Huh Daniel N, Maity Asim, Van Trieste Gerard P, Schley Nathan D, Powers David C, Tonks Ian A
Department of Chemistry, University of Minnesota - Twin Cities, Minneapolis, MN 55455, United States.
Department of Chemistry, Texas A&M University, College Station, TX 77843, United States.
Polyhedron. 2021 Oct 1;207. doi: 10.1016/j.poly.2021.115368. Epub 2021 Jul 28.
Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex , [(CpTi)(OCTMS)] has been revisited with EPR, confirming a predominantly Ti/Ti electronic structure. Reactions of with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic Ti center remained unperturbed, with reactions taking place at the pendent κ(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.
多金属氧化还原协同作用在生物无机反应和合成反应中都具有重要特征。在此，利用电子顺磁共振（EPR）重新研究了双金属Ti/Ti配合物[(CpTi)(OCTMS)]的电子结构，证实其主要为Ti/Ti电子结构。研究了该配合物与2,6 - 二甲基苯基异氰化物（CNXyl）、TMSCl、MeI和BnCl的反应，揭示了双金属核心的不同氧化还原化学性质。在与CNXyl和TMSCl的反应中，金属环戊二烯基钛中心未受干扰，反应发生在悬垂的κ(O,O)-二茂钛片段上，而与MeI的反应导致金属环戊二烯基钛中心的远程氧化，这表明存在协同氧化还原过程。所有结构均通过X射线衍射和EPR光谱分析进行了研究，并根据共价键分类（CBC）电子计数方法讨论了它们的电子结构。
