Jin Xiaoyang, Bai Yuna, Zhou Yangyu, Wang Guanjun, Zhao Lili, Zhou Mingfei, Frenking Gernot
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200438, China.
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, 211816, China.
Angew Chem Int Ed Engl. 2021 Jun 14;60(25):13865-13870. doi: 10.1002/anie.202103267. Epub 2021 May 10.
Heteronuclear calcium-iron carbonyl cation complexes in the form of [CaFe(CO) ] (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) fragment is bonded with a Ca(CO) fragment through two side-on bridging carbonyl ligands. Bonding analysis indicates that it is best described by the bonding interactions between a [Ca(CO) ] dication and an [Fe(CO) ] anion forming a Fe→Ca d-d dative bond in the [(CO) Ca-Fe(CO) ] 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.
气相中生成了[CaFe(CO)ₙ]（n = 5 - 12）形式的异核钙 - 铁羰基阳离子配合物。红外光解离光谱结合量子化学计算证实，n = 10的配合物是配位饱和离子，其中一个Fe(CO)片段通过两个侧基桥连羰基配体与一个Ca(CO)片段相连。键合分析表明，在[(CO)₅Ca - Fe(CO)₅]结构中，它最好用[Ca(CO)₅]²⁺阳离子和[Fe(CO)₅]⁻阴离子之间形成Fe→Ca d - d给体键的键合相互作用来描述，这丰富了模拟过渡金属化合物的钙的实验观察配合物库。该分子是第一个在钙和过渡金属之间具有d - d键的异核羰基配合物的例子。
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