Citation: Bo JIN, Jian-Hong BIAN, Xue-Feng ZHAO, Cai-Xia YUAN, Jin-Chang GUO, Yan-Bo WU. Planar Tetracoordinate Carbon in 6σ + 2π Double Aromatic CBe₄^2– Derivatives[J]. Chinese Journal of Structural Chemistry, ;2022, 41(3): 220321. doi: 10.14102/j.cnki.0254-5861.2011-3332 shu

Planar Tetracoordinate Carbon in 6σ + 2π Double Aromatic CBe₄^2– Derivatives

a.
Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China
b.
Department of Chemistry, Changzhi University, Changzhi 046011, China

Corresponding author: Yan-Bo WU, wyb@sxu.edu.cn
Received Date: 14 August 2021
Accepted Date: 21 October 2021

Fund Project: the National Natural Science Foundation of China 21720102006the National Natural Science Foundation of China 22073058the National Natural Science Foundation of China 21973055the Natural Science Foundation of Shanxi Province 201901D111018the Natural Science Foundation of Shanxi Province 201901D111014the Shanxi"1331 Project" Engineering Research Center PT201807

Figures(7)

As a typical electron deficient element, beryllium is potentially suitable for designing the species with novel non-classical planar hypercoordinate carbon due to high preference for the planar structures by small beryllium-containing clusters. In particular, the CBe₅^4– cluster with a planar pentacoordinate carbon (ppC) had been proved by many previous studies to be an excellent template structure for the systematic design of ppC species through attaching various monovalent atoms on the bridging position of Be–Be edges. In this work, based on the analysis and extension on our recently reported CBe₄M_n^n–2 (M = Li, Au, n = 1~3) species, we propose that ptC cluster CBe₄^2– is similar to CBe₅^4– in that it can also be employed as a template structure to systematically design the ptC species through binding various monovalent atoms on the bridging position of Be–Be edges. Our extensive screening suggests that the feasible bridging atoms (E) can be found in group 1 (H, Li, Na), group 11 (Cu, Ag, Au), and group 17 (F, Cl, Br, I) elements, leading to total thirty eligible ptC species with CBe₄ core moiety (CBe₄E_n^n–2). The ptC atoms in these species are involved into three delocalized σ bonds and a delocalized π bond, thereby not only obeying the octet rule, but also possessing novel 6σ +2π double aromaticity, which significantly stabilizes the ptC arrangement. In addition, the attached bridging atoms can stabilize the CBe₄ core ptC moiety by replacing the highly diffused Be–Be two-center two-electron bonds with the much less diffused Be–E two-center two-electron bonds or Be–E–Be three-center two-electron bonds, as reflected by the increasing HOMO-LUMO gaps when the number of bridging atoms increases. Remarkably, the stochastic search algorithm in combination with high level CCSD(T) calculations revealed that twenty-six of the thirty-one ptC species (including previously reported six species) were global energy minima on their corresponding potential energy surfaces, in which twenty-five of them were also confirmed to be dynamically viable. They are suitable for the generation and characterization in gas phase experiments and followed spectroscopic studies.
