N-nacnac Stabilized Tetrelenes: Formation of an N,P-Heterocyclic Germylene via C-C Bond Insertion
N-nacnac Stabilized Tetrelenes: Formation of an N,P-Heterocyclic Germylene via C-C Bond Insertion
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DOI：
10.1002/zaac.201800259
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发表时间：
2018-11-15
影响因子：
1.4
通讯作者：
Aldridge, Simon
中科院分区：
文献类型：
--
作者：
Dinh Cao Huan Do;Protchenko, Andrey V.;Aldridge, Simon
报道了氨基官能化的β-二酮亚胺（“N-nacnac”）配体在低价锗化学中的使用，以期与“常规”nacnac系统进行比较。来自锂的N-nacnac配体的transmetrobenzylene允许获得通用的氯锗烯体系，并且随后的取代基交换过程用于产生相关的邻苯二甲酸-和磷杂烯酮-锗烯。后者经历P-CO键的光解诱导裂解，产生不寻常的亚胺配位的N，P-杂环锗烯。DFT计算的基础上，提出这种转变发生通过协同攻击的N-nacnac骨架伴随CO损失的富电子的碳-碳键，而不是通过生成一个免费的膦。
The use of an amino-functionalized beta-diketiminate ("N-nacnac") ligand in low-valent germanium chemistry is reported, with a view to comparison with "conventional" nacnac systems. Transmetallation of the N-nacnac ligand from lithium allows access to a versatile chlorogermylene system, and subsequent substituent exchange processes are used to generate related hydrido-, and phosphaketenyl-germylenes. The latter undergoes photolytically-induced cleavage of the P-CO bond to yield an unusual imine-coordinated N,P-heterocyclic germylene. On the basis of DFT calculations this transformation is proposed to occur via concerted attack by the electron-rich carbon-carbon bond of the N-nacnac backbone accompanying CO loss, rather than via the generation of a free phosphinidene.