Abstract
The synthesis of cobaloxime and methylcobaloxime containing sterically hindered 2,6-di-tert-butylphenol fragments in the ligand is described. Spectral studies of the demethylation of methylbis(dimethylglyoximato)cobalt (1a), methylbis(diphenylglyoximato)cobalt (1b), methylbis[methyl-(3,5-di-tert-butyl-4-hydroxyphenyl)glyoximato]cobalt (1c) pyridinates were carried out in the presence of Cd2+, Hg2+, Sn4+, Pb2+, and Pb4+ ions, The free radical forms of the complexes containing a phenoxy radical W the ligand are formed during oxidation. The ESR spectra are given. The unpaired electron in the periphery of the methylcobaloxime ligand1c interacts with the Co-CH3 fragment through the conjugated systems, enhancing the donating properties of the equatorial ligand of the complex, which leads to the rapid cleavage of the Co-C bond. Therefore the demethylation of methylcobaloxime in the presence of heavy metal ions occurs in a significantly shorter time.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Organometallic Compounds in the Environment, Ed. P. J. Craig, Longman, UK, 1986.
The Biological Alkylation of the Heavy Elements, Ed. P. J. Craig, Royal Soc. Chem., London, 1988.
J. S. Thayer and F. E. Brinckman,Adv. Organomet. Chem., 1982,20, 314.
G. N. Schrauzer,Acc. Chem. Res., 1968,1, 97.
Weygand-Hilgetag,Organisch-Chemische Experimentierkunst, T. A. Barth Verlag, Leipzig, 1964.
G. N. Schrauzer and R. J. Windgassen,J. Am. Chem. Soc., 1966,88, 3738.
V. V. Ershov, G. A. Nikiforov, and A. A. Volod'kin,Prostransrvenno zatrudnennye fenoly [Sterically Hindered Phenols], Khimiya, Moscow, 1972, (in Russian).
A. Chakravorty,Coord. Chem. Rev., 1974,13, 1.
D. G. Brown,The Chemistry of Vitamin B 12 and Related Inorganic Model Systems, inProgr. Inorg. Chem., 1972, 177.
G. N. Schrauzer, L. P. Lee, and J. W. Sibert,J. Am. Chem. Soc., 1970,92, 2997.
M. V. Nekhoroshev, V. B. Panov, and O. Yu. Okhlobystin,Zh. Org, Khim., 1977,13, 662 [Org. Chem. USSR, 1977,13 (Engl. Transl)].
Author information
Authors and Affiliations
Additional information
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp, 1822–1827, July, 1996.
Rights and permissions
About this article
Cite this article
Milaeva, E.R., Androsova, A.V., Polyakova, O.V. et al. Influence of the redox state of the ligand on the dealkylation of substituted methylcobaloximes in the presence of heavy metal ions. Russ Chem Bull 45, 1734–1739 (1996). https://doi.org/10.1007/BF01431816
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF01431816