by means of in situ IR, ESI-MS and UV-visible spectral studies. In addition, the structures of complexes 2 ·3H _(2) O and 3 ·CH _(2) Cl _(2) have been established unambiguously through single crystal X-ray diffraction analysis. Interestingly, after nitration of imine proton twisting of one phenyl ring (near to –NO _(2) group) in complex 3 was obtained, leading to an unsymmetrical complex 3 (nitration of one imine proton only is supported by theoretical studies), possibly due to steric hindrance of –NO _(2) group and results of electrochemical studies of all complexes ( 1–3 ) were also examined.
机译:单核高旋转[Fe〜(II)(Gimpy)(Cl)_(2)],(1)和低旋转[Fe〜(II)(GIMPY)(CN)_(2)]·3H _( 2)O,(2·3H _(2)o)复合物,在哪里; Gimpy:(1,2-双(2-苯基-2-(吡啶-2-基)氢肼)乙烷),通过各种分析和光谱技术合成并表征。通过酸化亚硝酸盐溶液的络合物2·3H _(2)O的无反应性产生了两种不同络合物的混合物;一个配体硝化的非对称复合物[Fe(Gimpy -nO _(2))(CN)_(2)]·CH _(2)CL _(2),(3·CH _(2)CL _(2))通过亲电子途径以及金属中心的亚硝基化,形成不稳定的复合物[Fe(GIMPY)(NO)(CN)]〜(2+),(4)。通过从紫色的视觉颜色变化监测不稳定的复合物4的形成,并通过原位IR,ESI-MS和UV可见光光谱研究建立了这种复合物的褐红色的证据。另外,通过单晶X射线衍射分析明确地建立了复合物2·3H _(2)o和3·CH_(2)CL _(2)的结构。有趣的是,在得到一个苯环的亚胺质子捻度(靠近-NO _(2)组)中的亚胺质子捻度的硝化后,导致不对称复合物3(仅通过理论研究支持的一个亚胺质子的硝化硝化),可能由于-NO_(2)组的空间阻碍,还检查了所有复合物的电化学研究结果(1-3)。

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