Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence
Publication type: Journal Article
Publication date: 2015-12-01
scimago Q3
wos Q2
SJR: 0.385
CiteScore: 4.1
Impact factor: 2.4
ISSN: 0022328X, 18728561
Materials Chemistry
Organic Chemistry
Biochemistry
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
Room temperature reactions of the rhodium and iridium bromides (η-9-SMe2-7,8-Me2-7,8-C2B9H8)MBr2 (M = Rh (1a), Ir (1b)) with CpTl give the dicarbollide thioether complexes (η-9-SMe-7,8-Me2-7,8-C2B9H8)MCp (2a,b), as a result of demethylation of the SMe2 substituent. These reactions are accompanied by transformation of cage structure from pseudocloso to closo. Refluxing of the sulfonium derivatives [(η-9-SMe2-7,8-Me2-7,8-C2B9H8)MCp]+ (3a,b) with [Bu4N]Br also affords 2a,b. In the same manner ruthenacarboranes [(η-9-SMe2-7,8-C2B9H10)Ru(η-C6H6)]+ (4a) and [(η-10-SMe2-7,8-C2B9H10)Ru(η-C6H6)]+ (4b) react with halide ions giving the thioether complexes (η-9-SMe-7,8-C2B9H10)Ru(η-C6H6) (5a) and (η-10-SMe-7,8-C2B9H10)Ru(η-C6H6) (5b). Dependence of the demethylation rate on the nature of halide ion and solvent was studied both experimentally and theoretically. The structures of 2a and 3aPF6 were determined by X-ray diffraction.
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Vinogradov M. M. et al. Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence // Journal of Organometallic Chemistry. 2015. Vol. 798. pp. 257-262.
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Vinogradov M. M., Nelyubina Y. V., Loginov D. A., Kudinov A. R. Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence // Journal of Organometallic Chemistry. 2015. Vol. 798. pp. 257-262.
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TY - JOUR
DO - 10.1016/j.jorganchem.2015.04.007
UR - https://linkinghub.elsevier.com/retrieve/pii/S0022328X15001989
TI - Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence
T2 - Journal of Organometallic Chemistry
AU - Vinogradov, Mikhail M
AU - Nelyubina, Yulia V.
AU - Loginov, Dmitry A.
AU - Kudinov, Alexander R
PY - 2015
DA - 2015/12/01
PB - Elsevier
SP - 257-262
VL - 798
SN - 0022-328X
SN - 1872-8561
ER -
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@article{2015_Vinogradov,
author = {Mikhail M Vinogradov and Yulia V. Nelyubina and Dmitry A. Loginov and Alexander R Kudinov},
title = {Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence},
journal = {Journal of Organometallic Chemistry},
year = {2015},
volume = {798},
publisher = {Elsevier},
month = {dec},
url = {https://linkinghub.elsevier.com/retrieve/pii/S0022328X15001989},
pages = {257--262},
doi = {10.1016/j.jorganchem.2015.04.007}
}