Stoian Corina, Al Hussein Fawaz, Browne Wesley R, Hupf Emanuel, Beckmann Jens
Institute for Inorganic Chemistry and Crystallography, Faculty of Biology and Chemistry, University of Bremen, Leobener Straße 7, Bremen 28359, Germany.
Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, Groningen 9747, AG, The Netherlands.
ACS Org Inorg Au. 2024 Aug 17;4(5):545-556. doi: 10.1021/acsorginorgau.4c00034. eCollection 2024 Oct 2.
From a fundamental perspective, studies of novel mixed-valent complexes containing ferrocenyl units are motivated by the prospect of improving and extending electron transfer models and theories. Here, the series of triferrocenylpnictogens FcE was extended to the heavier analogues (E = As, Sb, and Bi), and the influence of the bridging atom was investigated with FcP as a reference. Electrochemical studies elucidate the effect of electrostatic contribution on the large redox splitting (Δ ) exhibited by the compounds and solvent stabilization in the case of FcAs. Structural characterization of the triferrocenylpnictogens combined with spectroelectrochemical studies indicates weak electronic couplings in the related cations [FcE], suggesting a through-space mechanism.
从基础层面来看，对含有二茂铁基单元的新型混合价配合物的研究是受改进和扩展电子转移模型及理论的前景所驱动。在此，三二茂铁基磷族元素化合物系列FcE扩展至较重的类似物（E = As、Sb和Bi），并以FcP作为参考研究了桥连原子的影响。电化学研究阐明了静电作用对化合物所表现出的大氧化还原分裂（Δ）的影响，以及在FcAs情况下的溶剂稳定作用。三二茂铁基磷族元素化合物的结构表征与光谱电化学研究相结合，表明相关阳离子[FcE]中存在弱电子耦合，这暗示了一种空间贯穿机制。
