Facile Oxidation-Based Synthesis of Sterically Encumbered Four-Coordinate Bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I) and Related Three-Coordinate Copper(I) Complexes
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- 作者：Bhavesh A. Gandhi ; Omar Green ; Judith N. Burstyn
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：May 14, 2007
- 年：2007
- 卷：46
- 期：10
- 页码：3816 - 3825
- 全文大小：160K
- 年卷期：v.46,no.10(May 14, 2007)
- ISSN：1520-510X
文摘
A new oxidation-based synthetic route was developed for synthesis of Cu(I) complexes with weakly coordinatingligands, leading to the synthesis of the elusive [Cu(dtbp)2]+ (dtbp, 2,9-di-tert-butyl-1,10-phenanthroline) complexthat may be useful as a sensor or as a dye for dye-sensitized solar cells. An acetone solution of either 1 or 2 equivof 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 resultsin 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 (4CH2Cl2), [Cu(dtbp)2][BF4]CH2Cl2 (5CH2Cl2), and [Cu(dtbp)2][SbF6]CH2Cl2 (6CH2Cl2).Complexes 1-6 were characterized by X-ray crystallography and NMR. The Cu atom in complexes 1-3 exhibiteddistorted trigonal coordination geometries, reflecting the steric effect of the bulky tert-butyl substituents. The structuresof the pseudotetrahedral complexes 4, 4CH2Cl2, 5CH2Cl2, and 6CH2Cl2 revealed the longest average Cu-Ndistances (2.11 Å, 2.11 Å, 2.10 Å, and 2.11 Å, respectively) in this class of compounds-longer by more than threestandard deviations from the average.
CH2Cl2 (4CH2Cl2), [Cu(dtbp)2][BF4]CH2Cl2 (5CH2Cl2), and [Cu(dtbp)2][SbF6]CH2Cl2 (6CH2Cl2).Complexes 1-6 were characterized by X-ray crystallography and NMR. The Cu atom in complexes 1-3 exhibiteddistorted trigonal coordination geometries, reflecting the steric effect of the bulky tert-butyl substituents. The structuresof the pseudotetrahedral complexes 4, 4CH2Cl2, 5CH2Cl2, and 6CH2Cl2 revealed the longest average Cu-Ndistances (2.11 Å, 2.11 Å, 2.10 Å, and 2.11 Å, respectively) in this class of compounds-longer by more than threestandard deviations from the average.