Coordination and bond activation in complexes of regioisomeric phenylpyridines with the nickel(II) chloride cation in the gas phase

Tsybizova A.; Rulí?ek L.; Schr?der D.; Rokob T.A.

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Coordination and bond activation in complexes of regioisomeric phenylpyridines with the nickel(II) chloride cation in the gas phase

机译：气相异构区域苯基吡啶与氯化镍（II）阳离子的配合物的配位和键活化

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Electrospray ionization of dilute solutions of phenylpyridines (phpy) in the presence of nickel(II) chloride leads to gaseous ions of the type [Ni(phpy)_m]~(2+) with m = 3-5 and [NiCl(phpy)_n]~+ with n = 1-3, which are characterized by various gas-phase experiments in combination with calculations using density functional theory. Of the regioisomeric phpy's, 2-phpy behaves drastically different compared to 3- and 4-phpy. Ion mobility mass spectrometry allows a differentiation of the gaseous ions and an elucidation of characteristic properties of the metal complexes. For 2-phpy, C-H bond activation in the [NiCl(phpy)_2]~+ complex is significant, whereas this route is almost suppressed for the corresponding complexes of 3- and 4-phpy and only occurs at elevated energies.

机译：在氯化镍（II）的存在下电喷雾离子化苯基吡啶（phpy）的稀溶液会产生[Ni（phpy）_m]〜（2+）类型的气态离子，其中m = 3-5和[NiCl（phpy） [n]〜+，n = 1-3，其特征是通过各种气相实验并结合使用密度泛函理论的计算来表征。在区域异构的phpy中，2-phpy的行为与3-phpy和4-phpy完全不同。离子迁移质谱可以区分气态离子并阐明金属络合物的特征。对于2-phpy，[NiCl（phpy）_2]〜+配合物中的C-H键激活非常重要，而对于3-phpy和4-phpy的相应配合物，该途径几乎被抑制，仅在能量升高时发生。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2013年第6期|共10页
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Tsybizova A.; Rulí?ek L.; Schr?der D.; Rokob T.A.;
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1. Coordination and bond activation in complexes of regioisomeric phenylpyridines with the nickel(II) chloride cation in the gas phase [J] . Tsybizova A., Rulí?ek L., Schr?der D., The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2013,第6期

机译：气相异构区域苯基吡啶与氯化镍（II）阳离子的配合物的配位和键活化
2. DFT study of olefin versus nitrogen bonding in the coordination of nitrogen-containing polar monomers to diimine and salicylaldiminato nickel(II) and palladium(II) complexes. Implications for copolymerization of olefins with nitrogen-containing polar [J] . Deubel DV., Ziegler T. Organometallics . 2002,第8期

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3. Nickel Complexes of a Pincer NN_2 Ligand: Multiple Carbon-Chloride Activation of CH_2CI_2 and CHCI_3 Leads to Selective Carbon-Carbon Bond Formation [J] . Zsolt Csok, Oleg Vechorkin, Seth B. Harkins, Journal of the American Chemical Society . 2008,第26期

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4. Chiral Counterion-Directed Cp*Rh(III)-Catalysis for Asymmetric Conjugate Addition of 2-Phenylpyridines via C-H Activation [C] . Shun Satake, Takumaru Kurihara, Keisuke Nishikawa 日本化学会春季年会講演予稿集 . 2018

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Coordination and bond activation in complexes of regioisomeric phenylpyridines with the nickel(II) chloride cation in the gas phase

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