WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.
Dalton Trans. 2010 Jul 21;39(27):6190-7. doi: 10.1039/c0dt00118j. Epub 2010 Jun 2.
Insertion of CO(2) into the metal-N bond of a series of synthetically important alkali-metal TMP (2,2,6,6-tetramethylpiperidide) complexes has been studied. Determined by X-ray crystallography, the molecular structure of the TMEDA-solvated Li derivative shows a central 8-membered (LiOCO)(2) ring lying in a chair conformation with distorted tetrahedral lithium centres. While trying to obtain crystals of a THF-solvated derivative, a mixed carbonato/carbamato dodecanuclear lithium cluster was formed containing two central (CO(3))(2-) fragments and eight O(2)CTMP ligands with four distinct bonding modes. A bisalkylaluminium carbamato complex has also been prepared via two different methods (CO(2) insertion into a pre-formed Al-N bond and ligand transfer from the corresponding lithium reagent) which adopts a dimeric structure in the solid state.
插入 CO(2) 到一系列合成上重要的碱金属 TMP（2,2,6,6-四甲基哌啶）配合物的金属-N 键中已经被研究过了。通过 X 射线晶体学确定，TMEDA 溶剂化的 Li 衍生物的分子结构显示了一个中央 8 元（LiOCO）（2）环，其处于扭曲四面体锂中心的椅式构象中。在试图获得 THF 溶剂化衍生物的晶体时，形成了一种混合的碳酸根/氨基甲酸盐十二核锂簇，其中包含两个中央（CO3）（2-）片段和八个 O2CTMP 配体，具有四种不同的键合模式。通过两种不同的方法（插入 CO2 到预先形成的 Al-N 键中和从相应的锂试剂转移配体）也制备了双烷基铝氨基甲酸盐配合物，其在固态中采用二聚体结构。