- planar hypercoordinate carbon,
- aromaticity,
- beryllium,
- DFT calculations,
- global energy minimum
1. [1]
  Wang, Z. X.; Zhang, C. G.; Chen, Z.; Schleyer, P. V. R. Planar tetracoordinate carbon species involving beryllium substituents. Inorg. Chem. 2008, 47, 1332‒1336. doi: 10.1021/ic7017709
2. [2]
  Wu, Y. B.; Jiang, J. L.; Zhang, R. W.; Wang, Z. X. Computationally designed families of flat, tubular, and cage molecules assembled with "starbenzene" building blocks through hydrogen-bridge Bonds. Chem. -Eur. J. 2010, 16, 1271‒1280. doi: 10.1002/chem.200901983
3. [3]
  Zhao, X. F.; Li, H.; Yuan, C. X.; Li, Y. Q.; Wu, Y. B.; Wang, Z. X. Linear, planar, and tubular molecular structures constructed by double planar tetracoordinate carbon D_2h C₂(BeH)₄ species via hydrogen-bridged -BeH₂Be-bonds. J. Comput. Chem. 2016, 37, 261‒269. doi: 10.1002/jcc.24018
4. [4]
  Guo, J. C.; Feng, L. Y.; Dong, C.; Zhai, H. J. Planar pentacoordinate versus tetracoordinate carbons in ternary CBe₄Li₄ and CBe₄Li₄²⁻ clusters. J. Phys. Chem. A 2018, 122, 8370‒8376. doi: 10.1021/acs.jpca.8b08573
5. [5]
  Guo, J. C.; Feng, L. Y.; Dong, C.; Zhai, H. J. Ternary 12-electron CBe₃X₃⁺ (X = H, Li, Na, Cu, Ag) clusters: planar tetracoordinate carbons and superalkali cations. Phys. Chem. Chem. Phys. 2019, 21, 22048‒22056. doi: 10.1039/C9CP04437J
6. [6]
  Guo, J. C.; Feng, L. Y.; Zhai, H. J. Ternary CBe₄Au₄ cluster: a 16-electron system with quasi-planar tetracoordinate carbon. Phys. Chem. Chem. Phys. 2018, 20, 6299‒6306. doi: 10.1039/C7CP08420J
7. [7]
  Jimenez Halla, J. O. C.; Wu, Y. B.; Wang, Z. X.; Islas, R.; Heine, T.; Merino, G. CAl₄Be and CAl₃Be₂⁻: global minima with a planar pentacoordinate carbon atom. Chem. Commun. 2010, 46, 8776‒8778. doi: 10.1039/c0cc03479g
8. [8]
  Wu, Y. B.; Duan, Y.; Lu, H. G.; Li, S. D. CAl₂Be₃²⁻ and its salt complex LiCAl₂Be₃⁻: anionic global minima with planar pentacoordinate carbon. J. Phys. Chem. A 2012, 116, 3290‒3294. doi: 10.1021/jp300302w
9. [9]
  Zhao, X. F.; Bian, J. H.; Huang, F.; Yuan, C.; Wang, Q.; Liu, P.; Li, D.; Wang, X.; Wu, Y. B. Stabilization of beryllium-containing planar pentacoordinate carbon species through attaching hydrogen atoms. RSC Adv. 2018, 8, 36521‒36526. doi: 10.1039/C8RA07664B
10. [10]
  Castro, A. C.; Martinez Guajardo, G.; Johnson, T.; Ugalde, J. M.; Wu, Y. B.; Mercero, J. M.; Heine, T.; Donald, K. J.; Merino, G. CBe₅E⁻ (E = Al, Ga, In, Tl): planar pentacoordinate carbon in heptaatomic clusters. Phys. Chem. Chem. Phys. 2012, 14, 14764‒14768. doi: 10.1039/c2cp40839b
11. [11]
  Luo, Q. Theoretical observation of hexaatomic molecules containing pentacoordinate planar carbon. Sci. China Ser. B 2008, 51, 1030‒1035. doi: 10.1007/s11426-008-0121-5
12. [12]
  Grande Aztatzi, R.; Cabellos, J. L.; Islas, R.; Infante, I.; Mercero, J. M.; Restrepo, A.; Merino, G. Planar pentacoordinate carbons in CBe₅⁴⁻ derivatives. Phys. Chem. Chem. Phys. 2015, 17, 4620‒4624. doi: 10.1039/C4CP05659K
13. [13]
  Guo, J. C.; Feng, L. Y.; Barroso, J.; Merino, G.; Zhai, H. J. Planar or tetrahedral? A ternary 17-electron CBe₅H₄⁺ cluster with planar pentacoordinate carbon. Chem. Commun. 2020, 56, 8305‒8308. doi: 10.1039/D0CC02973D
14. [14]
  Guo, J. C.; Ren, G. M.; Miao, C. Q.; Tian, W. J.; Wu, Y. B.; Wang, X. CBe₅H_nⁿ⁻⁴ (n = 2~5): hydrogen-stabilized CBe₅ pentagons containing planar or quasi-planar pentacoordinate carbons. J. Phys. Chem. A 2015, 119, 13101‒13106. doi: 10.1021/acs.jpca.5b10178
15. [15]
  Guo, J. C.; Tian, W. J.; Wang, Y. J.; Zhao, X. F.; Wu, Y. B.; Zhai, H. J.; Li, S. D. Star-like superalkali cations featuring planar pentacoordinate carbon. J. Chem. Phys. 2016, 144. 244303‒9.
16. [16]
  Wu, Y. B.; Duan, Y.; Lu, G.; Lu, H. G.; Yang, P.; Schleyer, P. V. R.; Merino, G.; Islas, R.; Wang, Z. X. D_3h CN₃Be₃⁺ and CO₃Li₃⁺: viable planar hexacoordinate carbonprototypes. Phys. Chem. Chem. Phys. 2012, 14, 14760–14763. doi: 10.1039/c2cp41822c
17. [17]
  Zhao, X. F.; Li, J. J.; Li, H. R.; Yuan, C.; Tian, X.; Li, S. D.; Wu, Y. B.; Guo, J. C.; Wang, Z. X. Viable aromatic Be_nH_n stars enclosing a planar hypercoordinate boron or late transition metal. Phys. Chem. Chem. Phys. 2018, 20, 7217‒7222. doi: 10.1039/C7CP06955C
18. [18]
  Xiao, B.; Cheng, J. B.; Liu, Z. B.; Li, Q. Z.; Li, W. Z.; Yang, X.; Yu, X. F. Beryllium decorated armchair BC₂N nanoribbons: coexistence of planar tetracoordinate carbon and nitrogen moieties. RSC Adv. 2015, 5, 73945‒73950. doi: 10.1039/C5RA12660F
19. [19]
  Li, J. J.; Mu, Y.; Tian, X.; Yuan, C.; Wu, Y. B.; Wang, Q.; Li, D.; Wang, Z. X.; Li, S. D. Zigzag double-chain C‒Be nanoribbon featuring planar pentacoordinate carbons and ribbon aromaticity. J. Mater. Chem. C 2017, 5, 408‒414. doi: 10.1039/C6TC04356A
20. [20]
  Wang, Y.; Li, F.; Li, Y.; Chen, Z. Semi-metallic Be₅C₂ monolayer global minimum with quasi-planar pentacoordinate carbons and negative Poisson's ratio. Nat. Commun. 2016, 7, 11488. doi: 10.1038/ncomms11488
21. [21]
  Li, Y.; Liao, Y.; Chen, Z. Be₂C Monolayer with quasi-planar hexacoordinate carbons: a global minimum structure. Angew. Chem. Int. Ed. 2014, 53, 7248‒7252. doi: 10.1002/anie.201403833
22. [22]
  Li, X. S.; Millam, J. M.; Schlegel, H. B. Ab initio molecular dynamics studies of the photodissociation of formaldehyde, H₂CO → H₂ + CO: direct classical trajectory calculations by MP2 and density functional theory. J. Chem. Phys. 2000, 113, 10062‒10067. doi: 10.1063/1.1323503
23. [23]
  Millam, J. M.; Bakken, V.; Chen, W.; Hase, W. L.; Schlegel, H. B. Ab initio classical trajectories on the Born-Oppenheimer surface: Hessian-based integrators using fifth-order polynomial and rational function fits. J. Chem. Phys. 1999, 111, 3800‒3805. doi: 10.1063/1.480037
24. [24]
  Schleyer, P. V. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. J. R. E. Nucleus-independent chemical shifts: a simple and efficient aromatic-city probe. J. Am. Chem. Soc. 1996, 118, 6317−6318. doi: 10.1021/ja960582d
25. [25]
  Schleyer, P. V. R.; Jiao, H.; Hommes, N. J. R. E.; Malkin, V. G.; Malkina, O. L. An evaluation of the aromaticity of inorganic rings: refined evidence from magnetic properties. J. Am. Chem. Soc. 1997, 119, 12669−12670. doi: 10.1021/ja9719135
