Ding Shuang, Li Jiancheng, Liu Rui, Fu Gang, Zhu Hongping, Liu Weiping, Ye Qingsong
State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
State Key Laboratory for Platinum Group Metals, Kunming Institute of Precious Metals, Kunming, Yunnan 650106, China.
ACS Omega. 2017 Jun 1;2(6):2405-2414. doi: 10.1021/acsomega.7b00236. eCollection 2017 Jun 30.
The N-geminal P/Al Lewis pair [PhPN(2,6-PrCH)AlEt] () has been prepared and studied for reaction with a series of alkynes. The reaction of with RC≡CR yielded zwitterionic CPNAl-heterocyclopentene Ph PN(2,6-PrCH)AlEt (R = Me (), Ph ()); with PhC≡CEt produced two isomers, Ph PN(2,6-PrCH)AlEt () and Ph PN(2,6-PrCH)AlEt (); and with other alkynes generated Ph PN(2,6-PrCH)AlEt (R, R = COEt, Ph (); SiMe, Ph (); PPh, Ph (); SiMe,H (); H, EtO ()). Natural bond orbital analysis of the charge separation of the C≡C bond of alkynes was carried out, and then, the electronic matching interaction mode between the combined Lewis acid (AlEt) and base (PPh) groups of and the C≡C bond of such alkynes was discussed. Reactions of with alkene, nitrile, and carbodiimide molecules were also carried out, and cycloaddition compounds - were produced.
已制备出N-偕二P/Al路易斯酸碱对[PhPN(2,6-PrCH)AlEt]（ ），并研究了其与一系列炔烃的反应。[PhPN(2,6-PrCH)AlEt] 与RC≡CR反应生成两性离子型CPNAl-杂环戊烯PhPN(2,6-PrCH)AlEt（R = 甲基（ ），苯基（ ））；与PhC≡CEt反应生成两种异构体，PhPN(2,6-PrCH)AlEt（ ）和PhPN(2,6-PrCH)AlEt（ ）；与其他炔烃反应生成PhPN(2,6-PrCH)AlEt（R、R = COEt、苯基（ ）；SiMe、苯基（ ）；PPh、苯基（ ）；SiMe、H（ ）；H、EtO（ ））。对炔烃C≡C键的电荷分离进行了自然键轨道分析，然后讨论了[PhPN(2,6-PrCH)AlEt] 中组合的路易斯酸（AlEt）和碱（PPh）基团与此类炔烃的C≡C键之间的电子匹配相互作用模式。还进行了[PhPN(2,6-PrCH)AlEt] 与烯烃、腈和碳二亚胺分子的反应，并生成了环加成化合物 - 。
