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Molecular structure and conformations of 1-phenyl-1-silacyclohexane from gas-phase electron diffraction and quantum chemical calculations

Abstract

Molecular structure and conformational behavior of the title compound 1 were studied experimentally by gas-phase electron diffraction (GED–MS) and theoretically (DFT and MP2). Only two of four possible conformers of 1 differing by axial or equatorial location of the phenyl group and the angle of rotation about the Si–CPh bond contribute to the equilibrium; these are the 1-eq conformer with the phenyl ring plane perpendicular to the averaged silacyclohexane plane and the 1-ax conformer with the phenyl ring and Si–C6 bond lying approximately in one plane. The ratio 1-eq:1-ax is 62 (10):38 (10), which is only slightly different from 78:22 in solution. The presence of up to 10 % of 1-ax_orth conformer cannot be excluded either. The corresponding ΔG values are 0.29 and 0.25 kcal mol−1. The GED molecular structure of 1 is nicely reproduced by DFT and MP2 calculations.

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References

  1. 1.

    Shen Q, Hilderbrandt RL, Mastryukov VS (1979) J Mol Struct 54:121–124

    CAS  Article  Google Scholar 

  2. 2.

    Arnason I, Kvaran A, Jonsdottir S, Gudnason PI, Oberhammer H (2002) J Org Chem 67:3827–3831

    CAS  Article  Google Scholar 

  3. 3.

    Sigolaev YuF, Semenov SG, Belyakov AV (2013) Russ J Gen Chem 83: 932–937. Zh Obshch Khim 83: 795–801

  4. 4.

    Bodi A, Kvaran Á, Jonsdottir S, Antonsson E, Wallevik SÓ, Arnason I, Belyakov AV, Baskakov AA, Hölbling M, Oberhammer H (2007) Organometallics 26:6544–6550

    CAS  Article  Google Scholar 

  5. 5.

    Belyakov AV, Baskakov AA, Ivanov AD, Garabadzhiu AV, Arnason I (2013) Struct Chem 24:763–768

    CAS  Article  Google Scholar 

  6. 6.

    Wallevik SÓ, Bjornsson R, Kvaran Á, Jonsdottir S, Arnason I, Belyakov AV, Kern T, Hassler K (2013) Organometallics 32:6996–7005

    CAS  Article  Google Scholar 

  7. 7.

    Belyakov AV, Baskakov AA, Naraev VN, Rykov AN, Oberhammer H, Arnason I, Wallevik SO (2011) Russ J Gen Chem 81: 2257–2261. Zh Obshch Khim 81: 1805–1809

  8. 8.

    Belyakov AV, Baskakov AA, Naraev VN, Rykov AN, Oberhammer H, Arnason I, Wallevik SÓ (2012) Russ J Phys Chem 86: 1563–1566. Zh Fiz Khim 86:1665–1668

  9. 9.

    Belyakov AV, Baskakov AA, Berger RJF, Mitzel NW, Oberhammer H, Arnason I, Wallevik SÓ (2012) J Mol Struct 1012:126–130

    CAS  Article  Google Scholar 

  10. 10.

    Girichev GV, Giricheva NI, Bodi A, Gudnason PI, Jonsdottir S, Kvaran A, Arnason I, Oberhammer H (2007) Chem-Eur J 13:1776–1783

    CAS  Article  Google Scholar 

  11. 11.

    Wallevik SÓ, Bjornsson R, Kvaran Á, Jonsdottir S, Arnason I, Belyakov AV, Baskakov AA, Hassler K, Oberhammer H (2010) J Phys Chem A 114:2127–2135

    CAS  Article  Google Scholar 

  12. 12.

    Bushweller CH (1995) In Conformational Behavior of Six-Membered Rings. Analysis, Dynamics, and Stereoelectronic Effects (Ed Juaristi E) pp 25–58.VCH, NY

  13. 13.

    Ribeiro DS, Rittner R (2003) J Org Chem 68:6780–6787

    CAS  Article  Google Scholar 

  14. 14.

    Taddei F, Kleinpeter E (2004) J Mol Struct (Theochem) 683:29–41

    CAS  Article  Google Scholar 

  15. 15.

    Shainyan BA, Kleinpeter E (2013) Tetrahedron 69:5927–5936

    CAS  Article  Google Scholar 

  16. 16.

    Weldon AJ, Tschumper GS (2007) Int J Quant Chem 107:2261–2265

    CAS  Article  Google Scholar 

  17. 17.

    Kern T, Hölbling M, Dzambaski A, Flock M, Hassler K, Wallevik SÓ, Arnason I, Bjornsson R (2012) J Raman Spectrosc 43:1337–1342

    CAS  Google Scholar 

  18. 18.

    Carcenac Y, Diter P, Wakselman C, Tordeux M (2006) New J Chem 30:442–446

    CAS  Article  Google Scholar 

  19. 19.

