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Evidence of substrate binding and product release via belt-sulfur mobilization of the nitrogenase cofactor.


ABSTRACT: The Mo-nitrogenase catalyses the ambient reduction of N2 to NH3 at the M-cluster, a complex cofactor that comprises two metal-sulphur partial cubanes ligated by an interstitial carbide and three belt-sulphurs. A recent crystallographic study suggests binding of N2 via displacement of the belt-sulphur(s) of the M-cluster upon turnover. However, the direct proof of N2 binding and belt-sulphur mobilization during catalysis remains elusive. Here we show that N2 is captured on the M-cluster via electron- and sulphur-depletion, and that the N2-captured state is catalytically competent in generating NH3. Moreover, we demonstrate that product release only occurs when sulphite is supplied along with a reductant, that sulphite is inserted as sulphide into the belt-sulphur displaced positions, and that there is a dynamic in-and-out of the belt-sulphurs during catalysis. Together, these results establish the mobilization of the cofactor belt-sulphurs as a crucial, yet overlooked, mechanistic element of the nitrogenase reaction.

SUBMITTER: Lee CC 

PROVIDER: S-EPMC9540607 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Evidence of substrate binding and product release via belt-sulfur mobilization of the nitrogenase cofactor.

Lee Chi Chung CC   Kang Wonchull W   Jasniewski Andrew J AJ   Stiebritz Martin T MT   Tanifuji Kazuki K   Ribbe Markus W MW   Hu Yilin Y  

Nature catalysis 20220516 5


The Mo-nitrogenase catalyses the ambient reduction of N<sub>2</sub> to NH<sub>3</sub> at the M-cluster, a complex cofactor that comprises two metal-sulphur partial cubanes ligated by an interstitial carbide and three belt-sulphurs. A recent crystallographic study suggests binding of N<sub>2</sub> via displacement of the belt-sulphur(s) of the M-cluster upon turnover. However, the direct proof of N<sub>2</sub> binding and belt-sulphur mobilization during catalysis remains elusive. Here we show th  ...[more]

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