Skip to main content
SpringerLink
Log in

Supertetrahedral B80H20, C80H20, and Al80H20 analogs of dodecahedrane and their substituted molecules

  • Original Research
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

Stability of the new B80H20, C80H20, and Al80H20 frame complexes containing tetrahedral B4H, C4H, and Al4H fragments instead of the C–H fragments at the vertices of the dodecahedron scaffold, respectively, is predicted based on the DFT formalism (B3LYP/6-311+G(d, p)). AdNDP, NBO, and Elf analyses have shown that the chemical bonding in C80H20 can be described in terms of classical 2c–2e C–C σ bonds, while electron-deficient B80H20 and Al80H20 analogs are shown to exhibit both 2c–2e and 3c–2e σ bonds, responsible for the bonding between and within tetrahedral fragments, respectively.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Greenberg A, Hargittai I, Lee-Ruff E (1991) Strained organic molecules: a special issue of structural chemistry. Wiley-VCH Verlag GmbH, Weinheim

    Google Scholar 

  2. Hopf H (2000) Classics in hydrocarbon chemistry. Wiley-VCH, Weinheim

    Google Scholar 

  3. Maier G, Neudert J, Wolf O, Pappusch D, Sekiguchi A, Tanaka M, Matsuo T (2002) Tetrakis(trimethylsilyl)tetrahedrane. J Am Chem Soc 124:13819–13826 (and references cited therein)

    Article  CAS  Google Scholar 

  4. Eaton PE, Cole TW (1964) The cubane system. J Am Chem Soc 86:962–964

    Article  CAS  Google Scholar 

  5. Gallucci JC, Doecke CW, Paquette LA (1986) X-ray structure analysis of the pentagonal dodecahedrane hydrocarbon (CH)20. J Am Chem Soc 108:1343–1344 (and references cited therein)

    Article  CAS  Google Scholar 

  6. Akasaka T, Nagase S (eds) (2002) Endofullerenes. Kluwer Academic Publishers, Dordrecht

    Google Scholar 

  7. Neretin IS, Slovohotov YuL (2004) Chemical crystallography of fullerenes. Usp Khim 73:492–525 (Russ Chem Rev 73:455–486)

    Article  Google Scholar 

  8. Cross RJ, Saunders M, Prinzbach H (1999) Putting helium inside dodecahedrane. Org Lett 1:1479–1481

    Article  CAS  Google Scholar 

  9. Mascal M (2002) The energetics of shooting ions into the dodecahedrane cage. J Org Chem 67:8644–8647

    Article  CAS  Google Scholar 

  10. Moran D, Stahl F, Jemmis ED, Schaefer HF III, Schleyer PVR (2002) Structures, stabilities, and ionization potentials of dodecahedrane endohedral complexes. J Phys Chem A 106:5144–5154

    Article  CAS  Google Scholar 

  11. Haunschild R, Frenking G (2009) Tetrahedranes. A theoretical study of singlet E4H4 molecules (E=C–Pb and B–Tl). Mol Phys 8-12:911-922 (and references cited therein)

  12. Grubisic A, Li X, Stokes ST, Cordes J, Ganteför GF, Bowen KH, Kiran B, Jena P, Burgert R, Schnöckel H (2007) Closo-alanes (Al4H4, AlnHn+2, 4≤n≤8): a new chapter in aluminum hydride chemistry. J Am Chem Soc 129:5969–5975

    Article  CAS  Google Scholar 

  13. Li X, Grubisic A, Stokes ST, Cordes J, Ganteför GF, Bowen KH, Kiran B, Willis M, Jena P, Burgert R, Schnöckel H (2007) Unexpected stability of Al4H6: a borane analog? Science 315:356–358

    Article  CAS  Google Scholar 

  14. Li X, Grubisic A, Bowen KH, Kandalam AK, Kiran B, Ganteför GF, Jena P (2010) Communications: chain and double-ring polymeric structures: observation of AlnH −3n+1 (n = 4–8) and Al4H14 −. J Chem Phys 132:241103-1–241103-4

    Google Scholar 

  15. Kiran B, Kandalam AK, Xu J, Ding YH, Sierka M, Bowen KH, Schnöckel H (2012) Al6H18: a baby crystal of γ-AlH3. J Chem Phys 137:134303-1–134303-5

    Article  Google Scholar 

  16. Kiran B, Jena P, Li X, Grubisic A, Stokes ST, Ganteför GF, Bowen KH, Burgert R, Schnöckel H (2007) Magic rule for AlnHm magic clusters. Phys Rev Lett 98:256802-1–256802-4

    Article  Google Scholar 

  17. Minyaev RM (2012) Supertetrahedrane and its boron analogs. Russ Chem Bull 61:1673–1680

    Article  CAS  Google Scholar 

  18. Burdett JK, Lee S (1985) Moments method and elemental structures. J Am Chem Soc 107:3063–3082

    Article  CAS  Google Scholar 

  19. Minyaev RM, Avakyan VE (2010) Supertetrahedrane—a new possible carbon allotrope. Dokl Chem 434:253–256

    Article  CAS  Google Scholar 

  20. Minyaev RM, Getmanskii IV, Minkin VI (2014) Supertetrahedral aluminum and silicon structures and their hybrid analogues. Russ J Inorg Chem 59:332–336

    Article  CAS  Google Scholar 

  21. Sheng X-L, Yan Q-B, Ye F, Zheng Q-R, Su G (2011) T-carbon: a novel carbon allotrope. Phys Rev Lett 106:155703-1–155703155703

    Article  Google Scholar 

  22. Minyaev RM, Minkin VI (2013) Supertetrahedral cubane C32H8 and supertetrahedral dodecahedrane C80H20 with tetrahedral C4H fragments in the vertices. Mendeleev Commun 23:131–132

    Article  CAS  Google Scholar 

  23. Morrison JA (1991) Chemistry of the polyhedral boron halides and the diboron tetrahalides. Chem Rev 91:35–48

    Article  CAS  Google Scholar 

  24. Sekiguchi A (2009) In: Dodziuk H (ed) Strained hydrocarbons: beyond the van-t Hoff and Le Bel Hypothesis. Wiley-VCH Verlag GmbH, Weinheim

    Google Scholar 

  25. Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100

    Article  CAS  Google Scholar 

  26. Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789

    Article  CAS  Google Scholar 

  27. Stevens PJ, Devlin JF, Chabalowski JF, Frisch MJ (1994) Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields. J Phys Chem 98:11623–11627

    Article  Google Scholar 

  28. Bartlett RJ, Purvis GD III (1978) Many-body perturbation-theory, coupled-pair many-electron theory, and importance of quadruple excitations for correlation problem. Int J Quant Chem 14:561–581

    Article  CAS  Google Scholar 

  29. Pople JA, Krishnan R, Schlegel HB, Binkley JS (1978) Electron correlation theories and their application to the study of simple reaction potential surfaces. Int J Quant Chem 14:545–560

    Article  CAS  Google Scholar 

  30. Purvis GD III, Bartlett RJ (1982) A full coupled-cluster singles and doubles model—the inclusion of disconnected triples. J Chem Phys 76:1910–1918

    Article  CAS  Google Scholar 

  31. McLean AD, Chandler GS (1980) Contracted Gaussian-basis sets for molecular calculations. I. 2nd row atoms, Z = 11–18. J Chem Phys 72:5639–5648

    Article  CAS  Google Scholar 

  32. Krishnan R, Binkley JS, Seeger R, Pople JA (1980) Self-consistent molecular orbital methods. XX. Basis set for correlated wave-functions. J Chem Phys 72:650–654

    Article  CAS  Google Scholar 

  33. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam MJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09. Revision D.01. Gaussian Inc, Wallingford

  34. Sergeeva AP, Averkiev BB, Zhai H-J, Boldyrev AI, Wang LS (2011) All-boron analogues of aromatic hydrocarbons: B17 − and B18 −. J Chem Phys 134:224304-1–224304-11

    Article  Google Scholar 

  35. Schlegel HB (1982) Optimization of equilibrium geometries and transition structures. J Comput Chem 3:214–218

    Article  CAS  Google Scholar 

  36. Zubarev DYu, Boldyrev AI (2008) Developing paradigms of chemical bonding: adaptive natural density partitioning. Phys Chem Chem Phys 10:5207–5217

    Article  CAS  Google Scholar 

  37. Foster JP, Weinhold F (1980) Natural hybrid orbitals. J Am Chem Soc 102:7211–7218

    Article  CAS  Google Scholar 

  38. Weinhold F, Landis C (2005) Valency and bonding: a natural bond orbital donor-acceptor perspective. Cambridge University Press, Cambridge

    Book  Google Scholar 

  39. Piazza ZA, Popov IA, Li W-L, Pal R, Zeng XC, Boldyrev AI, Wang L-S (2014) A photoelectron spectroscopy and Ab initio study of the structures and chemical bonding of the B25 − cluster. J Chem Phys 141:034303-1–034303-10

    Article  Google Scholar 

  40. Popov IA, Boldyrev AI (2013) Computational probing of all-boron Li2nB2nH2n+2 polyenes. Comp Theor Chem 1004:5–11

    Article  CAS  Google Scholar 

  41. Popov IA, Popov VF, Bozhenko KV, Černušàk I, Boldyrev AI (2013) Structural changes in the series of boron-carbon mixed clusters CxB −10−x (x = 3–10) upon substitution of boron by carbon. J Chem Phys 139:114307-1–114307-16

