Abstract
Kinetics and reaction mechanisms governing inversion of the tetrahedral configuration at the metal center in the series ofbis-chelate Zn(II) complexes of 3,2-, 1,2-, and 2,1-oxy(mercapto)naphthaldimines, respectively4–6, have been studied with the use of dynamic1H NMR spectroscopy. A polytopal rearrangement of the diagonal twist type has been found to be an energetically preferable pathway of the inversion reaction for complexes4 and5 with a ZnN2O2 coordination site, whereas the inversion reaction for complexes with a ZnN2S2 coordination site occurs by an intramolecular dissociation-recombination pathway that involves cleavage of a Zn-N coordination bond. In the case of complexes6, the inversion reaction is governed mainly by intramolecular degenerate ligand exchange reactions.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11. pp. 2261–2265, November, 1995.
This work was supported by the Russian Foundation for Basic Research (project No. 93-03-18692) and the International Science Foundation (grant No. RNJ 000).
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Minkin, V.I., Korobov, M.S., Olekhnovich, R.Y. et al. Synthesis and stereochemical nonrigidity of isomeric Zn(ii)bis-[N-isopropyloxy(mercapto)naphthaldiminates]. Russ Chem Bull 44, 2168–2171 (1995). https://doi.org/10.1007/BF00696725
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DOI: https://doi.org/10.1007/BF00696725