Gandhi Bhavesh A, Green Omar, Burstyn Judith N
Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Inorg Chem. 2007 May 14;46(10):3816-25. doi: 10.1021/ic0615224. Epub 2007 Feb 14.
A new oxidation-based synthetic route was developed for synthesis of Cu(I) complexes with weakly coordinating ligands, leading to the synthesis of the elusive [Cu(dtbp)2]+ (dtbp, 2,9-di-tert-butyl-1,10-phenanthroline) complex that may be useful as a sensor or as a dye for dye-sensitized solar cells. An acetone solution of either 1 or 2 equiv of dtbp was added to excess Cu(0) and 1 equiv of AgY (Y is O3SCF3-, BF4-, SbF6-, or B(C6F5)4-) in a nitrogen-filled glove box. Following filtration and evaporation under vacuum, crystallization from CH2Cl2 and hexanes results in X-ray quality crystals of Cu(dtbp)(O3SCF3) (1), Cu(dtbp)(BF4) (2), [Cu(dtbp)(acetone)][SbF6] (3), [Cu(dtbp)2][B(C6F5)4].CH2Cl2 (4.CH2Cl2), [Cu(dtbp)2][BF4].CH2Cl2 (5.CH2Cl2), and [Cu(dtbp)2][SbF6].CH2Cl2 (6.CH2Cl2). Complexes 1-6 were characterized by X-ray crystallography and NMR. The Cu atom in complexes 1-3 exhibited distorted trigonal coordination geometries, reflecting the steric effect of the bulky tert-butyl substituents. The structures of the pseudotetrahedral complexes 4, 4.CH2Cl2, 5.CH2Cl2, and 6.CH2Cl2 revealed the longest average Cu-N distances (2.11 A, 2.11 A, 2.10 A, and 2.11 A, respectively) in this class of compounds-longer by more than three standard deviations from the average.
开发了一种新的基于氧化的合成路线，用于合成具有弱配位配体的Cu(I)配合物，从而合成了难以捉摸的[Cu(dtbp)2]+（dtbp，2,9-二叔丁基-1,10-菲咯啉）配合物，该配合物可用作传感器或染料敏化太阳能电池的染料。在充满氮气的手套箱中，将1或2当量dtbp的丙酮溶液加入到过量的Cu(0)和1当量的AgY（Y为O3SCF3-、BF4-、SbF6-或B(C6F5)4-）中。过滤并真空蒸发后，从二氯甲烷和己烷中结晶得到Cu(dtbp)(O3SCF3)（1）、Cu(dtbp)(BF4)（2）、[Cu(dtbp)(丙酮)][SbF6]（3）、[Cu(dtbp)2][B(C6F5)4]·CH2Cl2（4·CH2Cl2）、[Cu(dtbp)2][BF4]·CH2Cl2（5·CH2Cl2）和[Cu(dtbp)2][SbF6]·CH2Cl2（6·CH2Cl2）的X射线级晶体。配合物1-6通过X射线晶体学和核磁共振进行了表征。配合物1-3中的Cu原子呈现出扭曲的三角配位几何结构，反映了庞大的叔丁基取代基的空间效应。假四面体配合物4、4·CH2Cl2、5·CH2Cl2和6·CH2Cl2的结构显示，在这类化合物中，其平均Cu-N距离最长（分别为2.11 Å、2.11 Å、2.10 Å和2.11 Å），比平均值长三个以上标准差。
