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A molecular orbital rationalization of ligand effects in N-2 activation

机译:N-2活化中配体效应的分子轨道合理化

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Molecular orbital theory has been used to study a series of [(mu-N-2){ML3}(2)] complexes as models for dinitrogen activation, with M=Mo, Th, W, Re and L = NH2, PH2, AsH2, SbH2 and N(BH2)(2). The main aims of this study have been to provide a thorough electronic analysis of the complexes and to extend previous work involving molecular orbital analyses. Molecular orbital diagrams have been used to rationalize why for L=NH2 ligand rotation is important for the singlet state but not the triplet, to confirm the effect of ligand pi donation, and to rationalize the importance of the metal d-electron configuration. The outcomes of this study will assist with a more in-depth understanding of the electronic basis for N-2 activation and allow clearer predictions to be made about the structure and multiplicity of systems involved in transition-metal catalysis.
机译:分子轨道理论已被用于研究一系列[(mu-N-2){ML3}(2)]配合物作为二氮激活的模型,其中M = Mo,Th,W,Re和L = NH2,PH2, AsH2,SbH2和N(BH2)(2)。这项研究的主要目的是提供对配合物的全面电子分析,并扩展涉及分子轨道分析的先前工作。已经使用分子轨道图合理化了为什么L = NH2配体旋转对于单重态而不是三重态重要的原因,以确认配体pi的作用,以及合理化金属d电子构型的重要性。这项研究的结果将有助于更深入地了解N-2活化的电子基础,并可以对涉及过渡金属催化的系统的结构和多样性做出更清晰的预测。

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