Citation: XIAO Yan-Hua, SUN Zhi-Kang, HU Xing-Xing, LI Liang, YANG Xiao-Jun, YUAN Hua, WU Yuan-Xin, DU Zhi-Ping. Syntheses, Crystal Structures and Catalytic Performances of Two Cu Complexes with 1,10-Phenanthroline Ligand[J]. Chinese Journal of Inorganic Chemistry, ;2016, 32(9): 1659-1666. doi: 10.11862/CJIC.2016.214 shu

Syntheses, Crystal Structures and Catalytic Performances of Two Cu Complexes with 1,10-Phenanthroline Ligand

XIAO Yan-Hua ¹ ,
SUN Zhi-Kang ¹ ,
HU Xing-Xing ¹ ,
LI Liang ² ,
YANG Xiao-Jun ¹ ,
YUAN Hua ¹ ,
WU Yuan-Xin ¹ ,
DU Zhi-Ping ^1,2,*,,

1.
Hubei Key Laboratory of Novel Reactor & Green Chemical Technology, Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan 430073, China
2.
Hubei Xunda Pharmaceutical Co., Ltd., Wuxue, Hubei 435400, China

Corresponding author: DU Zhi-Ping, dzpxyhry@163.com
Received Date: 21 June 2016
Revised Date: 6 August 2016

Figures(6)

Two novel Cu complexes, [Cu(Ⅱ)(phen)₂Br]₂[Cu(Ⅰ)₄Br₆] (1) and [Cu(Ⅱ)(phen)₂Br]Br·CH₃OH (2) (phen=1,10-phenanthroline), have been synthesized in alcohol and characterized by infrared spectroscopy, elemental analysis, thermal analysis, and X-ray diffraction single-crystal structure analysis. The structure of 1 with a Cu(Ⅰ)-Cu(Ⅱ) mixed valence can be described as a supramolecular network assembled via the combination of π-π interactions and C-H…Br hydrogen bonds. Its unit cell structure contains two [Cu(Ⅱ)(phen)₂Br]⁺ ions and one tetranuclear [Cu(Ⅰ)₄Br₆]^2- ion; four Cu atoms in the [Cu(Ⅰ)₄Br₆]^2- anion are at corners of a tetrahedron, and six bromine atoms bridging along its six sides constitute an octahedron. The complex 2 consists of [Cu(Ⅱ)(phen)₂Br]⁺, Br^- and CH₃OH, and a supramolecular framework is formed by π-π interactions. When 1 and 2 were used as catalysts for the oxidative carbonylation of methanol to dimethyl carbonate (DMC), 2 exhibits a turnover number of only 5.9 for DMC, while the [Cu(Ⅰ)₄Br₆]^2- anion in 1 provides a suitable environment for the oxidative carbonylation of methanol, and the turnover number for DMC are up to 54.7. CCDC: 1437662, 1; 1014482, 2.
- Cu complexes,
- solvothermal synthesis,
- dimethyl carbonate,
- oxidative carbonylation
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沈阳化工大学材料科学与工程学院沈阳 110142