Copper(I)-Olefin Complexes: The Effect of the Trispyrazolylborate Ancillary Ligand in Structure and Reactivity

被引:28
|
作者
Martin, Carmen [1 ]
Maria Munoz-Molina, Jose [1 ]
Locati, Abel [2 ]
Alvarez, Eleuterio [3 ]
Maseras, Feliu [2 ]
Belderrain, Tomas R. [1 ]
Perez, Pedro J. [1 ]
机构
[1] Univ Huelva, CIQSO, Dept Quim & Ciencia Mat, Lab Catalisis Homogenea,Unidad Asociada CSIC, Huelva 21007, Spain
[2] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain
[3] Univ Seville, CSIC, Inst Invest Quim, Seville 41092, Spain
关键词
COPPER-HOMOSCORPIONATE COMPLEXES; MOLECULAR-ORBITAL METHODS; CARBENE INSERTION; ACTIVE CATALYSTS; ETHYLENE; OLEFIN; ACTIVATION; CYCLOPROPANATION; COORDINATION; SPECTROSCOPY;
D O I
10.1021/om1002705
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The spectroscopic and structural characteristics and the relative reactivity of several Tp(Ms)Cu-(olefin) (olefin = ethylene, 1, 1-hexene, 2, ally! ethyl ether, ace, 3, cyclohexene, 4, and styrene, 5) complexes bearing the bulky hydrotris(3-mesitylpyrazolyl)borate ligand have been examined. Experimental data, including an unusual high-field chemical shift in the H-1 and C-13 NMR spectra, and DFT theoretical calculations support the proposal that the copper-olefin linkage is mainly sustained by sigma-donation, lacking a substantial degree of pi-back-donation.
引用
收藏
页码:3481 / 3489
页数:9
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