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Abiological nitrogen fixation using homogeneous catalysts

August 25, 2023

Abiological nitrogen fixation describes chemical processes that fix (react with) N2, usually with the goal of generating ammonia. The dominant technology for abiological nitrogen fixation is the Haber process, which uses an iron-based heterogeneous catalysts and H2 to convert N2 to NH3. This article focuses on homogeneous (soluble) catalysts for the same or similar conversions.[1]

Hypothesized cycle for M-catalysed nitrogen fixation according to Chatt et al.

Transition metals Edit

 
An early well-defined catalyst for nitrogen reduction.[2]
 
structure of Nishibayashi's Mo2(N2)3 complexes.
 
An Fe(0)-N2 catalyst.[1]
 
Dinitrogen activation by a borylene.

Vol'pin and Shur Edit

An early influential discovery of abiological nitrogen fixation was made by Vol'pin and co-workers in Russia in 1970. Aspects are described in an early review:

"using a non-protic Lewis acid, aluminium tribromide, were able to demonstrate the truly catalytic effect of titanium by treating dinitrogen with a mixture of titanium tetrachloride, metallic aluminium, and aluminium tribromide at 50 °C, either in the absence or in the presence of a solvent, e.g. benzene. As much as 200 mol of ammonia per mol of TiCl
4 was obtained after hydrolysis.…"[3]

These results led to many studies on dinitrogen complexes of titanium and zirconium.[4]

Mo- and Fe-based systems Edit

Because Mo and Fe are found at the active site of the most common and most active form of nitrogenase, these metals have been the focus of particular attention for homogeneous catalysis. Most catalytic systems operate according to the following stoichiometry:

N2 + 6 H+ + 6 e− → 2 NH3

The reductive protonation of metal dinitrogen complexes was popularized by Chatt and coworkers, using Mo(N2)2(dppe)2 as substrate. Treatment of this complex with acid gave substantial amounts of ammonium.[3] This work revealed the existence of several intermediates, including hydrazido complexes (Mo=N-NH2). Catalysis was not demonstrated. Schrock developed a related system based on the amido Mo(III) ocomplex Mo[(HIPTN)3N]. With this complex, catalytic nitrogen fixation occurred, albeit with only a few turnovers.[2]

Intense effort has focussed on family of pincer ligand-supported Mo(0)-N2 complexes. In terms of it donor set, and oxidation state, these pincer complexes are similar to Chatt's complexes. Their advantage is that they catalyze the hydrogenation of dinitrogen. A Mo-PCP (PCP = phosphine-[[NHC]-phosphine]] complex exhibits >1000 turnovers when the reducing agent is samarium(II) iodide and the proton source is methanol.[1][5]

Iron complexes of N2 are numerous. Derivatives of Fe(0) with C3-symmetric ligands catalyze nitrogen fixation.[1]

Photolytic routes Edit

Photolytic nitrogen splitting is also considered.[6][7][8][9][10]

p-Block systems Edit

Although nitrogen fixation is usually associated with transition metal complexes, a boron-based system has been described. One molecule of dinitrogen is bound by two transient Lewis-base-stabilized borylene species.[11] The resulting dianion was subsequently oxidized to a neutral compound, and reduced using water.

Nitriding Edit

In rare cases, metals react with nitrogen gas to give nitrides, a process called nitriding. For example, metallic lithium burns in an atmosphere of nitrogen, giving lithium nitride. Hydrolysis of the resulting nitride gives ammonia. In a related process, trimethylsilyl chloride, lithium and nitrogen react in the presence of a catalyst to give tris(trimethylsilyl)amine, which can be further elaborated.[12] Processes involving lithium metal are however of little practical interest since they are non-catalytic and re-reducing the Li+
 ion residue is difficult.

