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由芳基硅基酰胺支撑的重碱土环状（烷基）（氨基）卡宾配合物

Heavy Alkaline Earth Cyclic (Alkyl)(Amino)Carbene Complexes Supported by Aryl-Silyl Amides.

作者信息

Bowles Alex W J, Liu Yu, Stevens Matthew P, Ortu Fabrizio

机构信息

School of Chemistry, University of Leicester, University Road, Leicester LE1 7RH, U.K.

Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.

出版信息

Inorg Chem. 2024 Nov 18;63(46):22061-22073. doi: 10.1021/acs.inorgchem.4c03494. Epub 2024 Nov 6.

DOI:10.1021/acs.inorgchem.4c03494
PMID:39505707
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11577317/
Abstract

A series of 8 trigonal planar, heavy alkaline earth (AE = Ca-Ba) metal complexes containing cyclic (alkyl)(amino)carbene (CAAC) ligands were prepared from AE bis(amide) species. Complexation can be achieved by first generating the free carbene or by direct addition of the free carbene, with the former route giving rise to unexpected mixed-amide AE complexes. The frontier molecular orbitals of the highly equatorial, 3-coordinate AE-CAAC species were also probed computationally, revealing the lowest unoccupied molecular orbital (LUMO) consisting predominantly of the π* system located on the carbene ligand.

摘要

通过碱土金属双（酰胺）物种制备了一系列包含环（烷基）（氨基）卡宾（CAAC）配体的8个三角平面重碱土（AE = Ca - Ba）金属配合物。络合反应可以通过首先生成游离卡宾或直接加入游离卡宾来实现，前一种途径会产生意想不到的混合酰胺碱土金属配合物。还通过计算探测了高度赤道面的三配位AE - CAAC物种的前沿分子轨道，揭示了最低未占据分子轨道（LUMO）主要由位于卡宾配体上的π*体系组成。

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