Synthesis, structural characterization and reactivity of copper(I)-nitrile complexes:: Crystal and molecular structure of [Cu(BzCN)4][BF4]

被引:2
|
作者
Falcomer, Viviane A. S.
Lemos, Sebastiao S. [1 ]
Martins, Guilherme B. C.
Casagrande, Gleison A.
Burrow, Robert A.
Lang, Ernesto S.
机构
[1] Univ Brasilia, Inst Quim, BR-70904970 Brasilia, DF, Brazil
[2] Univ Fed Santa Maria, Dept Quim, BR-97105900 Santa Maria, RS, Brazil
关键词
copper(I)-nitrile complexes; Cu-63 NMR spectroscopy; (CU)-C-63 MAS NMR spectroscopy; X-ray structure; dynamic equilibrium;
D O I
10.1016/j.poly.2007.04.007
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Complexes of general formula [CuL4][BF4] (L = benzonitrile - PhCN 2 or phenylacetonitrile - BzCN 3) have been prepared and structurally characterized by NMR spectroscopy and X-ray crystallography. Their structure and reactivity have been compared to the well known [Cu(MeCN)(4)][BF4] (1). The Cu-63 line width and the Cu-63 chemical shift have been evaluated by varying the temperature and the concentration of the complex 2 in benzonitrile solutions. The phenylacetonitrile solutions of the complex 3 give extremely broad signals which are beyond detection. Accordingly, compound 3 has been studied by Cu-63 MAS NMR spectroscopy. The solution NMR data are consistent to the prevalence of dynamic equilibrium between tetra- and low-coordinated species in both complexes. The X-ray structure of 3 revealed that the copper(I) atom sits in a slightly distorted tetrahedral geometry, surrounded by four BzCN ligands. (c) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:3871 / 3875
页数:5
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