Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism

被引：34

作者：

Demissie, Taye B. ^{[1
]}

Garabato, Brady D. ^{[2
]}

Ruud, Kenneth ^{[1
]}

Kozlowski, Pawel M. ^{[2
,3
]}

机构：

[1] UiT Arctic Univ Norway, Ctr Theoret & Computat Chem, Dept Chem, N-9037 Tromso, Norway

[2] Univ Louisville, Dept Chem, 2320 South Brook St, Louisville, KY 40292 USA

[3] Med Univ Gdansk, Dept Food Sci, Al Gen J Hallera 107, PL-80416 Gdansk, Poland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 38期

关键词：

computational chemistry; density functional calculations; enzyme catalysis; reaction mechanisms; transition states; CO-C BOND; REDUCTIVE CLEAVAGE MECHANISM; DEPENDENT METHYLTRANSFERASES; METHIONINE SYNTHASE; CRYSTAL-STRUCTURE; CHEMISTRY; INSIGHTS; ELEMENTS; ENZYMES; HGCA;

D O I：

10.1002/anie.201606001

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The methylation of Hg-II(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 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.

引用

页码：11503 / 11506

页数：4

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