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Nucleophilic catalysis in deoxymercuration: The beta effect of mercury
Author(s) -
Lambert Joseph B.,
Emblidge Robert W.
Publication year - 1993
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610061005
Subject(s) - chemistry , nucleophile , leaving group , mercury (programming language) , solvent , catalysis , stereochemistry , medicinal chemistry , solvent effects , alkane stereochemistry , polarizability , molecule , organic chemistry , computer science , programming language
Deoxymercuration was examined in the antiperiplanar stereochemistry of trans ‐2‐acetoxycyclohexylmercury(II) acetate (6). The presence of the mercury group accelerates the departure of the beta leaving group by a factor of about 10 10 . This beta effect is larger than that of silicon and comparable to that of germanium. In contrast to these latter cases, the rate for 6 was found to increase with the nucleophilicity of the solvent. It is concluded that a molecule of solvent is coordinated with mercury in the transition state. This nucleophilic assistance raises the polarizability and nucleophilicity of the mercury group, enhancing its ability to stabilize the developing positive charge or to form a bridged intermediate.