点击活性铜（I）N，S-杂环卡宾配合物的化学计量灵敏度和结构多样性。

Stoichiometric sensitivity and structural diversity in click-active copper(I) N,S-heterocyclic carbene complexes.

机构信息

Department of Chemistry, National University of Singapore, 3 Science Drive 3, Kent Ridge, Singapore 117543, Singapore.

出版信息

Dalton Trans. 2014 Jan 21;43(3):1305-12. doi: 10.1039/c3dt52059e. Epub 2013 Nov 5.

DOI:10.1039/c3dt52059e

PMID:24192930

Abstract

A series of novel Cu(I) N,S-heterocyclic carbene (NSHC) complexes [Cu(μ-Br)(NSHC)]2, [Cu(μ-X)(NSHC)]4 (X = Br or I), [(NSHC)2Cu(μ-Br)2Cu(NSHC)], and [(NSHC)2CuBr] have been isolated from in situ generated CuO(t)Bu and N-substituted benzothiazolium halides and characterized by X-ray crystallography. Five structural motifs were observed, viz. M(x)L(y) where x : y = 2 : 2, 4 : 4, 2 : 3, 1 : 2 and 2 : 4, with Cu···Cu separation traversing over a wide range of 2.5626(7) to 3.4725(7) Å distances. A preliminary investigation of the catalytic activity of these compounds indicated that the unusual mononuclear complex 6 [(NSHC)2CuBr] is an active catalyst for the Huisgen 1,3-dipolar cycloaddition of azide and alkynes while complexes 1-5 and 7 were marginally less active.

摘要

一系列新型的 Cu(I) N，S-杂环卡宾 (NSHC) 配合物 [Cu(μ-Br)(NSHC)]2、[Cu(μ-X)(NSHC)]4（X = Br 或 I）、[(NSHC)2Cu(μ-Br)2Cu(NSHC)] 和 [(NSHC)2CuBr] 已从原位生成的 CuO(t)Bu 和 N-取代苯并噻唑鎓卤化物中分离出来，并通过 X 射线晶体学进行了表征。观察到了五个结构基序，即 M(x)L(y)，其中 x：y = 2：2、4：4、2：3、1：2 和 2：4，Cu···Cu 分离跨越了广泛的 2.5626(7) 至 3.4725(7) Å 距离。对这些化合物的催化活性的初步研究表明，不寻常的单核配合物 6 [(NSHC)2CuBr] 是叠氮化物和炔烃的 Huisgen 1,3-偶极环加成的有效催化剂，而配合物 1-5 和 7 的活性略低。