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- Title
Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism.
- Authors
Demissie, Taye B.; Garabato, Brady D.; Ruud, Kenneth; Kozlowski, Pawel M.
- Abstract
The methylation of HgII(SCH3)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 6p1/2 and 6p3/2 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.
- Subjects
METHYLATION; CORRINOIDS; METHYL radicals; CHEMICAL bonds; SPIN-orbit interactions; REACTION mechanisms (Chemistry)
- Publication
Angewandte Chemie International Edition, 2016, Vol 55, Issue 38, p11503
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201606001