Abstract
We report a comparative analysis of experimental and theoretical vibrational spectra recorded in the frequency region of 700-100 cm–1 for mono-o-iminosemiquinone tin(IV) complexes with general formulas LSnR2Cl (1-5) and LSnR3 (6, 7) (L is the 4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzoquinone radical anion, R = Me (1, 6), Et (2), n-Bu (3), t-Bu (4), Ph (5, 7)). It is established that absorption bands of ν(Sn–O) and ν(Sn–N) stretching vibrations in the studied compounds occur at 460-360 cm–1 and 340-350 cm–1, respectively. The position of the ν(Sn–O) absorption band correlates with the Sn–O bond length. In particular, the band is redshifted by 20 cm–1 in complex 6, where this bond is 0.2 Å longer than in other compounds. It is shown that parameters ν(Sn–O), a(117, 119Sn) and bond lengths d(Sn–O), d(Sn–N), and d(Sn–C) in the complexes depend on four (inductive, resonance, polarization, and steric) effects of tin-bonded substituents.
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Funding
The work was carried out within the State Contract (Theme 44.1 “Synthesis, dynamics, and reactivity of electron-labile (including redox-active) molecular systems” (No. 0094-2019-0001)). The studies were carried out using the equipment of the Shared Research Center “IOC RAS Analytical Center” of Razuvaev Institute of Organometallic Chemistry of RAS with the support of the Federal Targeted Program “Research and Development In Priority Areas of S&T Complex of Russia for 2014-2020” (Unique project identifier RFMEFI62120X0040).
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Khamaletdinova, N.M., Meshcheryakova, I.N., Piskunov, A.V. et al. VIBRATIONAL SPECTRA IN THE FAR IR REGION AND EFFECTS OF SUBSTITUENTS IN o-IMINOSEMIQUINONE TIN(IV) COMPLEXES. J Struct Chem 61, 1888–1897 (2020). https://doi.org/10.1134/S0022476620120069
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DOI: https://doi.org/10.1134/S0022476620120069