Nitrogenases-A Tale of Carbon Atom(s)

Yilin Hu; Markus W Ribbe

doi:10.1002/anie.201600010

Nitrogenases-A Tale of Carbon Atom(s)

Angew Chem Int Ed Engl. 2016 Jul 11;55(29):8216-26. doi: 10.1002/anie.201600010. Epub 2016 May 20.

Authors

Yilin Hu¹, Markus W Ribbe²

Affiliations

¹ Department of Molecular Biology and Biochemistry, Department of Chemistry, University of California, Irvine, Irvine, CA, 92697-3900, USA. yilinh@uci.edu.
² Department of Molecular Biology and Biochemistry, Department of Chemistry, University of California, Irvine, Irvine, CA, 92697-3900, USA. mribbe@uci.edu.

PMID: 27206025
DOI: 10.1002/anie.201600010

Abstract

Named after its ability to catalyze the reduction of nitrogen to ammonia, nitrogenase has a surprising rapport with carbon-both through the interstitial carbide that resides in the central cavity of its cofactor and through its ability to catalyze the reductive carbon-carbon coupling of small carbon compounds into hydrocarbon products. Recently, a radical-SAM-dependent pathway was revealed for the insertion of carbide, which signifies a novel biosynthetic route to complex bridged metalloclusters. Moreover, a sulfur-displacement mechanism was proposed for the activation of carbon monoxide by nitrogenase, which suggests an essential role of the interstitial carbide in maintaining the stability while permitting a certain flexibility of the cofactor structure during substrate turnover.

Keywords: CO activation; C−C coupling; interstitial carbide; nitrogenases; radicals.

Publication types

Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Review

MeSH terms

Carbon* / chemistry
Carbon* / metabolism
Models, Molecular
Nitrogenase* / chemistry
Nitrogenase* / metabolism

Substances

Carbon
Nitrogenase