Citation: Ya-Nan Yang, Zi-Sheng Li, Sourav Mondal, Lei Qiao, Cui-Cui Wang, Wen-Juan Tian, Zhong-Ming Sun, John E. McGrady. Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–[J]. Chinese Chemical Letters, ;2024, 35(8): 109048. doi: 10.1016/j.cclet.2023.109048 shu

Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–

Ya-Nan Yang ^{a, 1} ,
Zi-Sheng Li ^{b, 1} ,
Sourav Mondal ^b ,
Lei Qiao ^a ,
Cui-Cui Wang ^a ,
Wen-Juan Tian ^a ,
Zhong-Ming Sun ^{a, *,} ,
John E. McGrady ^{b, *,}

a.
State Key Laboratory of Element-Organic Chemistry, Tianjin Key Lab for Rare Earth Materials and Applications, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
b.
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, Oxford, OX1 3QR, United Kingdom

sunlab@nankai.edu.cn

john.mcgrady@chem.ox.ac.uk

Received Date: 8 August 2023
Revised Date: 29 August 2023
Accepted Date: 3 September 2023
Available Online: 7 September 2023

Figures(10)

We report here the synthesis and characterization of two new members of the M₂E₁₂ family of endohedral Zintl clusters, [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–, both of which contain open-shell metal dimers encapsulated inside a triple-decker cluster of main-group atoms. The 75-electron [Fe₂Sn₄Bi₈]^3– cluster has a D_4h-symmetric structure, while [Cr₂Sb₁₂]^3–, despite having the same 75-electron count, is strongly distorted to a geometry that resembles a CrSb₈ crown capped by a CrSb₄ unit. The structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transition metal, which leads, ultimately, to different electronic configurations in the two clusters. The trends precisely mirror those observed in the ME₁₀ and ME₁₂ families containing a single transition metal ion.
- Zintl anions,
- Endohedral clusters,
- Metal-metal bond,
- Second-order Jahn-Teller effect,
- DFT calculation
1. [1]
  B. Weinert, S. Dehnen, Binary and ternary intermetalloid Clusters, in: S. Dehnen (Ed.), Clusters – Contemporary Insight in Structure and Bonding, Springer International Publishing, Cham, 2017, pp. 99–134.
2. [2]
  J. Zhao, Q. Du, S. Zhou, V. Kumar, Chem. Rev. 120 (2020) 9021–9163. doi: 10.1021/acs.chemrev.9b00651
3. [3]
  B. Oelkers, M.V. Butovskii, R. Kempe, Chem. Eur. J. 18 (2012) 13566–13579. doi: 10.1002/chem.201200783
4. [4]
  N. Lichtenberger, R.J. Wilson, A.R. Eulenstein, et al., J. Am. Chem. Soc. 138 (2016) 9033–9036. doi: 10.1021/jacs.6b04363
5. [5]
  X. Min, I.A. Popov, F.X. Pan, et al., Angew. Chem. Int. Ed. 55 (2016) 5531–5535. doi: 10.1002/anie.201600706
6. [6]
  A.R. Eulenstein, Y.J. Franzke, N. Lichtenberger, et al., Nat. Chem. 13 (2021) 149–155. doi: 10.1038/s41557-020-00592-z
7. [7]
  C. Dong, Y. Li, D. Cheng, et al., ACS Catal. 10 (2020) 11011–11045. doi: 10.1021/acscatal.0c02818
8. [8]
  K. Mayer, J. Weßing, T.F. Fässler, R.A. Fischer, Angew. Chem. Int. Ed. 57 (2018) 14372–14393. doi: 10.1002/anie.201805897
9. [9]
  X. Jin, J.E. McGrady, Chapter eight - structure and bonding in endohedral transition metal clusters, in: R. van Eldik, R. Puchta (Eds.), Advances in Inorganic Chemistry, Academic Press, 2019, pp. 265–304.
10. [10]
  J.E. McGrady, F. Weigend, S. Dehnen, Chem. Soc. Rev. 51 (2022) 628–649. doi: 10.1039/d1cs00775k
