Abstract
An ideal synthesis of alkyl amines would involve the direct use of abundant and easily accessible molecules such as dinitrogen (N2) and feedstock alkenes1,2,3,4. However, this ambition remains a great challenge as it is usually difficult to simultaneously activate both N2 and a simple alkene and combine them together through carbon–nitrogen (C–N) bond formation. Currently, the synthesis of alkyl amines relies on the use of ammonia produced through the Haber–Bosch process and prefunctionalized electrophilic carbon sources. Here we report the hydroamination of simple alkenes with N2 in a trititanium hydride framework, which activates both alkenes and N2, leading to selective C–N bond formation and providing the corresponding alkyl amines on further hydrogenation and protonation. Computational studies reveal key mechanistic details of N2 activation and selective C–N bond formation. This work demonstrates a strategy for the transformation of N2 and simple hydrocarbons into nitrogen-containing organic compounds mediated by a multinuclear hydride framework.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
All data resulting from the experimental and computational studies of this work are included within this article and the Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2226119 (1′), 2184614 (3), 2184610 (4a), 2285950 (4f′), 2226120 (4g), 2184611 (5), 2184612 (6), 2184613 (8a) and 2226121 (8g′). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.
References
Streiff, S. & Jérôme, F. Hydroamination of non-activated alkenes with ammonia: a holy grail in catalysis. Chem. Soc. Rev. 50, 1512–1521 (2021).
Masero, F., Perrin, M. A., Dey, S. & Mougel, V. Dinitrogen fixation: rationalizing strategies utilizing molecular complexes. Chem. Eur. J. 27, 3892–3928 (2021).
Kim, S., Loose, F. & Chirik, P. J. Beyond ammonia: nitrogen–element bond forming reactions with coordinated dinitrogen. Chem. Rev. 120, 5637–5681 (2020).
Lv, Z.-J. et al. Direct transformation of dinitrogen: synthesis of N-containing organic compounds via N−C bond formation. Natl Sci. Rev. 7, 1564–1583 (2020).
Jennings, J. R. (ed.) Catalytic Ammonia Synthesis: Fundamentals and Practice (Springer, 1991).
Liu, H. Ammonia Synthesis Catalysts: Innovation and Practice (World Scientific Publishing & Chemical Industry Press China, 2013).
Amines Market—By Type (Ethanolamine, Monoethanolamine, Diethanolamine, Triethanolamine, Methyl diethanolamine (MDEA), By Application, By Function & Forecast, 2024–2032 (GMI, 2024); https://www.gminsights.com/industry-analysis/amines-market.
Arpe, H.-J. Industrial Organic Chemistry (Wiley-VCH, 2010).
Zhuo, Q., Zhou, X., Shima, T. & Hou, Z. Dinitrogen activation and addition to unsaturated C–E (E = C, N, O, S) bonds mediated by transition metal complexes. Angew. Chem. Int. Ed. 62, e202218606 (2023).
Shima, T., Zhuo, Q. & Hou, Z. Dinitrogen activation and transformation by multimetallic polyhydride complexes. Coord. Chem. Rev. 472, 214766 (2022).
Yang, J.-H. et al. Fixation of N2 into value-added organic chemicals. ACS Catal. 12, 2898–2906 (2022).
Forrest, S. J. K., Schluschaß, B., Yuzik-Klimova, E. Y. & Schneider, S. Nitrogen fixation via splitting into nitrido complexes. Chem. Rev. 121, 6522–6587 (2021).
Burford, R. J., Yeo, A. & Fryzuk, M. D. Dinitrogen activation by group 4 and group 5 metal complexes supported by phosphine-amido containing ligand manifolds. Coord. Chem. Rev. 334, 84–99 (2017).
Nishibayashi, Y. (ed.) Nitrogen Fixation (Springer, 2017).
Walter, M. D. Recent advances in transition metal-catalyzed dinitrogen activation. Adv. Organomet. Chem. 65, 261–377 (2016).
Mori, M. Activation of nitrogen for organic synthesis. J. Organomet. Chem. 689, 4210–4227 (2004).
Zhuo, Q. et al. Aza-Michael addition of dinitrogen to α,β-unsaturated carbonyl compounds in a dititanium framework. J. Am. Chem. Soc. 145, 22803–22813 (2023).
Xie, S.-J. et al. Direct incorporation of dinitrogen into an aliphatic C–H bond. J. Am. Chem. Soc. 145, 6773–6780 (2023).
Zhuo, Q. et al. Dinitrogen cleavage and functionalization by carbon dioxide at a dititanium dihydride framework. J. Am. Chem. Soc. 144, 6972–6980 (2022).
Itabashi, T. et al. Direct synthesis of cyanate anion from dinitrogen catalysed by molybdenum complexes bearing pincer-type ligand. Nat. Commun. 13, 6161 (2022).
Wang, K. et al. Synthesis of arylamines and N-heterocycles by direct catalytic nitrogenation using N2. Nat. Commun. 12, 248 (2021).
Song, J. et al. Conversion of dinitrogen into nitrile: cross-metathesis of N2-derived molybdenum nitride with alkynes. Angew. Chem. Int. Ed. 60, 12242–12247 (2021).
