Citation: Xue-Lu Ma, Meng Li, Jun-Bo Lu, Cong-Qiao Xu, Jun Li. Recent Developments of Dinitrogen Activation on Metal Complexes and Clusters[J]. Chinese Journal of Structural Chemistry, ;2022, 41(12): 221208. doi: 10.14102/j.cnki.0254-5861.2022-0197 shu

Recent Developments of Dinitrogen Activation on Metal Complexes and Clusters

Xue-Lu Ma ¹ ,
Meng Li ¹ ,
Jun-Bo Lu ² ,
Cong-Qiao Xu ² ,
Jun Li ^{2, 3,,}

1.
School of Chemical & Environmental Engineering, China University of Mining & Technology, Beijing 100083, China
2.
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China
3.
Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing 100084, China

Author Bio: Xue-Lu Ma is a lecture of School of Chemical & Environmental Engineering at China University of Mining & Technology—Beijing (CUMTB). She completed her PhD in 2016 at Beijing University of Chemical Technology and worked with a postdoctoral fellowship during 2016-2018 in Tsinghua University. Her research interests focus on the computational chemistry and theoretical catalysis
Meng Li received her BSc from Hebei Normal University of Science and Technology in 2020. She is currently studying for her master's degree at School of Chemical & Environmental Engineering, CUMTB. Her research work focuses on computational homogeneous catalysis
Jun-Bo Lu obtained his BSc from Lanzhou University in 2015, and PhD degree from Tsinghua University in 2020 under the supervision of Prof. Jun Li. He is now working on electronic structure of lanthanide and actinide systems. His current research focuses on computational actinide chemistry, which covers the application of quantum chemistry methods in the study of small molecule activation by homogeneous catalysts containing low-valent uranium and thorium
Cong-Qiao Xu received her PhD degree from the Department of Chemistry, Tsinghua University in 2017 under the supervision of Prof. Jun Li and then became a postdoctoral fellow at Tsinghua University from 2017 to 2019. She is currently a research associate professor at the Department of Chemistry at Southern University of Science and Technology. Her research interests focus on theoretical inorganic chemistry and computational catalysis science
Jun Li is a Professor in Theoretical Chemistry at the Department of Chemistry, Tsinghua University, China. He received his PhD from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in 1992 and carried out postdoctoral research at Siegen University (Germany) and Ohio State University (USA). He then worked at the Pacific Northwest National Laboratory as a Senior Research Scientist and Chief Scientist until 2009. His research interests include f-element relativistic quantum chemistry, computational catalysis, and theoretical cluster chemistry (group website: http://www.junlilab.org)
Corresponding author: Jun Li, junli@tsinghua.edu.cn
Received Date: 16 September 2022
Accepted Date: 4 October 2022
Available Online: 9 October 2022

Figures(5)

Dinitrogen (N₂) is the major component of the atmosphere and many factors bring about dinitrogen inertness with low reactivity. Dinitrogen activation on metal complexes and clusters under ambient condition is the long-standing goal in the modern chemistry. In this review, an attempt has been made to survey the mechanistic aspects of dinitrogen activation and functionalization based on different coordination binding modes of dinitrogen. Our goal is to provide a comprehensive survey of dinitrogen activation in order to guide the relevant research in the future.
- dinitrogen activation,
- binding mode,
- dinitrogen complex,
- metal cluster,
- synergistic mechanism
1. [1]
  Himmel, H. J.; Reiher, M. Intrinsic dinitrogen activation at bare metal atoms. Angew. Chem. Int. Ed. 2006, 45, 6264-6288. doi: 10.1002/anie.200502892
2. [2]
  Zhan, C. G.; Nichols, J. A.; Dixon, D. A. Ionization potential, electron affinity, electronegativity, hardness, and electron excitation energy: molecular properties from density functional theory orbital energies. J. Phys. Chem. A 2003, 107, 4184-4195. doi: 10.1021/jp0225774
3. [3]
  Hong, Q. S.; Li, T. Y.; Zheng, S. S.; Chen, H. B.; Chu, H. H.; Xu, K. D.; Li, S. N.; Mei, Z. W.; Zhao, Q. H.; Ren, W. J.; Zhao, W. G.; Pan, P. Tuning double layer structure of WO₃ nanobelt for promoting the electrochemical nitrogen reduction reaction in water. Chin. J. Struct. Chem. 2021, 40, 519-526.
4. [4]
  Stahl, S. S. Organotransition metal chemistry: from bonding to catalysis. J. Am. Chem. Soc. 2010, 132, 8524-8525.
5. [5]
  Liu, H. M.; Wei, L.; Liu, F.; Pei, Z. X.; Shi, J.; Wang, Z. J.; He, D.; Chen, Y. Homogeneous, heterogeneous, and biological catalysts for electrochemical N₂ reduction toward NH₃ under ambient conditions. ACS Catal. 2019, 9, 5245-5267. doi: 10.1021/acscatal.9b00994
6. [6]
  Fryzuk, M. D.; Johnson, S. A. The continuing story of dinitrogen activation. Coord. Chem. Rev. 2000, 200, 379-409.
