Synthesis and characterization of copper(II) 4′-phenyl-terpyridine compounds and catalytic application for aerobic oxidation of benzylic alcohols

被引:103
作者
Ma, Zhen [1 ,2 ]
Wei, Lijuan [1 ]
Alegria, Elisabete C. B. A. [2 ,3 ]
Martins, Luisa M. D. R. S. [2 ,3 ]
Guedes da Silva, M. Fatima C. [2 ,4 ]
Pombeiro, Armando J. L. [2 ]
机构
[1] Guangxi Univ, Sch Chem & Chem Engn, Guangxi 530004, Peoples R China
[2] Univ Lisbon, Inst Super Tecn, Ctr Quim Estrutural, P-1049001 Lisbon, Portugal
[3] ISEL, Dept Chem Engn, P-1959007 Lisbon, Portugal
[4] Univ Lusofona Humanidades & Tecnol, ULHT Lisbon, P-1749024 Lisbon, Portugal
关键词
SOLID-STATE PHOTOLUMINESCENCE; ELECTROCHEMICAL PARAMETRIZATION; CORRESPONDING ALDEHYDES; MOLECULAR-STRUCTURE; COMPLEX; TEMPO; CRYSTAL; KETONES; LIGAND; GREEN;
D O I
10.1039/c3dt53054j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reactions between 4'-phenyl-terpyridine (L) and nitrate, acetate or chloride Cu(II) salts led to the formation of [Cu(NO3)(2)L] (1), [Cu(OCOCH3)(2)L]center dot CH2Cl2 (2 center dot CH2Cl2)and [CuCl2L]center dot[Cu(Cl)(mu-Cl)L](2) (3), respectively. Upon dissolving 1 in mixtures of DMSO-MeOH or EtOH-DMF the compounds [Cu(H2O){OS(CH3)(2)}L]-(NO3)(2) (4) and [Cu(HO)(CH3CH2OH)L](NO3) (5) were obtained, in this order. Reaction of 3 with AgSO3CF3 led to [CuCl(OSO2CF3)L] (6). The compounds were characterized by ESI-MS, IR, elemental analysis, electrochemical techniques and, for 2-6, also by single crystal X-ray diffraction. They undergo, by cyclic voltammetry, two single-electron irreversible reductions assigned to Cu(II) -> Cu(I)and Cu(I) -> Cu(0) and, for those of the same structural type, the reduction potential appears to correlate with the summation of the values of the Lever electrochemical EL ligand parameter, which is reported for the first time for copper complexes. Complexes 1-6 in combination with TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl radical) can exhibit a high catalytic activity, under mild conditions and in alkaline aqueous solution, for the aerobic oxidation of benzylic alcohols. Molar yields up to 94% (based on the alcohol) with TON values up to 320 were achieved after 22 h.
引用
收藏
页码:4048 / 4058
页数:11
相关论文
共 82 条
[81]   Luminescent platinum(II) terpyridyl-capped carbon-rich molecular rods - An extension from molecular- to nanometer-scale dimensions [J].
Yam, VWW ;
Wong, KMC ;
Zhu, NY .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (12) :1400-1403
[82]   A new 2,2′:6′,2"-terpyridine-based ligand and its complexes: structures, photophysical properties and DFT calculations to evaluate the halogen effect on the TPA [J].
Zhou, Fei-Xia ;
Zheng, Zheng ;
Zhou, Hong-Ping ;
Ke, Wei-Zai ;
Wang, Jian-Qing ;
Yu, Zhi-Peng ;
Jin, Feng ;
Yang, Jia-Xiang ;
Wu, Jie-Ying ;
Tian, Yu-Peng .
CRYSTENGCOMM, 2012, 14 (17) :5613-5621