Abiological nitrogen fixation using homogeneous catalysts

Short description: Chemical process that converts nitrogen to ammonia

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

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 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]

## Contents

* 1 Background
* 2 Transition metals
* 2.1 Vol'pin and Shur
* 2.2 Mo- and Fe-based systems
* 2.3 Photolytic routes
* 3 p-Block systems
* 4 Nitriding
* 5 See also
* 6 References

## Background

Dinitrogen fixation is essential for human life. Currently[when?], the industry uses the Haber–Bosch process to convert N2 and H2 to NH3 based on the metal catalysis under very high pressure and temperature conditions. Alternative strategies that realize the transformation from N2 to NH3 under mild conditions are a long-lasting goal in chemistry. In the past decades[when?], a number of transition-metal species have been found to bind (and even functionalize) N2. The prevalence of transition metals in dinitrogen activation is attributed to the fact that the unoccupied and occupied d orbitals could be both energetically and symmetrically accessible to accept electron density from and back donate to N2. Nevertheless, the development of low-valent, low-coordinate main-group elements which mimic the electronic properties of transition metal provides more opportunities to unearth the N2 activation by main group elements.[2]

Lithium can also react with N2 at room temperature to give an isolable product Li3N.[3][4] However, it was until recently[when?] that the controllable, stepwise N2 activation by main group element began to thrive[editorializing], especially for those whose key intermediates were well structurally characterized and even isolated.

## Transition metals

An early well-defined catalyst for nitrogen reduction.[5] structure of Nishibayashi's Mo2(N2)3 complexes. An Fe(0)-N2 catalyst.[1] Dinitrogen activation by a borylene.

### Vol'pin and Shur

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...."[6]

These results led to many studies on dinitrogen complexes of titanium and zirconium.[7]

### Mo- and Fe-based systems

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.[6] 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.[5]

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][8]

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

### Photolytic routes

Photolytic nitrogen splitting is also considered.[9][10][11][12][13]

## p-Block systems

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.[14] The resulting dianion was subsequently oxidized to a neutral compound, and reduced using water.

## Nitriding

Particular metals can 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.[15] Processes that involve oxidising the lithium metal are however of little practical interest, since they are non-catalytic and re-reducing the Li+ ion residue is difficult. The hydrogenation of Li3N to produce ammonia has seen some exploration since the resulting lithium hydride can be thermally decomposed back to lithium metal.[16]

Some Mo(III) complexes also cleave N2:[17]

2 Mo(NR2)3 \+ N2 → 2 N≡Mo(NR2)3

This and related terminal nitrido complexes have been used to make nitriles.[18]

## See also

* Nitrogenase: enzymes used by organisms to fix nitrogen
* Transition metal dinitrogen complex
* Metal nitrido complex