    Google Scholar 

  42. Popov IA, Li W-L, Piazza ZA, Boldyrev AI, Wang L-S (2014) Complexes between planar boron clusters and transition metals: a photoelectron spectroscopy and Ab initio study of CoB12 – and RhB12 –. J Phys Chem A 118:8098–8105

    Article  CAS  Google Scholar 

  43. Sergeeva AP, Popov IA, Piazza ZA, Li W-L, Romanescu C, Wang L-S, Boldyrev AI (2014) Understanding boron through size-selected clusters: structure, chemical bonding, and fluxionality. Acc Chem Res 47:1349–1358

    Article  CAS  Google Scholar 

  44. Popov IA, Li Y, Chen Z, Boldyrev AI (2013) ‘‘Benzation’’ of graphene upon addition of monovalent chemical species. Phys Chem Chem Phys 15:6842–6848

    Article  CAS  Google Scholar 

  45. Ernzerhof M, Scuseria GE (1999) Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional. J Chem Phys 110:5029–5036

    Article  CAS  Google Scholar 

  46. Becke AD, Edgecombe KE (1990) A simple measure of electron localization in atomic and molecular systems. J Chem Phys 92:5397–5403

    Article  CAS  Google Scholar 

  47. Kohout M (2011) DGrid, version 4.6. Radebeul

  48. Paraview: Parallel visualization application, version 3.98.1. http://paraview.org Accessed 20 Nov 2014

  49. Baranov AI (2012) Visualization plug-in for paraview, version 3.98.0. Springer, Dresden

    Google Scholar 

  50. Zhurko GA. ChemCraft software, version 1.6. http://www.chemcraftprog.com Accessed 20 Nov 2014

  51. Varetto U (2009) Molekel 5.4.0.8. Swiss National Supercomputing Centre, Manno

  52. Olson JK, Boldyrev AI (2011) Ab initio search for global minimum structures of neutral and anionic B4H4 clusters. Chem Phys 379:1–5

    Article  CAS  Google Scholar 

  53. Olson JK, Boldyrev AI (2013) Planar to 3D transition in the B6Hy anions. J Phys Chem A 117:1614–1620

    Article  CAS  Google Scholar 

  54. Olson JK, Boldyrev AI (2011) Ab initio search for global minimum structures of neutral and anionic B4H5 clusters. optical isomerism in B4H5 and B4H5 –. Chem Phys Lett 517:62–67

    Article  CAS  Google Scholar 

  55. Olson JK, Boldyrev AI (2011) Ab initio characterization of the flexural B3H8 – anion found in the reversible dehydrogenation. Comput Theor Chem 967:1–4

    Article  CAS  Google Scholar 

  56. Zhai H-J, Zhao Y-F, Li W-L, Chen Q, Bai H, Hu H-S, Piazza ZA, Tian W-J, Lu H-G, Wu Y-B, Mu Y-W, Wei G-F, Liu Z-P, Li J, Li S-D, Wang L-S (2014) Observation of an all-boron fullerene. Nat Chem 6:727–731

    CAS  Google Scholar 

Download references

Acknowledgments

IAP and AIB thank the National Science Foundation (CHE-1361413) for their financial support. MRM and VVK thank the State Assignment of Russian Government for Research (Project N4.71.2014/K). VIM is gratefully acknowledged for financial support from the Council for Grants of the President of the Russian Federation for Support of Leading Scientific Schools (Grant No. NSh_927.2012.3). Compute, storage, and other resources from the Division of Research Computing in the Office of Research and Graduate Studies at Utah State University are gratefully acknowledged.

Author information

Authors and Affiliations

  1. Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachka Ave., Rostov-on-Don, 344090, Russian Federation

    Ruslan M. Minyaev, Vitaly V. Koval & Vladimir I. Minkin

  2. Department of Chemistry and Biochemistry, Utah State University, Logan, UT, 84322, USA

    Ivan A. Popov & Alexander I. Boldyrev

Authors
  1. Ruslan M. Minyaev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ivan A. Popov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vitaly V. Koval
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Alexander I. Boldyrev
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Vladimir I. Minkin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ruslan M. Minyaev.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 217 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Minyaev, R.M., Popov, I.A., Koval, V.V. et al. Supertetrahedral B80H20, C80H20, and Al80H20 analogs of dodecahedrane and their substituted molecules. Struct Chem 26, 223–229 (2015). https://doi.org/10.1007/s11224-014-0540-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-014-0540-1

Keywords

Search

Navigation