Some Mo(III) complexes also cleave N2:[13]

2 Mo(NR2)3 + N2 → 2 N≡Mo(NR2)3

This and related terminal nitrido complexes have been used to make nitriles.[14]

See also Edit

References Edit

  1. ^ a b c d Chalkley, Matthew J.; Drover, Marcus W.; Peters, Jonas C. (2020). "Catalytic N2-to-NH3 (Or -N2H4) Conversion by Well-Defined Molecular Coordination Complexes". Chemical Reviews. 120 (12): 5582–5636. doi:10.1021/acs.chemrev.9b00638. PMC 7493999. PMID 32352271.
  2. ^ a b Schrock, Richard R. (2006). "Reduction of Dinitrogen" (PDF). PNAS. 103 (46): 17087. Bibcode:2006PNAS..10317087S. doi:10.1073/pnas.0603633103. PMC 1859893. PMID 17088548.
  3. ^ a b Chatt, J.; Leigh, G. J. (1972). "Nitrogen Fixation". Chem. Soc. Rev. 1: 121. doi:10.1039/cs9720100121.
  4. ^ Chirik, Paul J. (2010). "Group 4 Transition Metal Sandwich Complexes: Still Fresh after Almost 60 Years". Organometallics. 29 (7): 1500–1517. doi:10.1021/om100016p.
  5. ^ Arashiba, Kazuya; Miyake, Yoshihiro; Nishibayashi, Yoshiaki (2011). "A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia". Nature Chemistry. 3 (2): 120–125. Bibcode:2011NatCh...3..120A. doi:10.1038/nchem.906. PMID 21258384.
  6. ^ Rebreyend, C.; de Bruin, B. (2014). "Photolytic N
    2     Splitting: A Road to Sustainable NH
    3     Production?". Angew. Chem. Int. Ed. 54 (1): 42–44. doi:10.1002/anie.201409727. PMID 25382116.
  7. ^ Solari, E.; Da Silva, C.; Iacono, B.; Hesschenbrouck, J.; Rizzoli, C.; Scopelliti, R.; Floriani, C. (2001). "Photochemical Activation of the N≡N Bond in a Dimolybdenum–Dinitrogen Complex: Formation of a Molybdenum Nitride". Angew. Chem. Int. Ed. 40 (20): 3907–3909. doi:10.1002/1521-3773(20011015)40:20<3907::AID-ANIE3907>3.0.CO;2-#. PMID 29712125.
  8. ^ Huss, Adam S.; Curley, John J.; Cummins, Christopher C.; Blank, David A. (2013). "Relaxation and Dissociation Following Photoexcitation of the (μ-N
    2    )[Mo(N[t-Bu]Ar)3]2 Dinitrogen Cleavage Intermediate". J. Phys. Chem. B. 117 (5): 1429–1436. doi:10.1021/jp310122x. PMID 23249096.
  9. ^ Kunkely, H.; Vogler, A. (2010). "Photolysis of Aqueous [(NH
    3    )5Os(μ-N
    2    )Os(NH
    3    )5]5+: Cleavage of Dinitrogen by an Intramolecular Photoredox Reaction". Angew. Chem. Int. Ed. 49 (9): 1591–1593. doi:10.1002/anie.200905026. PMID 20135653.
  10. ^ Miyazaki, T.; Tanaka, H.; Tanabe, Y.; Yuki, M.; Nakajima, K.; Yoshizawa, K.; Nishibayashi, Y. (2014). "Cleavage and Formation of Molecular Dinitrogen in a Single System Assisted by Molybdenum Complexes Bearing Ferrocenyldiphosphine". Angew. Chem. Int. Ed. 53 (43): 11488–11492. doi:10.1002/anie.201405673. PMID 25214300.
  11. ^ Broere, Daniël L. J.; Holland, Patrick L. (2018-02-23). "Boron compounds tackle dinitrogen". Science. 359 (6378): 871. Bibcode:2018Sci...359..871B. doi:10.1126/science.aar7395. ISSN 0036-8075. PMC 6101238. PMID 29472470.
  12. ^ Brook, Michael A. (2000). Silicon in Organic, Organometallic, and Polymer Chemistry. New York: John Wiley & Sons, Inc. pp. 193–194.
  13. ^ Laplaza, Catalina E.; Johnson, Marc J. A.; Peters, Jonas C.; Odom, Aaron L.; Kim, Esther; Cummins, Christopher C.; George, Graham N.; Pickering, Ingrid J. (1996). "Dinitrogen Cleavage by Three-Coordinate Molybdenum(III) Complexes: Mechanistic and Structural Data1". Journal of the American Chemical Society. 118 (36): 8623–8638. doi:10.1021/ja960574x.
  14. ^ Curley, John J.; Sceats, Emma L.; Cummins, Christopher C. (2006). "A Cycle for Organic Nitrile Synthesis via Dinitrogen Cleavage". J. Am. Chem. Soc. 128 (43): 14036–14037. doi:10.1021/ja066090a. PMID 17061880.

