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Bazhenova, M. A.; Bazhenova, T. A.; Петрова, Г. Н.; Mironova, S. A.

doi:10.1023/a:1019851707548

Cited by 8 publications

(7 citation statements)

References 28 publications

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“…This is extremely interesting, as it opens up for electrochemical experiments with the FeMoco [62]. It has been shown that the isolated FeMoco can reduce acetylene ( [63] and references therein) Furthermore, Pickett et al have shown that the isolated FeMo cofactor can be put in an electrochemical system and can be reduced by an applied potential and catalyze the formation of H 2 [64]. It has also been shown that the isolated FeMoco binds CO and shows vibrational frequency shifts similar to those observed in the enzyme [65,66].…”

Section: Enzyme Structurementioning

confidence: 99%

Catalysis by Enzymes: The Biological Ammonia Synthesis

2006

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Enzymes are nature's own catalysts and fundamental for life, as they catalyze essentially all biological processes. Compared to inorganic catalysts, however, their structure and function is immensely more complicated. Computational . modeling has played an increasing role in elucidating enzyme mechanisms, as it can provide information complementary to experimental techniques. Elucidating enzyme structure and mechanism is not only important to understand the basic functions of life, they can also help to find and develop inorganic catalysts. In this review, an overview of recent computational developments for the enzyme nitrogenase will be given. Nitrogenase catalyzes ammonia synthesis, which is also a very important reaction in inorganic catalysis, and insight on enzyme structure and function could provide understanding on how to design biomimetic catalysts for low temperature ammonia synthesis.

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Section: Enzyme Structurementioning

confidence: 99%

Catalysis by Enzymes: The Biological Ammonia Synthesis

2006

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“…2. Calculations qualitatively correctly reproduce small changes in the geometry of the cluster core, Mo 2 Mg 2 O 6 , upon reduction (complexes 1 and 2), namely, the de crease in the μ 3 Table 2) showed that the B3LYP method is somewhat less accurate than PBE.…”

Section: Resultsmentioning

confidence: 88%

“…2), which catalyzes the reduction of nitrogen under conditions similar to biolog ical ones. Recently, 3 it has been established that the ac tive site of nitrogenase (an Fe Mo cofactor) only can reversibly coordinate N 2 under identical conditions. Therefore, information on the structure of catalytically active polynuclear complex (Mo III ) 8 Mg 2 is of great im portance to gain a better insight into the specific role of the protein environment of the Fe Mo cofactor.…”

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confidence: 99%

Geometry and electronic structure of a heterometallic cluster Mo2Mg2 in different oxidation states of Mo: a DFT study

Savinykh

Shestakov

2008

Russ Chem Bull

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Reduction of tetranuclear heterometallic complex Mo 2 Mg 2 was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [Mo VI O 2 Mg(MeOH) 2 (OMe) 4 ] 2 and a partially reduced Mo V complex are in good agreement with experimental data. The reduced Mo III complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Мо atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes.Key words: quantum chemical calculations, DFT methods B3LYP and PBE, catalysts of dinitrogen fixation, binding energy, complex structure.Catalytic systems for dinitrogen reduction are usually based on transition metal ions with d 2 and d 3 electronic configurations. 1 Among them, of particular interest are molybdenum compounds (this element is a constituent of nitrogenase, a natural dinitrogen fixation enzyme). Based on a biomimetic approach, a unique catalytic system containing polynuclear Mo III complexes for dinitrogen fixation was developed (see Ref.2), which catalyzes the reduction of nitrogen under conditions similar to biolog ical ones. Recently, 3 it has been established that the ac tive site of nitrogenase (an Fe Mo cofactor) only can reversibly coordinate N 2 under identical conditions. Therefore, information on the structure of catalytically active polynuclear complex (Mo III ) 8 Mg 2 is of great im portance to gain a better insight into the specific role of the protein environment of the Fe Mo cofactor. Due to the experimental difficulties in the determination of the structure of the complex, it is of interest to elaborate a theoretical approach to the structure elucidation using modern quantum chemical methods that have become highly accurate recently. In the present study, theore tical methods of investigation of polynuclear Мо comp lexes were evaluated using tetranuclear comp lexes [Mo VI O 2 Mg(MeOH) 2 (OMe) 4 ] 2 (1) and [Mo V O 2 (OMe)Mg(MeOH) 2 (OMe) 4 ] 2 (2) as examples; these systems differ in the oxidation state of Mo and their crystal structures are known. 4 The oxidation state of Mo changes with conservation of electroneutrality of the sys

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“…Fortunately, much of this work has been reviewed previously. 15,[20][21][22][23][24][25][26][27][28][29] The goal of this review is to be comprehensive only with respect to the comparatively recent body of literature pertaining to catalytic N 2 RR that is mediated by nominally well-defined synthetic complexes, in the presence of H + /e − sources. We acknowledge at the outset that much of the fascinating literature preceding such catalyst discoveries will not be detailed, except in cases where introducing background is needed to set the stage for the catalyst discoveries that will be covered.…”

Section: Inspiration For Organometallic and Inorganic Chemistrymentioning

confidence: 99%

Catalytic N₂-to-NH₃(or -N₂H₄) Conversion by Well-Defined Molecular Coordination Complexes

2020

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Nitrogen fixation, the six-electron/six-proton reduction of N 2 , to give NH 3 , is one of the most challenging and important chemical transformations. Notwithstanding the barriers associated with this reaction, significant progress has been made in developing molecular complexes that reduce N 2 into its bioavailable form, NH 3 . This progress is driven by the dual aims of better understanding biological nitrogenases and improving upon industrial nitrogen fixation. In this review, we highlight both mechanistic understanding of nitrogen fixation that has been developed, as well as advances in yields, efficiencies, and rates that make molecular alternatives to nitrogen fixation increasingly appealing. We begin with a historical discussion of N 2 functionalization chemistry that traverses a timeline of events leading up to the discovery of the first bona fide molecular catalyst system and follow with a comprehensive overview of d-block compounds that have been targeted as catalysts up to and including 2019. We end with a summary of lessons learned from this significant research effort and last offer a discussion of key remaining challenges in the field.

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Cited by 8 publications

References 28 publications

Catalysis by Enzymes: The Biological Ammonia Synthesis

Catalysis by Enzymes: The Biological Ammonia Synthesis

Geometry and electronic structure of a heterometallic cluster Mo2Mg2 in different oxidation states of Mo: a DFT study

Catalytic N₂-to-NH₃(or -N₂H₄) Conversion by Well-Defined Molecular Coordination Complexes

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Untitled

Cited by 8 publications

References 28 publications

Catalysis by Enzymes: The Biological Ammonia Synthesis

Catalysis by Enzymes: The Biological Ammonia Synthesis

Geometry and electronic structure of a heterometallic cluster Mo2Mg2 in different oxidation states of Mo: a DFT study

Catalytic N2-to-NH3(or -N2H4) Conversion by Well-Defined Molecular Coordination Complexes

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Catalytic N₂-to-NH₃(or -N₂H₄) Conversion by Well-Defined Molecular Coordination Complexes