Falcone, M. et al. Nitrogen reduction and functionalization by a multimetallic uranium nitride complex. Nature 547, 332–335 (2017).
Nakanishi, Y., Ishida, Y. & Kawaguchi, H. Nitrogen–carbon bond formation by reactions of a titanium–potassium dinitrogen complex with carbon dioxide, tert-butyl isocyanate, and phenylallene. Angew. Chem. Int. Ed. 56, 9193–9197 (2017).
Guru, M. M., Shima, T. & Hou, Z. Conversion of dinitrogen to nitriles at a multinuclear titanium framework. Angew. Chem. Int. Ed. 55, 12316–12320 (2016).
Klopsch, I. et al. Conversion of dinitrogen into acetonitrile under ambient conditions. Angew. Chem. Int. Ed. 55, 4786–4789 (2016).
Semproni, S. P. & Chirik, P. J. N−H and N−C bond formation with an N2-derived dihafnium μ-nitrido complex. Organometallics 33, 3727–3737 (2014).
Semproni, S. P. & Chirik, P. J. Synthesis of a base-free hafnium nitride from N2 cleavage: a versatile platform for dinitrogen functionalization. J. Am. Chem. Soc. 135, 11373–11383 (2013).
Figueroa, J. S., Piro, N. A., Clough, C. R. & Cummins, C. C. A nitridoniobium(V) reagent that effects acid chloride to organic nitrile conversion: synthesis via heterodinuclear (Nb/Mo) dinitrogen cleavage, mechanistic insights, and recycling. J. Am. Chem. Soc. 128, 940–950 (2006).
Morello, L., Love, J. B., Patrick, B. O. & Fryzuk, M. D. Carbon–nitrogen bond formation via the reaction of terminal alkynes with a dinuclear side-on dinitrogen complex. J. Am. Chem. Soc. 126, 9480–9481 (2004).
Mou, L.-H. et al. Mutual functionalization of dinitrogen and methane mediated by heteronuclear metal cluster anions CoTaC2−. Chem. Sci. 13, 9366–9372 (2022).
Xu, X. et al. Direct amination of benzene with molecular nitrogen enabled by plasma–liquid interactions. Angew. Chem. Int. Ed. 61, e2022036 (2022).
McWilliams, S. F. et al. Coupling dinitrogen and hydrocabons through aryl migration. Nature 584, 221–226 (2020).
Bhutto, S. M., Hooper, R. X., Mercado, B. Q. & Holland, P. L. Mechanism of nitrogen–carbon bond formation from iron(IV) disilylhydrazido intermediates during N2 reduction. J. Am. Chem. Soc. 145, 4626–4637 (2023).
Shima, T. et al. Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex. Science 340, 1549–1552 (2013).
Hu, S., Shima, T. & Hou, Z. Carbon–carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride. Nature 512, 413–415 (2014).
Shoshani, M. M. & Johnson, S. A. Cooperative carbon-atom abstraction from alkenes in the core of a pentanuclear nickel cluster. Nat. Chem. 9, 1282–1285 (2017).
Hu, S. et al. Hydrodenitrogenation of pyridines and quinolines at a multinuclear titanium hydride framework. Nat. Commun. 8, 1866 (2017).
Takemori, T., Inagaki, A. & Suzuki, H. A novel type of carbon–carbon double bond cleavage of 1,1-disubstituted alkenes on a triruthenium polyhydrido cluster. J. Am. Chem. Soc. 123, 1762–1763 (2001).
Tahara, A. et al. Metathesis reaction of hydrocarbyl ligands across the triruthenium plane. Angew. Chem. Int. Ed. 49, 5898–5901 (2010).
del Horno, E. et al. Dinitrogen binding at a trititanium chloride complex and its conversion to ammonia under ambient conditions. Angew. Chem. Int. Ed. 61, e202204544 (2022).
Fryzuk, M. D. et al. New mode of coordination for the dinitrogen ligand: formation, bonding, and reactivity of a tantalum complex with a bridging N2 unit that is both side-on and end-on. J. Am. Chem. Soc. 123, 3960–3973 (2001).
Acknowledgements
This work was supported in part by a JSPS KAKENHI Grant-in-Aid for Scientific Research (A) (JP23H00300) and (B) (JP23H01981), and an Incentive Research Grant from RIKEN. We acknowledge RICC (RIKEN Integrated Cluster of Clusters) and Hefei Advanced Computing Center for computational support. We thank A. Karube, K. Suzuki, T. Nakamura, E. Imai and Y. Oshima for their support in microelemental analyses and mass spectral and electron spin resonance measurements.
Author information
Authors and Affiliations
Contributions
T.S., Q.Z., X.Z. and R.O. carried out the experiments. P.W. and G.L. carried out density functional theory calculations. T.S., Q.Z. and Z.H. analysed the data and co-wrote the paper with support from X.Z. Z.H. directed the project.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature thanks the anonymous reviewers for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
This file contains Supplementary Methods, Figs. 1–106 and Tables 1–4.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Shima, T., Zhuo, Q., Zhou, X. et al. Hydroamination of alkenes with dinitrogen and titanium polyhydrides. Nature 632, 307–312 (2024). https://doi.org/10.1038/s41586-024-07694-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-024-07694-5
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
