A Ruthenium Hydrido Dinitrogen Core Conserved across Multielectron/Multiproton Changes to the Pincer Ligand Backbone
A Ruthenium Hydrido Dinitrogen Core Conserved across Multielectron/Multiproton Changes to the Pincer Ligand Backbone
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DOI：
10.1021/acs.inorgchem.7b02889
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发表时间：
2018-02-19
影响因子：
4.6
通讯作者：
Miller, Alexander J. M.
中科院分区：
文献类型：
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作者：
Bruch, Quinton J.;Lindley, Brian M.;Miller, Alexander J. M.
合成了一系列不同形式氧化态的钳形配体负载的钌（II）双氮配合物，并对其进行了表征。用还原剂或碱处理由钳形配体双（二叔丁基膦基乙基）胺（H-PNP）支撑的二氯化钌络合物产生新的五配位顺式二氮钌络合物，每个络合物含有不同形式的钳形配体。进一步的配体转换提供了访问的第一个同构组的复合物具有所有六种不同形式的钳配体。保守的顺式-β-二氮结构有利于表征配体的π-供体、π-受体和/或σ-供体性质，并评估以配体为中心的多电子/多质子变化对N-2活化的影响。晶体学研究，红外光谱，和N-15 NMR光谱表明，N-2在所有情况下仍然弱激活，提供洞察不同的钳形配体状态的供体性质。在催化（钳）钌物种的应用分支被认为是。
A series of ruthenium(II) hydrido dinitrogen complexes supported by pincer ligands in different formal oxidation states have been prepared and characterized. Treating a ruthenium dichloride complex supported by the pincer ligand bis(di-tert-butylphosphinoethyl)amine (H-PNP) with reductant or base generates new five-coordinate cis-hydridodinitrogen ruthenium complexes each containing different forms of the pincer ligand. Further ligand transformations provide access to the first isostructural set of complexes featuring all six different forms of the pincer ligand. The conserved cis-hydridodinitrogen structure facilitates characterization of the pi-donor, pi-acceptor, and/or sigma-donor properties of the ligands and assessment of the impact of ligand-centered multielectron/multiproton changes on N-2 activation. Crystallographic studies, infrared spectroscopy, and N-15 NMR spectroscopy indicate that N-2 remains weakly activated in all cases, providing insight into the donor properties of the different pincer ligand states. Ramifications on applications of (pincer)Ru species in catalysis are considered.