锆环丁二烯配合物的光化学合成。

Photochemical synthesis of a zirconium cyclobutadienyl complex.

作者信息

Đ P Minh N, Akhmedov Novruz G, Petersen Jeffrey L, Dolinar Brian S, Milsmann Carsten

机构信息

C. Eugene Bennett Department of Chemistry, West Virginia University, 100 Prospect Street, Morgantown, WV 26505, USA.

出版信息

Chem Commun (Camb). 2020 May 19;56(40):5397-5400. doi: 10.1039/d0cc01104e.

DOI:10.1039/d0cc01104e

PMID:32286584

Abstract

Photolysis of (MePMPMe)2ZrBn2 (MePMPMe = 3,5-dimethyl-2-(2-pyridyl)pyrrolide) in the presence of diphenylacetylene yields the first η4-cyclobutadienyl zirconium complex, (MePMPMe)2Zr(η4-C4Ph4), through formal [2+2] cycloaddition of two alkynes at a putative low-valent zirconium intermediate. This unique reactivity expands the scope of alkyne coupling reactions at low-valent zirconium centers that traditionally produce zirconacyclopentadienes.

摘要

在二苯乙炔存在下，(MePMPMe)2ZrBn2（MePMPMe = 3,5 - 二甲基 - 2 - (2 - 吡啶基)吡咯化物）发生光解，通过两个炔烃在假定的低价锆中间体上进行形式上的[2 + 2]环加成反应，生成首个η4 - 环丁二烯基锆配合物(MePMPMe)2Zr(η4 - C4Ph4)。这种独特的反应活性扩展了低价锆中心炔烃偶联反应的范围，传统上该反应生成锆杂环戊二烯。