11. [11]
  Y. Wang, J.E. McGrady, Z.M. Sun, Acc. Chem. Res. 54 (2021) 1506–1516. doi: 10.1021/acs.accounts.0c00876
12. [12]
  R.J. Wilson, N. Lichtenberger, B. Weinert, S. Dehnen, Chem. Rev. 119 (2019) 8506–8554. doi: 10.1021/acs.chemrev.8b00658
13. [13]
  E.N. Esenturk, J. Fettinger, B. Eichhorn, J. Am. Chem. Soc. 128 (2006) 9178–9186. doi: 10.1021/ja061842m
14. [14]
  K. Wade, J. Chem. Soc. D: Chem. Commun. (1971) 792–793.
15. [15]
  B. Zhou, T. Krämer, A.L. Thompson, J.E. McGrady, J.M. Goicoechea, Inorg. Chem. 50 (2011) 8028–8037. doi: 10.1021/ic200329m
16. [16]
  T. Krämer, J.C.A. Duckworth, M.D. Ingram, et al., Dalton Trans. 42 (2013) 12120–12129. doi: 10.1039/c3dt50643f
17. [17]
  J.Q. Wang, S. Stegmaier, T.F. Fässler, Angew. Chem. Int. Ed. 48 (2009) 1998–2002. doi: 10.1002/anie.200805511
18. [18]
  B. Zhou, M.S. Denning, D.L. Kays, J.M. Goicoechea, J. Am. Chem. Soc. 131 (2009) 2802–2803. doi: 10.1021/ja900055j
19. [19]
  G. Espinoza-Quintero, J.C.A. Duckworth, W.K. Myers, J.E. McGrady, J.M. Goicoechea, J. Am. Chem. Soc. 136 (2014) 1210–1213. doi: 10.1021/ja411280v
20. [20]
  S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend, S. Dehnen, Nat. Commun. 7 (2016) 10480. doi: 10.1038/ncomms10480
21. [21]
  D.M.P. Mingos, Pure Appl. Chem. 63 (1991) 807–812. doi: 10.1351/pac199163060807
22. [22]
  F. Lips, R. Clérac, S. Dehnen, J. Am. Chem. Soc. 133 (2011) 14168–14171. doi: 10.1021/ja203302t
23. [23]
  C. Liu, X. Jin, L.J. Li, et al., Chem. Sci. 10 (2019) 4394–4401. doi: 10.1039/c8sc03948h
24. [24]
  H.W.T. Morgan, K.S. Csizi, Y.S. Huang, Z.M. Sun, J.E. McGrady, J. Phys. Chem. A 125 (2021) 4578–4588. doi: 10.1021/acs.jpca.1c02837
25. [25]
  H.W.T. Morgan, C.C. Shu, Z.M. Sun, J.E. McGrady, J. Am. Chem. Soc. 144 (2022) 8007–8017. doi: 10.1021/jacs.1c10106
26. [26]
  L. Qiao, C. Zhang, C.C. Shu, et al., J. Am. Chem. Soc. 142 (2020) 13288–13293. doi: 10.1021/jacs.0c04815
27. [27]
  V. Khanna, R. Singh, P. Claes, et al., J. Phys. Chem. A 126 (2022) 1617–1626. doi: 10.1021/acs.jpca.1c10027
28. [28]
  N.T. Mai, N.T. Tung, P.T. Thuy, N.T. Minh Hue, N.T. Cuong, Comput. Theoret. Chem. 1117 (2017) 124–129. doi: 10.1016/j.comptc.2017.08.012
29. [29]
  H.T. Pham, T.T. Phan, N.M. Tam, et al., Phys. Chem. Chem. Phys. 17 (2015) 17566–17570. doi: 10.1039/C5CP02257F
30. [30]
  V.T. Tran, Q.T. Tran, Int. J. Quant. Chem. 121 (2021) e26619. doi: 10.1002/qua.26619
31. [31]
  X. Li, P. Claes, M. Haertelt, et al., Phys. Chem. Chem. Phys. 18 (2016) 6291–6300. doi: 10.1039/C5CP07298K
32. [32]
  X.Q. Liang, X.J. Deng, S.J. Lu, et al., J. Phys. Chem. C 121 (2017) 7037–7046. doi: 10.1021/acs.jpcc.7b00943
33. [33]
  S.J. Lu, L.R. Hu, X.L. Xu, et al., Phys. Chem. Chem. Phys. 18 (2016) 20321–20329. doi: 10.1039/C6CP00373G
34. [34]
  M. Shibuta, T. Niikura, T. Kamoshida, H. Tsunoyama, A. Nakajima, Phys. Chem. Chem. Phys. 20 (2018) 26273–26279. doi: 10.1039/c8cp05580g
35. [35]
  H. Tsunoyama, H. Akatsuka, M. Shibuta, et al., J. Phys. Chem. C 121 (2017) 20507–20516. doi: 10.1021/acs.jpcc.7b06449
36. [36]
  M.F. Groh, U. Müller, A. Isaeva, M. Ruck, Zeitschrift für anorganische und allgemeine Chem. 645 (2019) 161–169. doi: 10.1002/zaac.201800441
