Ershova Irina V, Meshcheryakova Irina N, Trofimova Olesya Yu, Pashanova Kira I, Arsenyeva Kseniya V, Khamaletdinova Nadiya M, Smolyaninov Ivan V, Arsenyev Maxim V, Cherkasov Anton V, Piskunov Alexandr V
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina str., 603137 Nizhny Novgorod, Russia.
Astrakhan State Technical University, 16 Tatisheva str., 414056 Astrakhan, Russia.
Inorg Chem. 2021 Aug 16;60(16):12309-12322. doi: 10.1021/acs.inorgchem.1c01514. Epub 2021 Aug 2.
A series of complexes of metal halides with unreduced quinone-type ligands have been synthesized and characterized in detail. The 3,6-di--butyl--benzoquinone () and 4,6-di--butyl--aryl-substituted -iminobenzoquinones (-) (aryl is 2,6-dimethylphenyl in , 2-methyl-6-ethylphenyl in , 2,6-diethylphenyl in , and 2,6-diisopropylphenyl in ) were used to obtain the molecular complexes with metal 12 group halides as well as with indium(III) iodide. The molecular structures of five complexes, bearing an unreduced form of redox-active ligand, have been established by single-crystal X-ray analysis. The spectral data, electrochemical measurements, and DFT calculations indicate the significant transformations of the molecular orbitals of - upon complexation with Lewis acids. The reduction potentials of -(imino)quinones in complexes with metal halides shift into the anodic region versus uncoordinated ones. The choice of metal halide allows varying the shift magnitude up to 1.7 V in CdI. The change of the oxidizing ability of the - upon coordination with Lewis acids enables the oxidation of mercury and ferrocene, infeasible for free ligands.
一系列金属卤化物与未还原醌型配体的配合物已被合成并进行了详细表征。使用3,6 - 二叔丁基 - 对苯醌（ ）和4,6 - 二叔丁基 - 芳基取代的 - 亚氨基苯醌（ - ）（ 中的芳基为2,6 - 二甲基苯基， 中的芳基为2 - 甲基 - 6 - 乙基苯基， 中的芳基为2,6 - 二乙基苯基， 中的芳基为2,6 - 二异丙基苯基）来获得与第12族金属卤化物以及碘化铟（III）的分子配合物。通过单晶X射线分析确定了五种具有未还原形式氧化还原活性配体的配合物的分子结构。光谱数据、电化学测量和密度泛函理论（DFT）计算表明， - 与路易斯酸络合时分子轨道发生了显著变化。与未配位的 - （亚氨基）醌相比，其与金属卤化物形成的配合物中的还原电位向阳极区域移动。金属卤化物的选择使得在CdI中电位移动幅度可达1.7 V。 - 与路易斯酸配位后氧化能力的变化使得其能够氧化汞和二茂铁，而这对于游离配体来说是不可行的。