7. [7]
  Lv, Z. J.; Wei, J. N.; Zhang, W. X.; Chen, P.; Deng, D. H.; Shi, Z. J.; Xi, Z. F. Direct transformation of dinitrogen: synthesis of N-containing organic compounds via N-C bond formation. Natl. Sci. Rev. 2020, 7, 1564-1583. doi: 10.1093/nsr/nwaa142
8. [8]
  Honkala, K.; Hellman, A.; Remediakis, IN.; Logadottir, A.; Carlsson, A.; Dahl, S.; Christensen, C. H.; Norskov, J. K. Ammonia synthesis from first-principles calculations. Science 2005, 307, 555-558. doi: 10.1126/science.1106435
9. [9]
  Logadottir, A.; Nørskov, J. K. Ammonia synthesis over a Ru (0001) surface studied by density functional calculations. J. Catal. 2003, 220, 273-279. doi: 10.1016/S0021-9517(03)00156-8
10. [10]
  Hoffman, B. M.; Lukoyanov, D.; Yang, Z. Y.; Dean, D. R.; Seefeldt, L. C. Mechanism of nitrogen fixation by nitrogenase: the next stage. Chem. Rev. 2014, 114, 4041-4062. doi: 10.1021/cr400641x
11. [11]
  Burford, R. J.; Fryzuk, M. D. Examining the relationship between coordination mode and reactivity of dinitrogen. Nat. Rev. Chem. 2017, 1, 0026. doi: 10.1038/s41570-017-0026
12. [12]
  Musaev, D. G. Theoretical prediction of a new dinitrogen reduction process: utilization of four dihydrogen molecules and a Zr₂Pt₂ cluster. J. Phys. Chem. B 2004, 108, 10012-10018. doi: 10.1021/jp0482767
13. [13]
  Yamabe, T.; Hori, K.; Minato, T.; Fukui, K. Theoretical study on the bonding nature of transition-metal complexes of molecular nitrogen. Inorg. Chem. 1980, 19, 2154-2159. doi: 10.1021/ic50209a063
14. [14]
  Holland, P. L. Metal-dioxygen and metal-dinitrogen complexes: where are the electrons? Dalton Trans. 2010, 39, 5415-5425. doi: 10.1039/c001397h
15. [15]
  Henderson, R. Activation of dinitrogen at binuclear sites. Transition Met. Chem. 1990, 15, 330-336. doi: 10.1007/BF01061944
16. [16]
  Crossland, J. L.; Tyler, D. R. Iron-dinitrogen coordination chemistry: dinitrogen activation and reactivity. Coord. Chem. Rev. 2010, 254, 1883-1894. doi: 10.1016/j.ccr.2010.01.005
17. [17]
  Pan, F. Can structural chemistry point the way: exploring the relevance between structure and properties. Chin. J. Struct. Chem. 2020, 39, 7.
18. [18]
  Zhang, M. Y.; Zhang, Y. Y.; Zhang, H. X.; Wang, K.; Wang, Y. Q.; Zeng, Y. F.; Liu, G. Y. Synthesis, crystal structure and catalytic activity palladium (Ⅱ) complexes containing bulky azole ligands. Chin. J. Struct. Chem. 2020, 39, 1669-1674.
19. [19]
  Chirik, P. J. Dinitrogen functionalization with bis(cyclopentadienyl) complexes of zirconium and hafnium. Dalton Trans. 2007, 16-25.
20. [20]
  Pfirrmann, S.; Limberg, C.; Herwig, C.; Stößer, R.; Ziemer, B. A dinuclear nickel (Ⅰ) dinitrogen complex and its reduction in single-electron steps. Angew. Chem. Int. Ed. 2009, 48, 3357-3361. doi: 10.1002/anie.200805862
21. [21]
  Betley, T. A.; Peters, J. C. Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms. J. Am. Chem. Soc. 2003, 125, 10782-10783. doi: 10.1021/ja036687f
22. [22]
  Holland, P. L. Electronic structure and reactivity of three-coordinate iron complexes. Acc. Chem. Res. 2008, 41, 905-914. doi: 10.1021/ar700267b
23. [23]
  Lu, J. B.; Ma, X. L.; Wang, J. Q.; Jiang, Y. F.; Li, Y.; Hu, H. S.; Xiao, H.; Li, J. The df-d dative bonding in a uranium-cobalt heterobimetallic complex for efficient nitrogen fixation. Inorg. Chem. 2019, 58, 7433-7439. doi: 10.1021/acs.inorgchem.9b00598
24. [24]
  Ferreira, R. B.; Murray, L. J. Cyclophanes as platforms for reactive multimetallic complexes. Acc. Chem. Res. 2019, 52, 447-455. doi: 10.1021/acs.accounts.8b00559
25. [25]
  Eaton, M. C.; Catalano, V. J.; Shearer, J.; Murray, L. J. Dinitrogen insertion and cleavage by a metal-metal bonded tricobalt (Ⅰ) cluster. J. Am. Chem. Soc. 2021, 143, 5649-5653. doi: 10.1021/jacs.1c01840
26. [26]
  Allen, A. D.; Senoff, C. V. Nitrogenopentammineruthenium (Ⅱ) complexes. Chem. Commun. (London) 1965, 621-622.