## References

1. ↑ 1.0 1.1 1.2 1.3 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. PMID 32352271.
2. ↑ Liu, Tong-Tong; Zhai, Dan-Dan; Guan, Bing-Tao; Shi, Zhang-Jie (2022-05-23). "Nitrogen fixation and transformation with main group elements" (in en). Chemical Society Reviews 51 (10): 3846–3861. doi:10.1039/D2CS00041E. ISSN 1460-4744. PMID 35481498. https://pubs.rsc.org/en/content/articlelanding/2022/cs/d2cs00041e.
3. ↑ Rabenau, A.; Schulz, Heinz (1976-11-01). "Re-evaluation of the lithium nitride structure" (in en). Journal of the Less Common Metals 50 (1): 155–159. doi:10.1016/0022-5088(76)90263-0. ISSN 0022-5088.
4. ↑ Roy, Debjani; Navarro-Vazquez, Armando; Schleyer, Paul. v. R. (2009-08-24). "Modeling Dinitrogen Activation by Lithium: A Mechanistic Investigation of the Cleavage of N2 by Stepwise Insertion into Small Lithium Clusters". Journal of the American Chemical Society 131 (36): 13045–13053. doi:10.1021/ja902980j. ISSN 0002-7863. PMID 19702311. Bibcode: 2009JAChS.13113045R.
5. ↑ 5.0 5.1 Schrock, Richard R. (2006). "Reduction of Dinitrogen". PNAS 103 (46): 17087. doi:10.1073/pnas.0603633103. PMID 17088548. PMC 1859893. Bibcode: 2006PNAS..10317087S. http://www.pnas.org/content/pnas/103/46/17087.full.pdf.
6. ↑ 6.0 6.1 Chatt, J.; Leigh, G. J. (1972). "Nitrogen Fixation". Chem. Soc. Rev. 1: 121. doi:10.1039/cs9720100121.
7. ↑ 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.
8. ↑ 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. doi:10.1038/nchem.906. PMID 21258384. Bibcode: 2011NatCh...3..120A.
9. ↑ 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.N2+Splitting:+A+Road+to+Sustainable+NH3+Production?&rft.jtitle=Angew.+Chem.+Int.+Ed.&rft.aulast=Rebreyend&rft.aufirst=C.&rft.au=Rebreyend, C.&rft.au=de+Bruin, B.&rft.date=2014&rft.volume=54&rft.issue=1&rft.pages=42–44&rft_id=info:doi/10.1002/anie.201409727&rft_id=info:pmid/25382116&rfr_id=info:sid/en.wikibooks.org:Chemistry:Abiological_nitrogen_fixation_using_homogeneous_catalysts">
10. ↑ 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.
11. ↑ Huss, Adam S.; Curley, John J.; Cummins, Christopher C.; Blank, David A. (2013). "Relaxation and Dissociation Following Photoexcitation of the (μ-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.N2)[Mo(N[''t''-Bu]Ar)3]2+Dinitrogen+Cleavage+Intermediate&rft.jtitle=J.+Phys.+Chem.+B&rft.aulast=Huss&rft.aufirst=Adam+S.&rft.au=Huss, Adam+S.&rft.au=Curley, John+J.&rft.au=Cummins, Christopher+C.&rft.au=Blank, David+A.&rft.date=2013&rft.volume=117&rft.issue=5&rft.pages=1429–1436&rft_id=info:doi/10.1021/jp310122x&rft_id=info:pmid/23249096&rfr_id=info:sid/en.wikibooks.org:Chemistry:Abiological_nitrogen_fixation_using_homogeneous_catalysts">
12. ↑ Kunkely, H.; Vogler, A. (2010). "Photolysis of Aqueous [(NH3)5Os(μ-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.NH3)5Os(''μ''-N2)Os(NH3)5]5+:+Cleavage+of+Dinitrogen+by+an+Intramolecular+Photoredox+Reaction&rft.jtitle=Angew.+Chem.+Int.+Ed.&rft.aulast=Kunkely&rft.aufirst=H.&rft.au=Kunkely, H.&rft.au=Vogler, A.&rft.date=2010&rft.volume=49&rft.issue=9&rft.pages=1591–1593&rft_id=info:doi/10.1002/anie.200905026&rft_id=info:pmid/20135653&rfr_id=info:sid/en.wikibooks.org:Chemistry:Abiological_nitrogen_fixation_using_homogeneous_catalysts">
13. ↑ 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. Bibcode: 2014ACIE...5311488M.
14. ↑ Broere, Daniël L. J.; Holland, Patrick L. (2018-02-23). "Boron compounds tackle dinitrogen" (in en). Science 359 (6378): 871. doi:10.1126/science.aar7395. ISSN 0036-8075. PMID 29472470. Bibcode: 2018Sci...359..871B.
15. ↑ Brook, Michael A. (2000). Silicon in Organic, Organometallic, and Polymer Chemistry. New York: John Wiley & Sons, Inc.. pp. 193–194.
16. ↑ Goshome, Kiyotaka; Miyaoka, Hiroki; Yamamoto, Hikaru; Ichikawa, Tomoyuki; Ichikawa, Takayuki; Kojima, Yoshitsugu (2015). "Ammonia Synthesis via Non-Equilibrium Reaction of Lithium Nitride in Hydrogen Flow Condition" (in en). Materials Transactions 56 (3): 410–414. doi:10.2320/matertrans.M2014382. ISSN 1345-9678. https://www.jstage.jst.go.jp/article/matertrans/56/3/56_M2014382/_article.
17. ↑ 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. Bibcode: 1996JAChS.118.8623L. https://resolver.caltech.edu/CaltechAUTHORS:20141204-152547970.
18. ↑ 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. Bibcode: 2006JAChS.12814036C.

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