26. [26]
  Corminboeuf, C.; Heine, T.; Seifert, G.; von Rague Schleyer, P. V. R.; Weber, J. Induced magnetic fields in aromatic [n]-annulenes-interpretation of NICS tensor components. Phys. Chem. Chem. Phys. 2004, 6, 273−276. doi: 10.1039/B313383B
27. [27]
  Zubarev, D. Y.; Boldyrev, A. I. Developing paradigms of chemical bonding: adaptive natural density partitioning. Phys. Chem. Chem. Phys. 2008, 10, 5207‒5217. doi: 10.1039/b804083d
28. [28]
  Zubarev, D. Y.; Boldyrev, A. I. Revealing intuitively assessable chemical bonding patterns in organic aromatic molecules via adaptive natural density partitioning. J. Org. Chem. 2008, 73, 9251‒9258. doi: 10.1021/jo801407e
29. [29]
  Bera, P. P.; Sattelmeyer, K. W.; Saunders, M.; Schaefer, H. F.; Schleyer, P. V. R. Mindless chemistry. J. Phys Chem. A 2006, 110, 4287‒4290. doi: 10.1021/jp057107z
30. [30]
  Saunders, M. J. Stochastic search for isomers on a quantum mechanical surface. Comput. Chem. 2004, 25, 621‒626. doi: 10.1002/jcc.10407
31. [31]
  Wu, Y. B.; Lu, H. G.; Li, S. D.; Wang, Z. X. J. Simplest neutral singlet C₂E₄ (E = Al, Ga, In, and Tl) global minima with double planar tetracoordinate carbons: equivalence of C₂ Moieties in C₂E₄ to carbon centers in CAl₄²⁻ and CAl₅⁺. Phys. Chem. A 2009, 113, 3395‒3402. doi: 10.1021/jp8099187
32. [32]
  Lu, H. G., Wu, Y. B. in GXYZ 2.0, A Random Search Program. Shanxi University: Taiyuan 2015.
33. [33]
  Werner, H. J.; Knowles, P. J.; Knizia, G.; Manby, F. R.; Schütz, M. MolPro 2012.1. University College Cardiff Consultants Limited: Cardiff UK 2012.
34. [34]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, Jr. J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Revision A. 03. Gaussian, Inc., Wallingford CT 2016.
35. [35]
  Guo, J. C.; Feng, L. Y.; Zhai, H. J. Planar tetracoordinate carbon molecules with 14 valence electrons: examples of CBe₄M_nⁿ⁻² (M = Li, Au; n = 1~3) clusters. New J. Chem. 2020, 44, 18293. doi: 10.1039/D0NJ03944F
36. [36]
  Pyykkö, P. Additive covalent radii for single-, double-, and triple-bonded molecules and tetrahedrally bonded crystals: a summary. J. Phys. Chem. A 2015, 119, 2326‒2337. doi: 10.1021/jp5065819
37. [37]
  Yuan, C.; Zhao, X. F.; Wu, Y. B.; Wang, X. Ultrashort beryllium-beryllium distances rivalling those of metal-metal quintuple bonds between transition metals. Angew. Chem. Int. Ed. 2016, 55, 15651‒15655. doi: 10.1002/anie.201609455
38. [38]
  Zhao, X. F.; Yuan, C.; Li, S. D.; Wu, Y. B.; Wang, X. Simulating the effect of a triple bond to achieve the shortest main group metal-metal distance in diberyllium complexes: a computational study. Dalton Trans. 2018, 47, 14462‒14467. doi: 10.1039/C8DT02683A
39. [39]
  Wagner, F. R.; Noor, A.; Kempe, R. Ultrashort metal-metal distances and extreme bond orders. Nat. Chem. 2009, 1, 529‒536. doi: 10.1038/nchem.359
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沈阳化工大学材料科学与工程学院沈阳 110142

Planar Tetracoordinate Carbon in 6σ + 2π Double Aromatic CBe42– Derivatives

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Planar Tetracoordinate Carbon in 6σ + 2π Double Aromatic CBe₄^2– Derivatives