27. [27]
  Harrison, D. F.; Weissberger, E.; Taube, H. Binuclear ion containing nitrogen as a bridging group. Science 1968, 159, 320-322. doi: 10.1126/science.159.3812.320
28. [28]
  Pun, D.; Lobkovsky, E.; Chirik, P. J. Indenyl zirconium dinitrogen chemistry: N₂ coordination to an isolated zirconium sandwich and synthesis of side-on, end-on dinitrogen compounds. J. Am. Chem. Soc. 2008, 130, 6047-6054. doi: 10.1021/ja801021w
29. [29]
  Fryzuk, M. D. Side-on end-on bound dinitrogen: an activated bonding mode that facilitates functionalizing molecular nitrogen. Acc. Chem. Res. 2009, 42, 127-133. doi: 10.1021/ar800061g
30. [30]
  Chalkley, M. J.; Drover, M. W.; Peters, J. C. Catalytic N₂-to-NH₃ (or-N₂H₄) conversion by well-defined molecular coordination complexes. Chem. Rev. 2020, 120, 5582-5636. doi: 10.1021/acs.chemrev.9b00638
31. [31]
  Yandulov, D. V.; Schrock, R. R. Catalytic reduction of dinitrogen to ammonia at a single molybdenum center. Science 2003, 301, 76-78. doi: 10.1126/science.1085326
32. [32]
  Arashiba, K.; Miyake, Y.; Nishibayashi, Y. A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia. Nat. Chem. 2011, 3, 120-125. doi: 10.1038/nchem.906
33. [33]
  Anderson, J. S.; Rittle, J.; Peters, J. C. Catalytic conversion of nitrogen to ammonia by an iron model complex. Nature 2013, 501, 84-87. doi: 10.1038/nature12435
34. [34]
  Takahashi, T.; Mizobe, Y.; Sato, M.; Uchida, Y.; Hidai, M. Protonation reactions of molybdenum and tungsten dinitrogen complexes with halogen acids. Hydride hydrazido (2-) and diazenido complexes as intermediate stages of reduction. J. Am. Chem. Soc. 1980, 102, 7461-7467. doi: 10.1021/ja00545a011
35. [35]
  Oshita, H.; Mizobe, Y.; Hidai, M. Preparation and properties of molybdenum and tungsten dinitrogen complexes: XLI^*. Silylation and germylation of a coordinated dinitrogen in cis-[M(N₂)₂(PMe₂Ph)₄] (M = Mo, W) using R₃ECl/NaI and R₃ECl/Na mixtures (E = Si, Ge). X-ray structure of trans-[WI(NNGePh₃)(PMe₂Ph)₄]·C₆H₆. J. Organomet. Chem. 1993, 456, 213-220. doi: 10.1016/0022-328X(93)80428-E
36. [36]
  Hidai, M.; Mizobe, Y. Recent advances in the chemistry of dinitrogen complexes. Chem. Rev. 1995, 95, 1115-1133. doi: 10.1021/cr00036a008
37. [37]
  Tanabe, Y.; Nishibayashi, Y. Catalytic dinitrogen fixation to form ammonia at ambient reaction conditions using transition metal-dinitrogen complexes. Chem. Rec. 2016, 16, 1549-1577. doi: 10.1002/tcr.201600025
38. [38]
  Lee, Y.; Mankad, N. P.; Peters, J. C. Triggering N₂ uptake via redox-induced expulsion of coordinated NH₃ and N₂ silylation at trigonal bipyramidal iron. Nat. Chem. 2010, 2, 558-565. doi: 10.1038/nchem.660
39. [39]
  Moret, M. -E.; Peters, J. C. N₂ functionalization at iron metallaboratranes. J. Am. Chem. Soc. 2011, 133, 18118-18121. doi: 10.1021/ja208675p
40. [40]
  Suess, D. L.; Peters, J. C. H-H and Si-H bond addition to Fe≡NNR₂ intermediates derived from N₂. J. Am. Chem. Soc. 2013, 135, 4938-4941. doi: 10.1021/ja400836u
41. [41]
  Ung, G.; Peters, J. C. Low-temperature N₂ binding to two-coordinate L₂Fe⁰ enables reductive trapping of L₂FeN₂^- and NH₃ generation. Angew. Chem. Int. Ed. 2015, 54, 532-535.
