New Developments in Nitrogen Fixation

Tuczek, Felix; Lehnert, Nicolai

doi:10.1002/(sici)1521-3773(19981016)37:19<2636::aid-anie2636>3.0.co;2-q

Cited by 60 publications

(3 citation statements)

References 9 publications

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“…In each grouping, we highlight compounds of novel structure types or strategies, such as seminal examples of specific coordination modes. For those examples in which vibrational data are the exclusive criterion for discussion (i.e., structural novelty or proof of concept is not demonstrated), we consider the formally N 2 2– oxidation level as our benchmark, while acknowledging that the extent of activation is a sliding scale and any potential limiting criteria can be viewed as arbitrary . If vibrational data are lacking for a specific compound, we default to using the imperfect approach of comparing the N–N bond distances to gauge N 2 activation.…”

Section: Introductionmentioning

confidence: 99%

Activation of Dinitrogen by Polynuclear Metal Complexes

et al. 2020

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Activation of dinitrogen plays an important role in daily anthropogenic life, and the processes by which this fixation occurs have been a longstanding and significant research focus within the community. One of the major fields of dinitrogen activation research is the use of multimetallic compounds to reduce and/or activate N2 into a more useful nitrogen-atom source, such as ammonia. Here we report a comprehensive review of multimetallic-dinitrogen complexes and their utility toward N2 activation, beginning with the d-block metals from Group 4 to Group 11, then extending to Group 13 (which is exclusively populated by B complexes), and finally the rare-earth and actinide species. The review considers all polynuclear metal aggregates containing two or more metal centers in which dinitrogen is coordinated or activated (i.e., partial or complete cleavage of the N2 triple bond in the observed product). Our survey includes complexes in which mononuclear N2 complexes are used as building blocks to generate homo- or heteromultimetallic dinitrogen species, which allow one to evaluate the potential of heterometallic species for dinitrogen activation. We highlight some of the common trends throughout the periodic table, such as the differences between coordination modes as it relates to N2 activation and potential functionalization and the effect of polarizing the bridging N2 ligand by employing different metal ions of differing Lewis acidities. By providing this comprehensive treatment of polynuclear metal dinitrogen species, this Review aims to outline the past and provide potential future directions for continued research in this area.

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Section: Introductionmentioning

confidence: 99%

Activation of Dinitrogen by Polynuclear Metal Complexes

et al. 2020

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“…Transition-metal (TM) sulfide clusters are appealing in many fields ranging from catalysis to biology and material science. Their potential relationships with biology and nanotechnology, in particular, are exemplified by the iron-sulfide clusters that are involved in the electron-transfer process as well as in many other functions such as substrate binding, catalysis, regulation, and sensing. − From a fundamental point of view, TM sulfide clusters are interesting. Metallic and partially ionic bondings are expected to coexist because of the markedly different electronegativities of the TM element and sulfur, and the atomic and covalent radii of the TM elements are much larger than those of S. Therefore, doping TM clusters with an element like S could modify the magnetic exchange coupling in the TM host and its reactivity via possible electronic charge redistributions and structural changes.…”

Section: Introductionmentioning

confidence: 99%

Structural, Electronic, and Magnetic Properties of Iron Disulfide Fe_nS₂^0/±(n= 1–6) Clusters

Tazibt¹,

Chikhaoui

Bouarab

et al. 2017

J. Phys. Chem. A

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The structural, electronic, and magnetic properties of neutral and charged Fe n S 2 0/± (n = 1−6) clusters have been calculated in the framework of the density functional theory in the generalized gradient approximation for the exchange and correlation. The calculated adiabatic electron affinity and the vertical detachment energy are found to be in good agreement with the available experimental data. The impact of disulfide-doping of small iron clusters on the atomic structure, stability, magnetic moment, and reactivity is determined through the analysis of the binding energy per atom, electronic charge transfer, spin-polarized electronic densities of states, and global reactivity indicators like the electronegativity and chemical hardness. Our results provide an exhaustive characterization of these small iron-sulfide particles under vacuum, which is the first step to completely understand their role as components of proteins.

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“…However, this process requires harsh reaction conditions (15 to 25 MPa, 573 to 823 K), consumes 1 to 3% of global energy, and releases more than 300 million tons of greenhouse gases. 2,3 The energy-intensive issue of the Haber–Bosch process has stimulated many scientists to probe into alternative strategies for low-energy ammonia synthesis at room temperature and pressure, such as photocatalysis, 4–6 electrocatalysis 7–9 and enzyme catalysis, 10,11 where photocatalysis is highly attractive and has great potential as a sustainable energy solution. Photocatalytic nitrogen fixation was first proposed by Schrauzer, 12 who pointed out that rutile titanium dioxide could be used as a photocatalyst for photocatalytic nitrogen fixation.…”

Section: Introductionmentioning

confidence: 99%