Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, USA.
Inorg Chem. 2013 Feb 4;52(3):1584-90. doi: 10.1021/ic302455y. Epub 2013 Jan 22.
Cationic copper(I) dicarbonyl complexes supported by N-heterocyclic carbene ligands, SIPr and IPr*, have been synthesized. [(SIPr)Cu(CO)(2)][SbF(6)] and [(IPr*)Cu(CO)(2)][SbF(6)] have a trigonal planar, three-coordinate copper atom with an average Cu-CO distance of 1.915 Å and display C-O stretching frequencies higher than that of the free CO (2143 cm(-1)). The high CO stretching frequencies suggest that the Cu(I)-CO interaction in these cationic adducts is dominated by electrostatic and OC → Cu σ-donor components. [(SIPr)Cu(CO)(2)][SbF(6)] and [(IPr*)Cu(CO)(2)][SbF(6)] readily form the corresponding [(SIPr)Cu(CO)(H(2)O)][SbF(6)] and [(IPr*)Cu(CO)(H(2)O)][SbF(6)] with loss of a CO even with traces of water, but they can be converted back to the dicarbonyl adducts using excess CO. The synthesis and structure of [(IPr*)Cu(H(2)O)][SbF(6)] are also reported. It is a two-coordinate copper adduct with a Cu-O distance of 1.874(2) Å. It reacts with excess CO to form [(IPr*)Cu(CO)(2)][SbF(6)].
已合成了由 N-杂环卡宾配体 SIPr 和 IPr* 支撑的阳离子铜(I)二羰基配合物。[(SIPr)Cu(CO)2][SbF6]和[(IPr*)Cu(CO)2][SbF6]具有三角平面的三配位铜原子，平均 Cu-CO 距离为 1.915 Å，且显示出高于游离 CO 的 C-O 伸缩频率（2143 cm-1）。高 CO 伸缩频率表明，这些阳离子加合物中 Cu(I)-CO 相互作用主要由静电和 OC → Cu σ-供体部分主导。[(SIPr)Cu(CO)2][SbF6]和[(IPr*)Cu(CO)2][SbF6]很容易形成相应的[(SIPr)Cu(CO)(H2O)][SbF6]和[(IPr*)Cu(CO)(H2O)][SbF6]，即使有痕量水存在也会失去 CO，但可以使用过量的 CO 将它们转换回二羰基加合物。[(IPr*)Cu(H2O)][SbF6]的合成和结构也有报道。它是一个两配位的铜加合物，Cu-O 距离为 1.874(2) Å。它与过量的 CO 反应形成[(IPr*)Cu(CO)2][SbF6]。