37. [37]
  F. Lips, S. Dehnen, Angew. Chem. Int. Ed. 50 (2011) 955–959. doi: 10.1002/anie.201005496
38. [38]
  R. Ababei, J. Heine, M. Hołyńska, et al., Chem. Commun. 48 (2012) 11295–11297. doi: 10.1039/c2cc35318k
39. [39]
  R.J. Wilson, F. Hastreiter, K. Reiter, et al., Angew. Chem. Int. Ed. 57 (2018) 15359–15363. doi: 10.1002/anie.201807180
40. [40]
  S. Charles, B.W. Eichhorn, S.G. Bott, J. Am. Chem. Soc. 115 (1993) 5837–5838. doi: 10.1021/ja00066a067
41. [41]
  S.C. Critchlow, J.D. Corbett, Inorg. Chem. 21 (1982) 3286–3290. doi: 10.1021/ic00139a008
42. [42]
  L.O. Spreer, I. Shah, Inorg. Chem. 20 (1981) 4025–4027. doi: 10.1021/ic50225a093
43. [43]
  G. Sheldrick, Acta Cryst. A 71 (2015) 3–8. doi: 10.1107/S2053273314026370
44. [44]
  O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, J. Appl. Crystal. 42 (2009) 339–341. doi: 10.1107/S0021889808042726
45. [45]
  G. te Velde, F.M. Bickelhaupt, E.J. Baerends, et al., J. Comput. Chem. 22 (2001) 931–967. doi: 10.1002/jcc.1056
46. [46]
  J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865–3868. doi: 10.1103/PhysRevLett.77.3865
47. [47]
  E. van Lenthe, A. Ehlers, E.J. Baerends, J. Chem. Phys. 110 (1999) 8943–8953. doi: 10.1063/1.478813
48. [48]
  Y. Zhao, D.G. Truhlar, J. Chem. Phys. 125 (2006) 194101. doi: 10.1063/1.2370993
49. [49]
  C. Adamo, V. Barone, J. Chem. Phys. 110 (1999) 6158–6170. doi: 10.1063/1.478522
50. [50]
  E. Van Lenthe, E.J. Baerends, J. Comput. Chem. 24 (2003) 1142–1156. doi: 10.1002/jcc.10255
51. [51]
  M. Franchini, P.H.T. Philipsen, L. Visscher, J. Comput. Chem. 34 (2013) 1819–1827. doi: 10.1002/jcc.23323
52. [52]
  C.C. Pye, T. Ziegler, Theoret. Chem. Acc. 101 (1999) 396–408. doi: 10.1007/s002140050457
53. [53]
  F.M. Bickelhaupt, E.J. Baerends, Rev. Comput. Chem. (2000) 1–86. doi: 10.1002/9780470125922.ch1
54. [54]
  B. Kesanli, J. Fettinger, B. Eichhorn, J. Am. Chem. Soc. 125 (2003) 7367–7376. doi: 10.1021/ja034207e
55. [55]
  Z. Li, W. Wu, S. Li, J. Mol. Struct. Theochem. 908 (2009) 73–78. doi: 10.1016/j.theochem.2009.05.006
56. [56]
  H.G. von Schnering, J. Wolf, D. Weber, R. Ramirez, T. Meyer, Angew. Chem. Int. Ed. 25 (1986) 353–354. doi: 10.1002/anie.198603531
57. [57]
  S. Dehnen, C. Zimmermann, Zeitschrift für anorganische und allgemeine Chem. 628 (2002) 2463–2469. doi: 10.1002/1521-3749(200211)628:11<2463::AID-ZAAC2463>3.0.CO;2-Y
58. [58]
  C.H.E. Belin, J.D. Corbett, A. Cisar, J. Am. Chem. Soc. 99 (1977) 7163–7169. doi: 10.1021/ja00464a011
59. [59]
  T.F. Fässler, Coord. Chem. Rev. 215 (2001) 347–377. doi: 10.1016/S0010-8545(01)00321-6
60. [60]
  T.F. Fässler, U. Schütz, Inorg. Chem. 38 (1999) 1866–1870. doi: 10.1021/ic981157j
61. [61]
  J. Rienmüller, A. Schmidt, N.J. Yutronkie, et al., Angew. Chem. Int. Ed. 61 (2022) e202210683. doi: 10.1002/anie.202210683
62. [62]
  J.M. Goicoechea, J.E. McGrady, Dalton Trans. 44 (2015) 6755–6766. doi: 10.1039/C4DT03573A
63. [63]
  E.D. Jemmis, M.M. Balakrishnarajan, P.D. Pancharatna, J. Am. Chem. Soc. 123 (2001) 4313–4323. doi: 10.1021/ja003233z
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Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–