Journal
CHEMICAL REVIEWS
Volume 120, Issue 12, Pages 5194-5251Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemrev.9b00544
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Funding
- Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT) [19H02733, 18H04246]
- Takeda Science Foundation
- Yazaki Memorial Foudation
- Grants-in-Aid for Scientific Research [19H02733, 18H04246] Funding Source: KAKEN
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Transition metal-sulfur (M-S) compounds are an indispensable means for biological systems to convert N-2 into NH3 (biological N-2 fixation), and these may have emerged by chemical evolution from a prebiotic N-2 fixation system. With a main focus on synthetic species, this article provides a comprehensive review of the chemistry of M-S compounds related to the conversion of N-2 and the structures/functions of the nitrogenase cofactors. Three classes of M-S compounds are highlighted here: multinuclear M-S clusters structurally or functionally relevant to the nitrogenase cofactors, mono- and dinuclear transition metal complexes supported by sulfur-containing ligands in N-2 and N2Hx (x = 2, 4) chemistry, and metal sulfide-based solid materials employed in the reduction of N-2. Fair assessments on these classes of compounds revealed that our understanding is still limited in N-2 reduction and related substrate reductions. Our aims of this review are to compile a collection of studies performed at atomic to mesoscopic scales and to present potential opportunities for elucidating the roles of metal and sulfur atoms in the biological N-2 fixation that might be helpful for the development of functional materials.
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