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Complexes of Metal Halides with Unreduced -(Imino)quinones. | LitMetric

AI Article Synopsis

Article Abstract

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.

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http://dx.doi.org/10.1021/acs.inorgchem.1c01514DOI Listing

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