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Highly Coordinated Heteronuclear Calcium-Iron Carbonyl Cation Complexes [CaFe(CO)_n ]⁺ (n=5-12) with d-d Bonding.

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.

SUBMITTER: Jin X

PROVIDER: S-EPMC8251804 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Highly Coordinated Heteronuclear Calcium-Iron Carbonyl Cation Complexes [CaFe(CO)n ]+ (n=5-12) with d-d Bonding.

Jin Xiaoyang X Bai Yuna Y Zhou Yangyu Y Wang Guanjun G Zhao Lili L Zhou Mingfei M Frenking Gernot G

Angewandte Chemie (International ed. in English) 20210510 25

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 intera ...[more]

PMID: 33826215

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