Hydrogen Bonds Dictate the Coordination Geometry of Copper: Characterization of a Square-Planar Copper(I) Complex
Hydrogen Bonds Dictate the Coordination Geometry of Copper: Characterization of a Square-Planar Copper(I) Complex
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DOI：
10.1002/anie.201511527
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发表时间：
2016-02-24
影响因子：
16.6
通讯作者：
Szymczak, Nathaniel K.
中科院分区：
文献类型：
--
作者：
Dahl, Eric W.;Szymczak, Nathaniel K.
合成了6，6-二（2，4，6-三甲基苯胺基）三联吡啶（H（2）Tpy（NMes）），它是一种刚性的三齿钳形配体，二级配位层中含有侧链苯胺作为氢键供体基团.（H（2）Tpy（NMes））铜（I）-卤化物（Cl、Br和I）配合物的配位几何形状由NH-卤化物氢键的强度决定。（CuCl）-Cl-I和（CuCl）-Cl-II络合物几乎是同构的，前者呈现出非常不寻常的关于Cu-I的正方形平面几何形状。二级相互作用提供的几何约束让人想起蓝铜蛋白，其中约束的几何形状或熵态允许极其快速的Cu-I/Cu-II电子转移自交换速率。Cu（H（2）Tpy（NMes））Cl具有与生物体系相同数量级的快速电子转移（约10（5）m（-1）s（-1））。
6,6-Bis(2,4,6-trimethylanilido)terpyridine (H(2)Tpy(NMes)) was prepared as a rigid, tridentate pincer ligand containing pendent anilines as hydrogen bond donor groups in the secondary coordination sphere. The coordination geometry of (H(2)Tpy(NMes))copper(I)-halide (Cl, Br and I) complexes is dictated by the strength of the NH-halide hydrogen bond. The (CuCl)-Cl-I and (CuCl)-Cl-II complexes are nearly isostructural, the former presenting a highly unusual square-planar geometry about Cu-I. The geometric constraints provided by secondary interactions are reminiscent of blue copper proteins where a constrained geometry, or entatic state, allows for extremely rapid Cu-I/Cu-II electron-transfer self-exchange rates. Cu(H(2)Tpy(NMes))Cl shows similar fast electron transfer (approximate to 10(5)m(-1)s(-1)) which is the same order of magnitude as biological systems.