Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, China.
J Phys Chem A. 2013 Aug 22;117(33):7810-7. doi: 10.1021/jp405250y. Epub 2013 Aug 8.
Infrared spectra of mass-selected homoleptic copper carbonyl cluster cations including dinuclear Cu2(CO)6(+) and Cu2(CO)7(+), trinuclear Cu3(CO)7(+), Cu3(CO)8(+), and Cu3(CO)9(+), and tetranuclear Cu4(CO)8(+) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Cu2(CO)6(+) cation is characterized to have an unbridged D3d structure with a Cu-Cu half bond. The Cu2(CO)7(+) cation is determined to be a weakly bound complex involving a Cu2(CO)6(+) core ion. The trinuclear Cu3(CO)7(+) and Cu3(CO)8(+) cluster cations are determined to have triangle Cu3 core structures with C2 symmetry involving two Cu(CO)3 groups and one Cu(CO)x group (x = 1 or 2). In contrast, the trinuclear Cu3(CO)9(+) cluster cation is determined to have an open chain-like (OC)3Cu-Cu(CO)3-Cu(CO)3 structure. The tetranuclear Cu4(CO)8(+) cluster cation is characterized to have a tetrahedral Cu4(+) core structure with all carbonyl groups terminally bonded.
通过红外光解离光谱技术，在羰基伸缩频率区域内测量了质量选择的同核铜羰基簇阳离子的红外光谱，包括双核 Cu2(CO)6(+)和 Cu2(CO)7(+)、三核 Cu3(CO)7(+)、Cu3(CO)8(+)和 Cu3(CO)9(+)以及四核 Cu4(CO)8(+)。通过将实验光谱与密度泛函计算得到的模拟光谱进行比较，确定了这些结构。Cu2(CO)6(+)阳离子的结构被表征为具有无桥接 D3d 结构和 Cu-Cu 半键。Cu2(CO)7(+)阳离子被确定为一个弱结合的配合物，其中包含一个 Cu2(CO)6(+)核心离子。三核 Cu3(CO)7(+)和 Cu3(CO)8(+)簇阳离子被确定为具有 C2 对称的三角形 Cu3 核结构，其中包含两个 Cu(CO)3 基团和一个 Cu(CO)x 基团（x = 1 或 2）。相比之下，三核 Cu3(CO)9(+)簇阳离子被确定为具有开链状（OC）3Cu-Cu(CO)3-Cu(CO)3 结构。四核 Cu4(CO)8(+)簇阳离子的结构被表征为具有四面体 Cu4(+)核心结构，所有的羰基基团都是端接的。
