混合N-杂环卡宾-恶唑啉基硼酸锌烷基配合物的氧插入反应

Oxygen insertion reactions of mixed N-heterocyclic carbene-oxazolinylborato zinc alkyl complexes.

作者信息

Xu Songchen, Everett William C, Ellern Arkady, Windus Theresa L, Sadow Aaron D

机构信息

Department of Chemistry, Iowa State University, 1605 Gilman Hall, Ames, IA 50011, USA.

出版信息

Dalton Trans. 2014 Oct 14;43(38):14368-76. doi: 10.1039/c4dt01011f.

DOI:10.1039/c4dt01011f

PMID:24938822

Abstract

We report the synthesis of a new mixed oxazoline-carbene scorpionate ligand, bis(4,4-dimethyl-2-oxazolinyl)(1-mesitylimidazolyl)phenylborate (PhB(Ox(Me2))2Im(Mes)). Reactions of the protonated form PhB(Ox(Me2))2(Im(Mes)H) with dialkylzinc compounds provide four-coordinate zinc alkyl complexes, and X-ray diffraction studies of the {PhB(Ox(Me2))2Im(Mes)}ZnR (R = Me, Et) compounds show significant structural distortions involving the R groups shifting away from the carbene donor. The reaction of {PhB(Ox(Me2))2Im(Mes)}ZnEt (3) and O2 provides an isolable mononuclear zinc alkylperoxide {PhB(Ox(Me2))2Im(Mes)}ZnOOEt (4), which has been characterized by single crystal X-ray diffraction and (17)O NMR spectroscopy.

摘要

我们报道了一种新型混合恶唑啉-卡宾螯合配体双(4,4-二甲基-2-恶唑啉基)(1-均三甲苯咪唑基)苯基硼酸盐(PhB(Ox(Me2))2Im(Mes))的合成。质子化形式PhB(Ox(Me2))2(Im(Mes)H)与二烷基锌化合物反应生成四配位锌烷基配合物，对{PhB(Ox(Me2))2Im(Mes)}ZnR (R = Me, Et)化合物的X射线衍射研究表明，存在显著的结构畸变，涉及R基团从卡宾供体处移开。{PhB(Ox(Me2))2Im(Mes)}ZnEt (3)与O2反应生成可分离的单核锌烷基过氧化物{PhB(Ox(Me2))2Im(Mes)}ZnOOEt (4)，该化合物已通过单晶X射线衍射和(17)O NMR光谱进行了表征。