Highly Coordinated Heteronuclear Calcium–Iron Carbonyl Cation Complexes [CaFe(CO)n]+ (n=5–12) with d−d Bonding. (10th May 2021)

• Record Type: Journal Article
• Authors: Jin, Xiaoyang; Bai, Yuna; Zhou, Yangyu; Wang, Guanjun; Zhao, Lili; Zhou, Mingfei; Frenking, Gernot
• Is Part Of: Angewandte Chemie. Volume 133:Number 25(2021)
• Page Start: 13984
• Page End: 13989
• Publication Date: 2021-05-10
• Subjects: bonding analysis -- heteronuclear complexes -- infrared spectroscopy -- matrix isolation -- quantum chemical calculations; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202103267
• Languages: English
• ISSNs: 0044-8249

Abstract

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. Abstract : The [CaFe(CO)10 ] + cation is characterized to be a coordination saturated ion where a Fe(CO)4 fragment is bonded with a Ca(CO)6 moiety through two side‐on bridging carbonyl ligands. The complex 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 that is enhanced by the attraction between Ca and the bridging CO ligands.