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
Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx