Manzur Carolina, Millán Lorena, Fuentealba Mauricio, Hamon Jean-René, Toupet Loïc, Kahlal Samia, Saillard Jean-Yves, Carrillo David
Laboratorio de Química Inorgánica, Instituto de Química, Pontificia Universidad Católica de Valparaíso, Avenida Brasil 2950, Valparaíso, Chile.
Inorg Chem. 2007 Feb 19;46(4):1123-34. doi: 10.1021/ic0613098.
Representative members of a new family of covalently bonded charge-transfer molecular hybrids, of general formula [(eta5-C5H5)Fe(mu,eta6:eta1-p-RC6H4NN)Mo(eta2-S2CNEt2)3] +PF6- (R: H, 5+PF6-; Me, 6+PF6-; MeO, 7+PF6-) and [(eta5-C5Me5)Fe(mu,eta6:eta1-C6H5NN)Mo(eta2-S2CNEt2)3]+PF6-, 8+PF6-, have been synthesized by reaction of the corresponding mixed-sandwich organometallic hydrazines [(eta5-C5H5)Fe(eta6-p-RC6H4NHNH2)]+PF6- (R: H, 1+PF6-; Me, 2+PF6-; MeO, 3+PF6-) and [(eta5-C5Me5)Fe(eta6-C6H5NHNH2)]+PF6-, 4+PF6-, with cis-dioxomolybdenum(VI) bis(diethyldithiocarbamato) complex, [MoO2(S2CNEt2)2], in the presence of sodium diethyldithiocarbamato trihydrate, NaSC(=S)NEt2.3H2O, in refluxing methanol. These iron-molybdenum complexes consist of organometallic and inorganic fragments linked each other through a pi-conjugated aryldiazenido bridge coordinated in eta6 and eta1 modes, respectively. These complexes were fully characterized by FT-IR, UV-visible, and 1H NMR spectroscopies and, in the case of complex 7+PF6-, by single-crystal X-ray diffraction analysis. Likewise, the electrochemical and solvatochromic properties were studied by cyclic voltammetry and UV-visible spectroscopy, respectively. The electronic spectra of these hybrids show an absorption band in the 462-489 and 447-470 nm regions in CH2Cl2 and DMSO, respectively, indicating the existence of a charge-transfer transition from the inorganic donor to the organometallic acceptor fragments through the aryldiazenido spacer. A rationalization of the properties of 5+PF6--8+PF6- is provided through DFT calculations on a simplified model of 7+PF6-. Besides the heterodinuclear complexes 5+PF6--8+PF6-, the mononuclear molybdenum diazenido derivatives, [(eta1-p-RC6H4NN)Mo(eta2-S2CNEt2)3] (R: H, 9; Me, 10; MeO, 11), resulting from the decoordination of the [(eta5-C5H5)Fe]+ moiety of complexes 5+PF6--7+PF6-, were also isolated. For comparative studies, the crystalline and molecular structure of complex 10.Et2O was also determined by X-ray diffraction analysis and its electronic structure computed.
一类新的共价键合电荷转移分子杂化物的代表性成员，其通式为[(η⁵-C₅H₅)Fe(μ,η⁶:η¹-p-RC₆H₄NN)Mo(η²-S₂CNEt₂)₃]⁺PF₆⁻（R：H，5⁺PF₆⁻；Me，6⁺PF₆⁻；MeO，7⁺PF₆⁻）和[(η⁵-C₅Me₅)Fe(μ,η⁶:η¹-C₆H₅NN)Mo(η²-S₂CNEt₂)₃]⁺PF₆⁻，8⁺PF₆⁻，是通过相应的混合夹心有机金属肼[(η⁵-C₅H₅)Fe(η⁶-p-RC₆H₄NHNH₂)]⁺PF₆⁻（R：H，1⁺PF₆⁻；Me，2⁺PF₆⁻；MeO，3⁺PF₆⁻）和[(η⁵-C₅Me₅)Fe(η⁶-C₆H₅NHNH₂)]⁺PF₆⁻，4⁺PF₆⁻，与顺式二氧代钼(VI)双(二乙基二硫代氨基甲酸酯)配合物[MoO₂(S₂CNEt₂)₂]，在三水合二乙基二硫代氨基甲酸钠NaSC(=S)NEt₂·3H₂O存在下，于回流甲醇中反应合成的。这些铁-钼配合物由有机金属和无机片段组成，它们通过分别以η⁶和η¹模式配位的π共轭芳基二氮烯桥相互连接。这些配合物通过傅里叶变换红外光谱、紫外-可见光谱和¹H核磁共振光谱进行了全面表征，对于配合物7⁺PF₆⁻，还通过单晶X射线衍射分析进行了表征。同样，分别通过循环伏安法和紫外-可见光谱研究了其电化学和溶剂化显色性质。这些杂化物的电子光谱在CH₂Cl₂和DMSO中分别在462 - 489和447 - 470 nm区域显示出一个吸收带，表明存在通过芳基二氮烯间隔基从无机供体到有机金属受体片段的电荷转移跃迁。通过对7⁺PF₆⁻的简化模型进行密度泛函理论计算，对5⁺PF₆⁻ - 8⁺PF₆⁻的性质进行了合理化解释。除了异双核配合物5⁺PF₆⁻ - 8⁺PF₆⁻外，还分离出了由配合物5⁺PF₆⁻ - 7⁺PF₆⁻的[(η⁵-C₅H₅)Fe]⁺部分解配位产生的单核钼二氮烯衍生物[(η¹-p-RC₆H₄NN)Mo(η²-S₂CNEt₂)₃]（R：H，9；Me，10；MeO，11）。为了进行比较研究，还通过X射线衍射分析确定了配合物10·Et₂O的晶体和分子结构，并计算了其电子结构。