42. [42]
  Higuchi, J.; Kuriyama, S.; Eizawa, A.; Arashiba, K.; Nakajima, K.; Nishibayashi, Y. Preparation and reactivity of iron complexes bearing anionic carbazole-based PNP-type pincer ligands toward catalytic nitrogen fixation. Dalton Trans. 2018, 47, 1117-1121. doi: 10.1039/C7DT04327A
43. [43]
  Bezdek, M. J.; Guo, S.; Chirik, P. J. Terpyridine molybdenum dinitrogen chemistry: synthesis of dinitrogen complexes that vary by five oxidation states. Inorg. Chem. 2016, 55, 3117-3127. doi: 10.1021/acs.inorgchem.6b00053
44. [44]
  Klopsch, I.; Finger, M.; Wurtele, C.; Milde, B.; Werz, D. B.; Schneider, S. Dinitrogen splitting and functionalization in the coordination sphere of rhenium. J. Am. Chem. Soc. 2014, 136, 6881-6883. doi: 10.1021/ja502759d
45. [45]
  Tanaka, H.; Nishibayashi, Y.; Yoshizawa, K. Interplay between theory and experiment for ammonia synthesis catalyzed by transition metal complexes. Acc. Chem. Res. 2016, 49, 987-995. doi: 10.1021/acs.accounts.6b00033
46. [46]
  Fryzuk, M. D.; Kozak, C. M.; Bowdridge, M. R.; Patrick, B. O.; Rettig, S. J. Nitride formation by thermolysis of a kinetically stable niobium dinitrogen complex. J. Am. Chem. Soc. 2002, 124, 8389-8397. doi: 10.1021/ja025997f
47. [47]
  Evans, W. J.; Chamberlain, L.; Ulibarri, T. A.; Ziller, J. W. Reactivity of trimethylaluminum with (C₅Me₅)₂Sm(THF)₂: synthesis, structure, and reactivity of the samarium methyl complexes (C₅Me₅)₂Sm[(μ-Me)AlMe₂-(μ-Me)]₂Sm(C₅Me₅)₂ and (C₅Me₅)₂SmMe(THF). J. Am. Chem. Soc. 1988, 110, 6423-6432. doi: 10.1021/ja00227a023
48. [48]
  MacLachlan, E. A.; Fryzuk, M. D. Synthesis and reactivity of side-on-bound dinitrogen metal complexes. Organometallics 2006, 25, 1530-1543. doi: 10.1021/om051055i
49. [49]
  Ma, X.; Tang, Y.; Lei, M. Bent and planar structures of μ-η²: η²-N₂ dinuclear early transition metal complexes. Dalton Trans. 2014, 43, 11658-11666. doi: 10.1039/C4DT00646A
50. [50]
  Ding, K. Y.; Pierpont, A. W.; Brennessel, W. W.; Lukat-Rodgers, G.; Rodgers, K. R.; Cundari, T. R.; Bill, E.; Holland, P. L. Cobalt-dinitrogen complexes with weakened N-N bonds. J. Am. Chem. Soc. 2009, 131, 9471-9472. doi: 10.1021/ja808783u
51. [51]
  Fryzuk, M. D.; Love, J. B.; Rettig, S. J.; Young, V. G. Transformation of coordinated dinitrogen by reaction with dihydrogen and primary silanes. Science 1997, 275, 1445-1447. doi: 10.1126/science.275.5305.1445
52. [52]
  Falcone, M.; Chatelain, L.; Scopelliti, R.; Živković, I.; Mazzanti, M. Nitrogen reduction and functionalization by a multimetallic uranium nitride complex. Nature 2017, 547, 332-335. doi: 10.1038/nature23279
53. [53]
  Fryzuk, M. D.; Johnson, S. A.; Rettig, S. J. New mode of coordination for the dinitrogen ligand: a dinuclear tantalum complex with a bridging N₂ unit that is both side-on and end-on. J. Am. Chem. Soc. 1998, 120, 11024-11025. doi: 10.1021/ja982377z
54. [54]
  Fryzuk, M. D.; Johnson, S. A.; Patrick, B. O.; Albinati, A.; Mason, S. A.; Koetzle, T. F. 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. 2001, 123, 3960-3973. doi: 10.1021/ja0041371
55. [55]
  Figg, T. M.; Holland, P. L.; Cundari, T. R. Cooperativity between low-valent iron and potassium promoters in dinitrogen fixation. Inorg. Chem. 2012, 51, 7546-7550. doi: 10.1021/ic300150u
56. [56]
  MacLeod, K. C.; Vinyard, D. J.; Holland, P. L. A multi-iron system capable of rapid N₂ formation and N₂ cleavage. J. Am. Chem. Soc. 2014, 136, 10226-10229. doi: 10.1021/ja505193z
57. [57]
  Singh, D.; Buratto, W. R.; Torres, J. F.; Murray, L. J. Activation of dinitrogen by polynuclear metal complexes. Chem. Rev. 2020, 120, 5517-5581. doi: 10.1021/acs.chemrev.0c00042
58. [58]
  Smith, J. M.; Sadique, A. R.; Cundari, T. R.; Rodgers, K. R.; Lukat-Rodgers, G.; Lachicotte, R. J.; Flaschenriem, C. J.; Vela, J.; Holland, P. L. Studies of low-coordinate iron dinitrogen complexes. J. Am. Chem. Soc. 2006, 128, 756-769. doi: 10.1021/ja052707x
59. [59]
  Chiang, K. P.; Bellows, S. M.; Brennessel, W. W.; Holland, P. L. Multimetallic cooperativity in activation of dinitrogen at iron-potassium sites. Chem. Sci. 2014, 5, 267-274. doi: 10.1039/C3SC52487F
60. [60]
  McWilliams, S. F.; Holland, P. L. Dinitrogen binding and cleavage by multinuclear iron complexes. Acc. Chem. Res. 2015, 48, 2059-2065. doi: 10.1021/acs.accounts.5b00213
61. [61]
  Reiners, M.; Baabe, D.; Munster, K.; Zaretzke, M. K.; Freytag, M.; Jones, P. G.; Coppel, Y.; Bontemps, S.; del Rosal, I.; Maron, L.; Walter, M. D. NH₃ formation from N₂ and H₂ mediated by molecular tri-iron complexes. Nat. Chem. 2020, 12, 740-746. doi: 10.1038/s41557-020-0483-7
62. [62]
  Xin, X.; Douair, I.; Zhao, Y.; Wang, S.; Maron, L.; Zhu, C. Dinitrogen cleavage by a heterometallic cluster featuring multiple uranium-rhodium bonds. J. Am. Chem. Soc. 2020, 142, 15004-15011. doi: 10.1021/jacs.0c05788
63. [63]
  Jori, N.; Barluzzi, L.; Douair, I.; Maron, L.; Fadaei-Tirani, F.; Zivkovic, I.; Mazzanti, M. Stepwise reduction of dinitrogen by a uranium-potassium complex yielding a U(Ⅵ)/U(Ⅳ) tetranitride cluster. J. Am. Chem. Soc. 2021, 143, 11225-11234. doi: 10.1021/jacs.1c05389
64. [64]
  Forrest, S. J.; Schluschaß, B.; Yuzik-Klimova, E. Y.; Schneider, S. Nitrogen fixation via splitting into nitrido complexes. Chem. Rev. 2021, 121, 6522-6587. doi: 10.1021/acs.chemrev.0c00958
65. [65]
  Cui, C. N.; Zhang, H. Y.; Luo, Z. X.; Pan, F. Preparation and reaction of naked metal clusters for catalysis and genetic materials. Chin. J. Struct. Chem. 2020, 39, 989-998.
66. [66]
  Han, Y.; Jiang, Y.; Yang, J. J.; Lin, S. C.; Tang, Z. C.; Zheng, L. S. Tuning solvent composition to enhance the stability of metal clusters in mass spectrometry. Chin. J. Struct. Chem. 2022, 41, 2204034-2204039.
67. [67]
  Kuganathan, N.; Green, J. C.; Himmel, H. -J. Dinitrogen fixation and activation by Ti and Zr atoms, clusters and complexes. New J. Chem. 2006, 30, 1253-1262. doi: 10.1039/b606328d
68. [68]
  Zhao, Y.; Cui, J. T.; Wang, M.; Valdivielso, D. Y.; Fielicke, A.; Hu, L. R.; Cheng, X.; Liu, Q. Y.; Li, Z. Y.; He, S. G.; Ma, J. B. Dinitrogen fixation and reduction by Ta₃N₃H_{0, 1}^- cluster anions at room temperature: hydrogen-assisted enhancement of reactivity. J. Am. Chem. Soc. 2019, 141, 12592-12600. doi: 10.1021/jacs.9b03168
69. [69]
  Li, Z. Y.; Mou, L. H.; Wei, G. P.; Ren, Y.; Zhang, M. Q.; Liu, Q. Y.; He, S. G. C-N coupling in N₂ fixation by the ditantalum carbide cluster anions Ta₂C₄^-. Inorg. Chem. 2019, 58, 4701-4705. doi: 10.1021/acs.inorgchem.8b03502
70. [70]
  Geng, C.; Li, J.; Weiske, T.; Schwarz, H. Complete cleavage of the N≡N triple bond by Ta₂N⁺ via degenerate ligand exchange at ambient temperature: a perfect catalytic cycle. Proc. Natl. Acad. Sci. U. S. A. 2019, 116, 21416-21420. doi: 10.1073/pnas.1913664116
71. [71]
  Li, Z. Y.; Li, Y.; Mou, L. H.; Chen, J. J.; Liu, Q. Y.; He, S. G.; Chen, H. A facile N≡N bond cleavage by the trinuclear metal center in vanadium carbide cluster anions V₃C₄^-. J. Am. Chem. Soc. 2020, 142, 10747-10754. doi: 10.1021/jacs.0c02021
72. [72]
  Wang, X. Y.; Peng, X. B.; Zhang, Y. F.; Ni, J.; Au, C. T.; Jiang, L. L. Efficient ammonia synthesis over a core-shell Ru/CeO₂ catalyst with a tunable CeO₂ size: DFT calculations and XAS spectroscopy studies. Inorg. Chem. Front. 2019, 6, 396-406. doi: 10.1039/C8QI01244J
73. [73]
  Himmel, H. J.; Hübner, O.; Klopper, W.; Manceron, L. Cleavage of the N₂ triple bond by the Ti dimer: a route to molecular materials for dinitrogen activation? Angew. Chem. Int. Ed. 2006, 45, 2799-2802. doi: 10.1002/anie.200503709
74. [74]
  Zhou, M.; Jin, X.; Gong, Y.; Li, J. Remarkable dinitrogen activation and cleavage by the Gd dimer: from dinitrogen complexes to ring and cage nitrides. Angew. Chem. Int. Ed. 2007, 46, 2911-2914. doi: 10.1002/anie.200605218
75. [75]
  Gong, Y.; Zhao, Y.; Zhou, M. Formation and characterization of the tetranuclear scandium nitride: Sc₄N₄. J. Phys. Chem. A. 2007, 111, 6204-6207. doi: 10.1021/jp070816n
76. [76]
  Jiang, G. D.; Li, Z. Y.; Mou, L. H.; He, S. G. Dual iron sites in activation of N₂ by iron-sulfur cluster anions Fe₅S₂^- and Fe₅S₃^-. J. Phys. Chem. Lett. 2021, 12, 9269-9274. doi: 10.1021/acs.jpclett.1c02683
77. [77]
  Mou, L. H.; Li, Y.; Li, Z. Y.; Liu, Q. Y.; Ren, Y.; Chen, H.; He, S. G. Dinitrogen activation and functionalization by heteronuclear metal cluster anions FeV₂C₂^- at room temperature. J. Phys. Chem. Lett. 2020, 11, 9990-9994. doi: 10.1021/acs.jpclett.0c02921
78. [78]
  Ma, X. L.; Liu, J. C.; Xiao, H.; Li, J. Surface single-cluster catalyst for N₂-to-NH₃ thermal conversion. J. Am. Chem. Soc. 2018, 140, 46-49. doi: 10.1021/jacs.7b10354
79. [79]
  Liu, J. C.; Ma, X. L.; Li, Y.; Wang, Y. G.; Xiao, H.; Li, J. Heterogeneous Fe₃ single-cluster catalyst for ammonia synthesis via an associative mechanism. Nat. Commun. 2018, 9, 1610. doi: 10.1038/s41467-018-03795-8
80. [80]
  Cherkasov, N.; Ibhadon, A.; Fitzpatrick, P. A review of the existing and alternative methods for greener nitrogen fixation. Chem. Eng. Process. 2015, 90, 24-33. doi: 10.1016/j.cep.2015.02.004
81. [81]
  Zhang, X.; Chen, A.; Zhang, Z.; Zhou, Z. Double-atom catalysts: transition metal dimer-anchored C₂N monolayers as N₂ fixation electrocatalysts. J. Mater. Chem. A 2018, 6, 18599-18604. doi: 10.1039/C8TA07683A
82. [82]
  Chen, Z. W.; Yan, J. M.; Jiang, Q. Single or double: which is the altar of atomic catalysts for nitrogen reduction reaction? Small Methods 2019, 3, 1800291. doi: 10.1002/smtd.201800291
83. [83]
  Han, B.; Meng, H.; Li, F.; Zhao, J. Fe₃ cluster anchored on the C₂N monolayer for efficient electrochemical nitrogen fixation. Catalysts 2020, 10, 974. doi: 10.3390/catal10090974
84. [84]
  Ma, D.; Zeng, Z.; Liu, L.; Huang, X.; Jia, Y. Computational evaluation of electrocatalytic nitrogen reduction on TM single-, double-, and triple-atom catalysts (TM = Mn, Fe, Co, Ni) based on graphdiyne monolayers. J. Phys. Chem. C 2019, 123, 19066-19076. doi: 10.1021/acs.jpcc.9b05250
85. [85]
  Li, M.; Cui, Y.; Zhang, X.; Luo, Y.; Dai, Y.; Huang, Y. Screening a suitable Mo form supported on graphdiyne for effectively electrocatalytic N₂ reduction reaction: from atomic catalyst to cluster catalyst. J. Phys. Chem. Lett. 2020, 11, 8128-8137. doi: 10.1021/acs.jpclett.0c02354
86. [86]
  Chen, Z. W.; Chen, L. X.; Jiang, M.; Chen, D.; Wang, Z. L.; Yao, X.; Singh, C. V.; Jiang, Q. A triple atom catalyst with ultrahigh loading potential for nitrogen electrochemical reduction. J. Mater. Chem. A 2020, 8, 15086-15093. doi: 10.1039/D0TA04919K
87. [87]
  Zheng, G.; Li, L.; Tian, Z.; Zhang, X.; Chen, L. Heterogeneous single-cluster catalysts (Mn₃, Fe₃, Co₃, and Mo₃) supported on nitrogen-doped graphene for robust electrochemical nitrogen reduction. J. Energy Chem. 2021, 54, 612-619. doi: 10.1016/j.jechem.2020.06.048
88. [88]
  Cui, C. N.; Zhang, H. C.; Luo, Z. X. Nitrogen reduction reaction on small iron clusters supported by N-doped graphene: a theoretical study of the atomically precise active-site mechanism. Nano Res. 2020, 13, 2280-2288. doi: 10.1007/s12274-020-2847-0
89. [89]
  Zhang, H. C.; Cui, C. N.; Luo, Z. X. MoS₂-supported Fe₂ clusters catalyzing nitrogen reduction reaction to produce ammonia. J. Phys. Chem. C 2020, 124, 6260-6266. doi: 10.1021/acs.jpcc.0c00486
90. [90]
  Yao, C. H.; Guo, N.; Xi, S. B.; Xu, C. Q.; Liu, W.; Zhao, X. X.; Li, J.; Fang, H. Y.; Su, J.; Chen, Z. X. Atomically-precise dopant-controlled single cluster catalysis for electrochemical nitrogen reduction. Nat. Commun. 2020, 11, 4389. doi: 10.1038/s41467-020-18080-w
91. [91]
  Ma, X. L.; Yang, Y.; Xu, L. M.; Xiao, H.; Yao, W. Z.; Li, J. Theoretical investigation on hydrogenation of dinitrogen triggered by singly dispersed bimetallic sites. J. Mater. Chem. A 2022, 10, 6146-6152. doi: 10.1039/D1TA08350C
92. [92]
  Luo, Y.; Li, M.; Dai, Y.; Zhao, R.; Jiang, F.; Wang, S.; Huang, Y. Transition metal-modified Co₄ clusters supported on graphdiyne as an effective nitrogen reduction reaction electrocatalyst. Inorg. Chem. 2021, 60, 18251-18259. doi: 10.1021/acs.inorgchem.1c02880
93. [93]
  Wang, Q.; Pan, J.; Guo, J.; Hansen, H. A.; Xie, H.; Jiang, L.; Hua, L.; Li, H.; Guan, Y.; Wang, P. Ternary ruthenium complex hydrides for ammonia synthesis via the associative mechanism. Nat. Catal. 2021, 4, 959-967. doi: 10.1038/s41929-021-00698-8
94. [94]
  Liu, C.; Wang, Q.; Guo, J.; Vegge, T.; Chen, P.; Hansen, H. A. Formation of a complex active center by Ba₂RuH₆ for nondissociative dinitrogen activation and ammonia formation. ACS Catal. 2022, 12, 4194-4202. doi: 10.1021/acscatal.2c00180
95. [95]
  Wang, X. Y.; Li, L. L.; Fang, Z. P.; Zhang, Y. F.; Ni, J.; Lin, B. Y.; Zheng, L. R.; Au, C. -T.; Jiang, L. L. Atomically dispersed Ru catalyst for low-temperature nitrogen activation to ammonia via an associative mechanism. ACS Catal. 2020, 10, 9504-9514. doi: 10.1021/acscatal.0c00549
96. [96]
  Wang, X. Y.; Peng, X. B.; Chen, W.; Liu, G. Y.; Zheng, A. M.; Zheng, L. R.; Ni, J.; Au, C. T.; Jiang, L. L. Insight into dynamic and steady-state active sites for nitrogen activation to ammonia by cobalt-based catalyst. Nat. Commun. 2020, 11, 653. doi: 10.1038/s41467-020-14287-z
97. [97]
  Hu, H. S.; Xu, X.; Xu, C.; Li. J. Recent progresses in experimental and theoretical studies of actinide clusters. Chin. J. Struct. Chem. 2020, 39, 1201-1212.
98. [98]
  Liu, J. C.; Xiao, H.; Zhao, X. K.; Zhang, N. N.; Liu, Y.; Xing, D. H.; Yu, X. H.; Hu, H. S.; Li, J. Computational prediction of graphdiyne-supported three-atom single-cluster catalysts. CCS Chem. 2022, DOI: 10.31635/ccschem.022.202201796. doi: 10.31635/ccschem.022.202201796
1. [1]
  Yuanjin Chen , Xianghui Shi , Dajiang Huang , Junnian Wei , Zhenfeng Xi . Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand. Chinese Chemical Letters, 2024, 35(7): 109292-. doi: 10.1016/j.cclet.2023.109292
2. [2]
  Guoju Guo , Xufeng Li , Jie Ma , Yongjia Shi , Jian Lv , Daoshan Yang . Photocatalyst/metal-free sequential C–N/C–S bond formation: Synthesis of S-arylisothioureas via photoinduced EDA complex activation. Chinese Chemical Letters, 2024, 35(11): 110024-. doi: 10.1016/j.cclet.2024.110024
3. [3]
  Huazhe Wang , Chenghuan Qiao , Chuchu Chen , Bing Liu , Juanshan Du , Qinglian Wu , Xiaochi Feng , Shuyan Zhan , Wan-Qian Guo . Synergistic adsorption and singlet oxygenation of humic acid on alkali-activated biochar via peroxymonosulfate activation. Chinese Chemical Letters, 2025, 36(5): 110244-. doi: 10.1016/j.cclet.2024.110244
4. [4]
  Fengrui Yang , Debing Wang , Xinying Zhang , Jie Zhang , Zhichao Wu , Qiaoying Wang . Synergistic effects of peroxydisulfate on UV/O₃ process for tetracycline degradation: Mechanism and pathways. Chinese Chemical Letters, 2024, 35(10): 109599-. doi: 10.1016/j.cclet.2024.109599
5. [5]
  Xiaotao Jin , Yanlan Wang , Yingping Huang , Di Huang , Xiang Liu . Percarbonate activation catalyzed by nanoblocks of basic copper molybdate for antibiotics degradation: High performance, degradation pathways and mechanism. Chinese Chemical Letters, 2024, 35(10): 109499-. doi: 10.1016/j.cclet.2024.109499
6. [6]
  Shenglan Zhou , Haijian Li , Hongyi Gao , Ang Li , Tian Li , Shanshan Cheng , Jingjing Wang , Jitti Kasemchainan , Jianhua Yi , Fengqi Zhao , Wengang Qu . Recent advances in metal-loaded MOFs photocatalysts: From single atom, cluster to nanoparticle. Chinese Chemical Letters, 2025, 36(1): 110142-. doi: 10.1016/j.cclet.2024.110142
7. [7]
  Xuying Yu , Jiarong Mi , Yulan Han , Cai Sun , Mingsheng Wang , Guocong Guo . A stable radiochromic semiconductive viologen-based metal–organic framework for dual-mode direct X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109233-. doi: 10.1016/j.cclet.2023.109233
8. [8]
  Wenjuan Jin , Zelong Chen , Yi Wang , Jiaxuan Li , Jiahui Li , Yuxin Pei , Zhichao Pei . Nano metal-photosensitizer based on Aza-BODIPY-Cu complex for CDT-enhanced dual phototherapy. Chinese Chemical Letters, 2024, 35(7): 109328-. doi: 10.1016/j.cclet.2023.109328
9. [9]
  Chunxiu Yu , Zelin Wu , Hongle Shi , Lingyun Gu , Kexin Chen , Chuan-Shu He , Yang Liu , Heng Zhang , Peng Zhou , Zhaokun Xiong , Bo Lai . Insights into the electron transfer mechanisms of peroxydisulfate activation by modified metal-free acetylene black for degradation of sulfisoxazole. Chinese Chemical Letters, 2024, 35(8): 109334-. doi: 10.1016/j.cclet.2023.109334
10. [10]
