Synthesis and reactivity of copper(I) complexes with an ethylene-bridged bis(imidazolin-2-imine) ligand.
Synthesis and reactivity of copper(I) complexes with an ethylene-bridged bis(imidazolin-2-imine) ligand.
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具有乙烯桥联双(咪唑啉-2-亚胺)配体的铜(I)配合物的合成和反应性。
DOI：
10.1039/b715590e
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
Tamm,Matthias
中科院分区：
文献类型：
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作者：
Petrovic,Dejan;Hill,LyndalMR;Jones,PeterG;Tolman,WilliamB;Tamm,Matthias
一系列的铜（I）配合物的空间位阻，双齿配体，BLiPr，来自一个N-杂环卡宾前体已被分离，其特征在于和它们的反应性进行了研究。亚乙基桥连的双（咪唑啉-2-亚胺）配体（BLiPr）提供了用于稳定铜（I）金属中心的强供体N-供体原子，使其具有反应性。配合物[（BLiPr）Cu（XyNC）] PF 6（4）和[（BLiPr）CuCl]（5）的晶体结构经X射线衍射分析表明，配合物在铜中心呈三角配位。在低温下研究了[（BLiPr）Cu] SbF 6对分子氧的反应性，表明形成了具有强烈UV/维斯特征和在625 cm−1（18 O2为599 cm−1）处的同位素敏感振动的热敏中间体。该中间体被认为含有双（µ-氧代）二铜（III）核心[2]（PF 6）2，相关的稳定氢氧化形式结晶为[{（BLiPr）Cu}2（µ-OH）2]（PF 6）2，[3]（PF 6）2。根据反应动力学和聚合物性质评估了5作为苯乙烯ATR聚合催化剂的反应性，对于分子量高达30 000 g mol−1的聚合物实现了低PDI值。
A series of copper(I) complexes with a sterically hindered, bidentate ligand, BLiPr, derived from an N-heterocyclic carbene precursor have been isolated, characterized and their reactivity studied. The ethylene-bridged bis(imidazolin-2-imine) ligand (BLiPr) provides strongly donating N-donor atoms for the stabilization of a copper(I) metal center, priming it for reactivity. The complexes [(BLiPr)Cu(XyNC)]PF6 (4) and [(BLiPr)CuCl] (5) were characterized by X-ray crystallography and exhibit trigonal coordination at the copper centers. The reactivity of [(BLiPr)Cu]SbF6 toward dioxygen was studied at low temperature, indicating formation of a thermally sensitive intermediate with intense UV/Vis features and an isotope-sensitive vibration at 625 cm−1 (599 cm−1 with 18O2). The intermediate is assigned as containing the bis(µ-oxo)dicopper(III) core, [2](PF6)2, and the related, stable hydroxo form was crystallized as [{(BLiPr)Cu}2(µ-OH)2](PF6)2, [3](PF6)2. The reactivity of 5 as a catalyst for the ATR polymerization of styrene was assessed in terms of reaction kinetics and polymer properties, with low PDI values achieved for polymers with molecular weights up to 30 000 g mol−1.