德国马尔堡大学Gernot Frenking团队首次报道了具有d-d键的高配位异核钙铁羰基阳离子络合物[CaF（CO）n]+（n=5-12）。相关研究成果发表在2021年4月7日出版的《德国应用化学》。

气相中产生[CaF（CO）n]+（n=5-12）形式的异核钙铁羰基阳离子络合物。红外光解光谱结合量子化学计算证实n=10络合物是配位饱和离子，其中Fe（CO）4片段通过两个侧桥羰基配体与Ca（CO）6片段结合。

成键分析表明，[Ca（CO）6]2+指示物和在[（CO）6 Ca‐Fe（CO）4]+结构中形成Fe→Ca d‐d与格键的[Fe（CO）4]阴离子之间的成键相互作用是最好的描述，这丰富了实验观察到的模拟过渡金属化合物的钙络合物库。

该分子是第一个具有钙和过渡金属间d-d键的异核羰基络合物的例子。

附：英文原文

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

Author: Gernot Frenking, Xiaoyang Jin, Yangyu Zhou, Guanjun Wang, Yuna Bai, Lili Zhao, Mingfei Zhou

Issue&Volume: 2021-04-07

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.

DOI: 10.1002/anie.202103267

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202103267