    Penman KG, Kitching W, Adcock W (1989) J Org Chem 54:5390–5391

    CAS  Article  Google Scholar 

  20. 20.

    Shen Q, Rhodes S, Cochran JC (1992) Organometallics 11:485–486

    CAS  Article  Google Scholar 

  21. 21.

    Durig JR, Ward RM, Conrad AR, Tubergen MG, Giurgis GA, Gounev TK (2009) J Mol Struct 922:19–29

    CAS  Article  Google Scholar 

  22. 22.

    Wiberg KB, Hammer JD, Castejon H, Bailey WF, DeLeon EL, Jarret RM (1999) J Org Chem 64:2085–2095

    CAS  Article  Google Scholar 

  23. 23.

    Favero LB, Velino B, Caminati W, Arnason I, Kvaran Á (2006) Organometallics 26:3813–3816

    Article  Google Scholar 

  24. 24.

    Manoharan M, Eliel EL (1984) Tetrahedron Lett 25:3267–3268

    CAS  Article  Google Scholar 

  25. 25.

    Eliel EL, Manoharan M (1981) J Org Chem 46:1959–1962

    Article  Google Scholar 

  26. 26.

    Abraham RJ, Bergen HA, Chadwick DJ (1981) Tetrahedron Lett 22:2807–2810

    CAS  Article  Google Scholar 

  27. 27.

    Wiberg KB, Castejon H, Bailey WF, Ochterski J (2000) J Org Chem 65:1181–1187

    CAS  Article  Google Scholar 

  28. 28.

    Shainyan BA, Kleinpeter E (2012) Tetrahedron 68:114–125

    CAS  Article  Google Scholar 

  29. 29.

    Campanelli AR, Domenicano A, Ramondo F, Hargittai I (2011) Struct Chem 22:361–369

    CAS  Article  Google Scholar 

  30. 30.

    Shainyan BA, Kirpichenko SV, Kleinpeter E, Shlykov SA, Osadchiy DYu, Chipanina NN, Oznobikhina LP (2013) J Org Chem 78:3939–3947

    CAS  Article  Google Scholar 

  31. 31.

    Campanelli R, Ramondo F, Domenicano A, Hargittai I (1997) J Organomet Chem 536:309–318

    Article  Google Scholar 

  32. 32.

    Sipachev VA (2001) J Mol Struct 567–568:67–72

    Article  Google Scholar 

  33. 33.

    Sipachev VA (1985) J Mol Struct (Theochem) 121:143–151

    Article  Google Scholar 

  34. 34.

    Hamilton WC (1965) Acta Crystallogr 18:502–510

    CAS  Article  Google Scholar 

  35. 35.

    Allinger NL, Tribble MT (1971) Tetrahedron Lett 3259–3262

  36. 36.

    Squillacote ME, Neth JM (1987) J Am Chem Soc 109:198–202

    CAS  Article  Google Scholar 

  37. 37.

    West RJ (1954) J Am Chem Soc 76:6012–6014

    CAS  Article  Google Scholar 

  38. 38.

    Girichev GV, Utkin AN, Revichev YuF (1984) Prib Tekh Eksp 2:187–190 (in Russian)

    Google Scholar 

  39. 39.

    Girichev GV, Shlykov SA, Revichev YuF (1986) Ibid 4:167–169 (in Russian)

    Google Scholar 

  40. 40.

    Girichev GV, Shlykov SA, Petrova VN, Subbotina NYu, Lapshina SB, Danilova TG (1988) Izv Vyssh Uchebn Zaved, Khim Khim Tekhnol 31:46–51 (in Russian)

    CAS  Google Scholar 

  41. 41.

    Girichev EG, Zakharov AV, Girichev GV, Bazanov MI (2000) Izv Vyssh Uchebn Zaved Tekhnol Tekst Prom 2:142–146

    Google Scholar 

  42. 42.

    Andersen B, Seip HM, Strand TG, Stølevik R (1969) Acta Chem Scand 23:3224–3234

    CAS  Article  Google Scholar 

  43. 43.

    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, Kitao O, 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 JM, 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 O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09 revision A 02. Gaussian, Inc., Wallingford

    Google Scholar 

  44. 44.

    Valiev M, Bylaska EJ, Govind N, Kowalski K, Straatsma TP, van Dam HJJ, Wang D, Nieplocha J, Apra E, Windus TL, de Jong WA (2010) Computer Phys Commun 181:1477–1489

    CAS  Article  Google Scholar 

Download references

Acknowledgments

The financial support of this work by the Russian Foundation for Basic Research (Grant 14-03-00923) is greatly acknowledged.

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Correspondence to Bagrat A. Shainyan.

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. The online version of this article contains supplementary material (optimized geometries, energies vibration frequencies, vibration amplitudes, scattering intensities and backgrounds, experimental details), which is available to authorized users. (DOC 1514 kb)

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Shainyan, B.A., Kirpichenko, S.V., