Huang Minxue, Corbin Joshua R, Dolan Nicholas S, Fry Charles G, Vinokur Anastasiya I, Guzei Ilia A, Schomaker Jennifer M
Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
Inorg Chem. 2017 Jun 5;56(11):6725-6733. doi: 10.1021/acs.inorgchem.7b00838. Epub 2017 May 16.
An array of silver complexes supported by nitrogen-donor ligands catalyze the transformation of C═C and C-H bonds to valuable C-N bonds via nitrene transfer. The ability to achieve high chemoselectivity and site selectivity in an amination event requires an understanding of both the solid- and solution-state behavior of these catalysts. X-ray structural characterizations were helpful in determining ligand features that promote the formation of monomeric versus dimeric complexes. Variable-temperature H and DOSY NMR experiments were especially useful for understanding how the ligand identity influences the nuclearity, coordination number, and fluxional behavior of silver(I) complexes in solution. These insights are valuable for developing improved ligand designs.
一系列由含氮配体支撑的银配合物通过氮烯转移催化碳碳双键和碳氢键转化为有价值的碳氮键。在胺化反应中实现高化学选择性和位点选择性的能力需要了解这些催化剂的固态和溶液态行为。X射线结构表征有助于确定促进单体与二聚体配合物形成的配体特征。变温氢谱和扩散排序谱核磁共振实验对于理解配体特性如何影响溶液中银（I）配合物的核性、配位数和动态行为特别有用。这些见解对于开发改进的配体设计很有价值。
