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Highly Coordinated Heteronuclear Calcium-Iron Carbonyl Cation Complexes [CaFe(CO)n ]+ (n=5-12) with d-d Bonding
Xiaoyang Jin1, Yuna Bai2, Yangyu Zhou1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200438, China.
Abstract:
Heteronuclear calcium-iron carbonyl cation complexes in the form of [CaFe(CO)n ]+ (n=5-12) are produced in the gas phase. Infrared photodissociation spectroscopy in conjunction with quantum chemical calculations confirm that the n=10 complex is the coordination saturated ion where a Fe(CO)4 fragment is bonded with a Ca(CO)6 fragment through two side-on bridging carbonyl ligands. Bonding analysis indicates that it is best described by the bonding interactions between a [Ca(CO)6 ]2+ dication and an [Fe(CO)4 ]- anion forming a Fe→Ca d-d dative bond in the [(CO)6 Ca-Fe(CO)4 ]+ structure, which enriches the pool of experimentally observed complexes of calcium that mimic transition metal compounds. The molecule is the first example of a heteronuclear carbonyl complex featuring a d-d bond between calcium and a transition metal.
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