Hydroxylation of N-heterocycle ligands observed in two unusual mixed-valence Cu(I)/Cu(II) complexes.
Hydroxylation of N-heterocycle ligands observed in two unusual mixed-valence Cu(I)/Cu(II) complexes.
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DOI：
10.1002/1521-3773(20020315)41:6
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发表时间：
2002-03
影响因子：
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通讯作者：
Xian‐Ming Zhang;M. Tong;Xiao‐Ming Chen
中科院分区：
文献类型：
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作者：
Xian‐Ming Zhang;M. Tong;Xiao‐Ming Chen
螯合配体 2,2-联吡啶 (bpy)、1,10-菲咯啉 (phen) 及其取代衍生物在配位化学的发展中发挥了重要作用，[1, 2] 几十年来，在其金属配合物的反应中报道了许多所谓的异常现象。为了合理化[M(bpy)3]和[M(phen)3]等配合物的反常性质，Gillard借鉴了有机文献中TM共价水合物∫的思想，提出了一个有趣的机制，[3]其核心是氢氧根离子对配位杂环配体的亲核攻击，形成共价水合物（CH）；在形成最终产品之前，这可能会通过 OH 或 H2O 的分子内转移到金属上而进一步发生反应（方案 1）。机制
The chelate ligands 2,2 -bipyridine (bpy), 1,10-phenanthroline (phen), and their substituted derivatives have played an important role in the development of coordination chemistry,[1, 2] and over the decades a number of so-called anomalies have been reported in reactions of their metal complexes. To rationalize the anomalous properties of complexes such as [M(bpy)3] and [M(phen)3] , Gillard borrowed the idea of TMcovalent hydrates∫ from the organic literature and proposed an interesting mechanism,[3] the core of which is nucleophilic attack of a hydroxide ion on a coordinated heterocyclic ligand to form a covalent hydrate (CH); this may react further by intramolecular shift of OH or H2O onto the metal before the formation of the final products (Scheme 1). The mechanism