Investigation of phosphine donor properties to vanadium(V) nitrides
Investigation of phosphine donor properties to vanadium(V) nitrides
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DOI：
10.1016/j.rechem.2022.100344
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发表时间：
2022-01-01
影响因子：
2.3
通讯作者：
Odom, Aaron L.
中科院分区：
文献类型：
--
作者：
Mo, Linqing;Barr, Hannah, I;Odom, Aaron L.
多年来，通过表征配体的给体和空间性质的方法极大地帮助了催化剂优化。在这里，我们研究了钒模型系统NV（NH 2）（2）L，以确定与酰胺旋转相关的光致势垒是否在一定范围内，该范围将使其成为用于通过实验确定L的供体能力的合成目标，例如，通过H-1 NMR中酰胺质子的自旋饱和转移。除了确定旋转的障碍应该服从这种方法，我们研究了各种膦供体性质如何影响d（0）金属的酰胺旋转，并将其与后过渡金属系统进行了对比。计算表明，一些PX 3配体的功能，如孤对的X取代基，可能会导致增加在高氧化态系统中，它们是吸电子在低氧化态系统。这种电子差异的原因进行了研究，使用自然共振理论。
Catalyst optimization has been greatly aided over the years by methods of characterizing donor and steric properties of ligands. Here, we investigated a vanadium model system, NV(NH2)(2)L, to determine if the enthalpic barriers associated with amide rotation are in a range that would make this a synthetic target for determining the donor ability of L experimentally, e.g., by spin saturation transfer of the amide protons in the H-1 NMR. In addition to determining that the barriers to rotation should be amenable to this method, we investigated how various phosphine donor properties affected amide rotation for the d(0) metal and contrasted this with a late transition metal system. The calculations suggest that some PX3 ligand features, such as lone pairs on the X substituent, may lead to increases in the high oxidation state system where they are electron withdrawing in the low oxidation state systems. The cause of this electronic difference was investigated using Natural Resonance Theory.