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Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism
Author(s) -
Demissie Taye B.,
Garabato Brady D.,
Ruud Kenneth,
Kozlowski Pawel M.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201606001
Subject(s) - chemistry , mercury (programming language) , reaction mechanism , computational chemistry , methylation , corrinoid , chemical reaction , photochemistry , relativistic quantum chemistry , stereochemistry , organic chemistry , catalysis , atomic physics , physics , biochemistry , computer science , methyltransferase , gene , programming language
The methylation of Hg II (SCH 3 ) 2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p 1/2 and 6p 3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin–orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.