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Nitrogen reduction by the Fe sites of synthetic [Mo 3 S 4 Fe] cubes.

Authors :
Ohki Y
Munakata K
Matsuoka Y
Hara R
Kachi M
Uchida K
Tada M
Cramer RE
Sameera WMC
Takayama T
Sakai Y
Kuriyama S
Nishibayashi Y
Tanifuji K
Source :
Nature [Nature] 2022 Jul; Vol. 607 (7917), pp. 86-90. Date of Electronic Publication: 2022 Jul 06.
Publication Year :
2022

Abstract

Nitrogen (N <subscript>2</subscript> ) fixation by nature, which is a crucial process for the supply of bio-available forms of nitrogen, is performed by nitrogenase. This enzyme uses a unique transition-metal-sulfur-carbon cluster as its active-site co-factor ([(R-homocitrate)MoFe <subscript>7</subscript> S <subscript>9</subscript> C], FeMoco) <superscript>1,2</superscript> , and the sulfur-surrounded iron (Fe) atoms have been postulated to capture and reduce N <subscript>2</subscript> (refs. <superscript>3-6</superscript> ). Although there are a few examples of synthetic counterparts of the FeMoco, metal-sulfur cluster, which have shown binding of N <subscript>2</subscript> (refs. <superscript>7-9</superscript> ), the reduction of N <subscript>2</subscript> by any synthetic metal-sulfur cluster or by the extracted form of FeMoco <superscript>10</superscript> has remained elusive, despite nearly 50 years of research. Here we show that the Fe atoms in our synthetic [Mo <subscript>3</subscript> S <subscript>4</subscript> Fe] cubes <superscript>11,12</superscript> can capture a N <subscript>2</subscript> molecule and catalyse N <subscript>2</subscript> silylation to form N(SiMe <subscript>3</subscript> ) <subscript>3</subscript> under treatment with excess sodium and trimethylsilyl chloride. These results exemplify the catalytic silylation of N <subscript>2</subscript> by a synthetic metal-sulfur cluster and demonstrate the N <subscript>2</subscript> -reduction capability of Fe atoms in a sulfur-rich environment, which is reminiscent of the ability of FeMoco to bind and activate N <subscript>2</subscript> .<br /> (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Details

Language :
English
ISSN :
1476-4687
Volume :
607
Issue :
7917
Database :
MEDLINE
Journal :
Nature
Publication Type :
Academic Journal
Accession number :
35794270
Full Text :
https://doi.org/10.1038/s41586-022-04848-1