August 25, 2023
abiological, nitrogen, fixation, using, homogeneous, catalysts, abiological, nitrogen, fixation, describes, chemical, processes, that, react, with, usually, with, goal, generating, ammonia, dominant, technology, abiological, nitrogen, fixation, haber, process,. Abiological nitrogen fixation describes chemical processes that fix react with N2 usually with the goal of generating ammonia The dominant technology for abiological nitrogen fixation is the Haber process which uses an iron based heterogeneous catalysts and H2 to convert N2 to NH3 This article focuses on homogeneous soluble catalysts for the same or similar conversions 1 Hypothesized cycle for M catalysed nitrogen fixation according to Chatt et al Contents 1 Transition metals 1 1 Vol pin and Shur 1 2 Mo and Fe based systems 1 3 Photolytic routes 2 p Block systems 3 Nitriding 4 See also 5 ReferencesTransition metals Edit An early well defined catalyst for nitrogen reduction 2 structure of Nishibayashi s Mo2 N2 3 complexes An Fe 0 N2 catalyst 1 Dinitrogen activation by a borylene Vol pin and Shur Edit An early influential discovery of abiological nitrogen fixation was made by Vol pin and co workers in Russia in 1970 Aspects are described in an early review using a non protic Lewis acid aluminium tribromide were able to demonstrate the truly catalytic effect of titanium by treating dinitrogen with a mixture of titanium tetrachloride metallic aluminium and aluminium tribromide at 50 C either in the absence or in the presence of a solvent e g benzene As much as 200 mol of ammonia per mol of TiCl4 was obtained after hydrolysis 3 These results led to many studies on dinitrogen complexes of titanium and zirconium 4 Mo and Fe based systems Edit Because Mo and Fe are found at the active site of the most common and most active form of nitrogenase these metals have been the focus of particular attention for homogeneous catalysis Most catalytic systems operate according to the following stoichiometry N2 6 H 6 e 2 NH3The reductive protonation of metal dinitrogen complexes was popularized by Chatt and coworkers using Mo N2 2 dppe 2 as substrate Treatment of this complex with acid gave substantial amounts of ammonium 3 This work revealed the existence of several intermediates including hydrazido complexes Mo N NH2 Catalysis was not demonstrated Schrock developed a related system based on the amido Mo III ocomplex Mo HIPTN 3N With this complex catalytic nitrogen fixation occurred albeit with only a few turnovers 2 Intense effort has focussed on family of pincer ligand supported Mo 0 N2 complexes In terms of it donor set and oxidation state these pincer complexes are similar to Chatt s complexes Their advantage is that they catalyze the hydrogenation of dinitrogen A Mo PCP PCP phosphine NHC phosphine complex exhibits gt 1000 turnovers when the reducing agent is samarium II iodide and the proton source is methanol 1 5 Iron complexes of N2 are numerous Derivatives of Fe 0 with C3 symmetric ligands catalyze nitrogen fixation 1 Photolytic routes Edit Photolytic nitrogen splitting is also considered 6 7 8 9 10 p Block systems EditAlthough nitrogen fixation is usually associated with transition metal complexes a boron based system has been described One molecule of dinitrogen is bound by two transient Lewis base stabilized borylene species 11 The resulting dianion was subsequently oxidized to a neutral compound and reduced using water Nitriding EditIn rare cases metals react with nitrogen gas to give nitrides a process called nitriding For example metallic lithium burns in an atmosphere of nitrogen giving lithium nitride Hydrolysis of the resulting nitride gives ammonia In a related process trimethylsilyl