Metal-Metal Quadruple Bonds (M = Mo or W) Supported by 4-[2-(4-Pyridinyl)ethenyl] Benzoates and their Complexes with Tris(pentafluorophenyl)boron.
Metal-Metal Quadruple Bonds (M = Mo or W) Supported by 4-[2-(4-Pyridinyl)ethenyl] Benzoates and their Complexes with Tris(pentafluorophenyl)boron.
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由 4-[2-(4-吡啶基)乙烯基]苯甲酸酯及其与三(五氟苯基)硼的配合物支持的金属-金属四键（M = Mo 或 W）。
DOI：
10.1021/acs.inorgchem.5b01520
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发表时间：
2015
影响因子：
4.6
通讯作者：
Ziehm,ChristopherJ
中科院分区：
文献类型：
--
作者：
Chisholm,MalcolmH;Ziehm,ChristopherJ
From the reactions between M2(TiPB)4and two equivalents of the acids LH, the compoundstrans-M2(TiPB)2L2were isolated where M = Mo, compoundI, and M = W,II, TiPB = 2,4,6-triisopropylbenzoate, and LH = 4-[2-(4-Pyridinyl)ethenyl]benzoic acid. In related reactions when tris(pentafluorophenyl)boron, A, was added, the Lewis acid–Lewis base complexes Mo2(TiPB)2(LA)2,IB, and W2(TiPB)2(LA)2,IIB, were isolated. CompoundsIandIBare red and purple, respectively, whileIIandIIBare green. The new compounds have been characterized by1H NMR, UV–visible-NIR absorption spectroscopy, and electrochemical studies, which are tied together with density functional theory, DFT, and time-dependent DFT calculations. Chemical reduction ofIBandIIByields anions where the single electron occupies a ligand-based orbital as indicated by EPR spectroscopy. The LUMO and LUMO+1 are ligand-based, and are close in energy, and upon reduction, no IVCT is observed.
