Insertion/Rearrangement Reactivity of a Lutetacyclopentadiene towards N,N-Diphenylcarbodiimide: Cooperative Effect of the Metal Center, Concentration of LiCl, and Solvent
Insertion/Rearrangement Reactivity of a Lutetacyclopentadiene towards N,N-Diphenylcarbodiimide: Cooperative Effect of the Metal Center, Concentration of LiCl, and Solvent
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十环戊二烯对 N,N-二苯基碳二亚胺的插入/重排反应性：金属中心、LiCl 浓度和溶剂的协同作用
DOI：
10.1002/chem.201502135
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Xi Zhenfeng
中科院分区：
文献类型：
--
作者：
Xu Ling;Wei Junnian;Zhang Wen-Xiong;Xi Zhenfeng
系统研究了六环戊二烯与N，N′-二苯基碳二亚胺（DPC）的反应性，有效地构建了三种新型的含氮稠环配合物.这些反应的结果显着依赖于金属中心，LiCl的浓度，DPC的当量数，和溶剂。首次发现了脒基的两种反应模式，并将其归因于脒基在刚性七元环驱动下的κ 1配位模式。这些结果与之前研究充分的锆环戊二烯形成鲜明对比，锆环戊二烯与DPC反应，通过β，β′ C → C键断裂得到氮杂环戊烯和炔。lutetacyclopentadiene和zirconacyclopentadiene之间的反应性的差异可以归因于高离子特性的Lu-C（sp2）键。DFT计算结果与实验结果吻合较好。
The reactivity of lutetacyclopentadiene towardsN,N′‐diphenylcarbodiimide (DPC) was systematically investigated to efficiently construct three types of new N‐containing fused cyclic complexes. The outcome of these reactions significantly depended on the the metal center, the concentration of LiCl, the number of equivalents of DPC, and the solvent. Thus, two unexpected reaction modes of amidinate were discovered for the first time, which were ascribed to an unusual κ1coordination mode of amidinate driven by a rigid seven‐membered ring. These results are in striking contrast with the previously well‐investigated zirconacyclopentadiene, which reacts with DPC to give azazirconacyclopentene and alkyne through β,β′ CC bond cleavage. The difference in reactivity between lutetacyclopentadiene and zirconacyclopentadiene can be attributed to the highly ionic character of the LuC(sp2) bonds. DFT calculations agreed well with the experimental results.