chloride lithium and nitrogen react in the presence of a catalyst to give tris trimethylsilyl amine which can be further elaborated 12 Processes involving lithium metal are however of little practical interest since they are non catalytic and re reducing the Li ion residue is difficult Some Mo III complexes also cleave N2 13 2 Mo NR2 3 N2 2 N Mo NR2 3This and related terminal nitrido complexes have been used to make nitriles 14 See also EditNitrogenase enzymes used by organisms to fix nitrogen Transition metal dinitrogen complex Metal nitrido complexReferences Edit a b c d Chalkley Matthew J Drover Marcus W Peters Jonas C 2020 Catalytic N2 to NH3 Or N2H4 Conversion by Well Defined Molecular Coordination Complexes Chemical Reviews 120 12 5582 5636 doi 10 1021 acs chemrev 9b00638 PMC 7493999 PMID 32352271 a b Schrock Richard R 2006 Reduction of Dinitrogen PDF PNAS 103 46 17087 Bibcode 2006PNAS 10317087S doi 10 1073 pnas 0603633103 PMC 1859893 PMID 17088548 a b Chatt J Leigh G J 1972 Nitrogen Fixation Chem Soc Rev 1 121 doi 10 1039 cs9720100121 Chirik Paul J 2010 Group 4 Transition Metal Sandwich Complexes Still Fresh after Almost 60 Years Organometallics 29 7 1500 1517 doi 10 1021 om100016p Arashiba Kazuya Miyake Yoshihiro Nishibayashi Yoshiaki 2011 A molybdenum complex bearing PNP type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia Nature Chemistry 3 2 120 125 Bibcode 2011NatCh 3 120A doi 10 1038 nchem 906 PMID 21258384 Rebreyend C de Bruin B 2014 Photolytic N2 Splitting A Road to Sustainable NH3 Production Angew Chem Int Ed 54 1 42 44 doi 10 1002 anie 201409727 PMID 25382116 Solari E Da Silva C Iacono B Hesschenbrouck J Rizzoli C Scopelliti R Floriani C 2001 Photochemical Activation of the N N Bond in a Dimolybdenum Dinitrogen Complex Formation of a Molybdenum Nitride Angew Chem Int Ed 40 20 3907 3909 doi 10 1002 1521 3773 20011015 40 20 lt 3907 AID ANIE3907 gt 3 0 CO 2 PMID 29712125 Huss Adam S Curley John J Cummins Christopher C Blank David A 2013 Relaxation and Dissociation Following Photoexcitation of the m N2 Mo N t Bu Ar 3 2 Dinitrogen Cleavage Intermediate J Phys Chem B 117 5 1429 1436 doi 10 1021 jp310122x PMID 23249096 Kunkely H Vogler A 2010 Photolysis of Aqueous NH3 5Os m N2 Os NH3 5 5 Cleavage of Dinitrogen by an Intramolecular Photoredox Reaction Angew Chem Int Ed 49 9 1591 1593 doi 10 1002 anie 200905026 PMID 20135653 Miyazaki T Tanaka H Tanabe Y Yuki M Nakajima K Yoshizawa K Nishibayashi Y 2014 Cleavage and Formation of Molecular Dinitrogen in a Single System Assisted by Molybdenum Complexes Bearing Ferrocenyldiphosphine Angew Chem Int Ed 53 43 11488 11492 doi 10 1002 anie 201405673 PMID 25214300 Broere Daniel L J Holland Patrick L 2018 02 23 Boron compounds tackle dinitrogen Science 359 6378 871 Bibcode 2018Sci 359 871B doi 10 1126 science aar7395 ISSN 0036 8075 PMC 6101238 PMID 29472470 Brook Michael A 2000 Silicon in Organic Organometallic and Polymer Chemistry New York John Wiley amp Sons Inc pp 193 194 Laplaza Catalina E Johnson Marc J A Peters Jonas C Odom Aaron L Kim Esther Cummins Christopher C George Graham N Pickering Ingrid J 1996 Dinitrogen Cleavage by Three Coordinate Molybdenum III Complexes Mechanistic and Structural Data1 Journal of the American Chemical Society 118 36 8623 8638 doi 10 1021 ja960574x Curley John J Sceats Emma L Cummins Christopher C 2006 A Cycle for Organic Nitrile Synthesis via Dinitrogen Cleavage J Am Chem Soc 128 43 14036 14037 doi 10 1021 ja066090a PMID 17061880 Retrieved from https en wikipedia org w index php title Abiological nitrogen fixation using homogeneous catalysts amp oldid 1108819351, wikipedia, wiki, book, books, library,

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