Infrared Photodissociation Spectroscopic and Theoretical Study of Homoleptic Dinuclear Chromium Carbonyl Cluster Cations with a Linear Bridging Carbonyl Group

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• 作者：Xiaojie Zhou ; Jieming Cui ; Zhen Hua Li ; Guanjun Wang ; Mingfei Zhou
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：December 20, 2012
• 年：2012
• 卷：116
• 期：50
• 页码：12349-12356
• 全文大小：382K
• 年卷期：v.116,no.50(December 20, 2012)
• ISSN：1520-5215

文摘

Infrared spectra of mass-selected homoleptic dinuclear chromium carbonyl cluster cations Cr₂(CO)_n⁺ with n = 7鈥? are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region in the gas phase. The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations. The Cr₂(CO)_n⁺ cluster cations are characterized to have the (OC)₅Cr鈥揅鈥揙鈥揅r(CO)_n鈭?⁺ structures with a linear bridging carbonyl group bonded to one chromium atom through its carbon atom and to the other chromium atom through its oxygen atom. The cluster cations all have a sextet ground state with the positive charge and the unpaired electrons located on the Cr(CO)_n鈭? moiety. The formation of the linear bridging structures without Cr鈥揅r bonding can be rationalized that chromium forms strong Cr鈥揅O bonds but weak Cr鈥揅r bonds.