  Yinyin Xu , Yuanyuan Li , Jingbo Feng , Chen Wang , Yan Zhang , Yukun Wang , Xiuwen Cheng . Covalent organic frameworks doped with manganese-metal organic framework for peroxymonosulfate activation. Chinese Chemical Letters, 2024, 35(4): 108838-. doi: 10.1016/j.cclet.2023.108838
11. [11]
  Boqiang Wang , Yongzhuo Xu , Jiajia Wang , Muyang Yang , Guo-Jun Deng , Wen Shao . Transition-metal free trifluoromethylimination of alkenes enabled by direct activation of N-unprotected ketimines. Chinese Chemical Letters, 2024, 35(9): 109502-. doi: 10.1016/j.cclet.2024.109502
12. [12]
  Yanjun Cai , Yong Jiang , Yu Chen , Erzhuo Cheng , Yuan Gu , Yuwei Li , Qianqian Liu , Jian Zhang , Jifang Liu , Shisong Han , Bin Yang . Amplifying STING activation and immunogenic cell death by metal-polyphenol coordinated nanomedicines for enhanced cancer immunotherapy. Chinese Chemical Letters, 2025, 36(5): 110437-. doi: 10.1016/j.cclet.2024.110437
13. [13]
  Fahui Xiang , Lu Li , Zhen Yuan , Wuji Wei , Xiaoqing Zheng , Shimin Chen , Yisi Yang , Liangji Chen , Zizhu Yao , Jianwei Fu , Zhangjing Zhang , Shengchang Xiang . Enhanced C₂H₂/CO₂ separation in tetranuclear Cu(Ⅱ) cluster-based metal-organic frameworks by adjusting divider length of pore space partition. Chinese Chemical Letters, 2025, 36(3): 109672-. doi: 10.1016/j.cclet.2024.109672
14. [14]
  Panpan Wang , Hongbao Fang , Mengmeng Wang , Guandong Zhang , Na Xu , Yan Su , Hongke Liu , Zhi Su . A mitochondria targeting Ir(III) complex triggers ferroptosis and autophagy for cancer therapy: A case of aggregation enhanced PDT strategy for metal complexes. Chinese Chemical Letters, 2025, 36(1): 110099-. doi: 10.1016/j.cclet.2024.110099
15. [15]
  Chunhui Zhang , Jie Wang , Jieyang Zhan , Runmin Yang , Guanggang Gao , Jiayuan Zhang , Linlin Fan , Mengqi Wang , Hong Liu . Highly sensitive hydrazine detection through a novel Raman scattering quenching mechanism enabled by a crystalline and noble metal–free polyoxometalate substrate. Chinese Chemical Letters, 2025, 36(3): 109719-. doi: 10.1016/j.cclet.2024.109719
16. [16]
  Haiming Wu , Gaya N. Andrew , Rajini Anumula , Zhixun Luo . Corrigendum to 'How ligand coordination and superatomic-states accommodate the structure and property of a metal cluster: Cu₄ (dppy)₄ Cl₂ vs. Cu₂₁ (dppy)₁₀ with altered photoluminescence' [Chin. Chem. Lett. 35 (2024) 108340]. Chinese Chemical Letters, 2024, 35(12): 109912-. doi: 10.1016/j.cclet.2024.109912
17. [17]
  Mochou GAO , Shan MENG , Jinzhong ZHANG , Wenhua FENG , Shuo DONG , Jianping CHEN , Yanbao ZHAO , Laigui YU , Rongrong YING , Xueyan ZOU . Dual‐surface capped hydroxyapatite nano‐amendment with tuned alternate long‐short chain configuration for efficient adsorption towards multi‐heavy metal ions in complex‐contaminated systems. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1427-1438. doi: 10.11862/CJIC.20240431
18. [18]
  Xianghe Kong , Xiaoli Liao , Zhenkun Huang , Lei Mei , Hongqing Wang , Kongqiu Hu , Weiqun Shi . Designed assembly of heterometallic cluster organic frameworks based on Th₆ cluster. Chinese Chemical Letters, 2024, 35(11): 109642-. doi: 10.1016/j.cclet.2024.109642
19. [19]
  Zhenyang Lin . A classification scheme for inorganic cluster compounds based on their electronic structures and bonding characteristics. Chinese Journal of Structural Chemistry, 2024, 43(5): 100254-100254. doi: 10.1016/j.cjsc.2024.100254
20. [20]
  Wu-Jian Long , Yang Yu , Chuang He . A novel and promising engineering application of carbon dots: Enhancing the chloride binding performance of cement. Chinese Chemical Letters, 2024, 35(6): 108943-. doi: 10.1016/j.cclet.2023.108943

Get Citation

PDF

XML

Metrics

PDF Downloads(32)
Abstract views(1884)
HTML views(88)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142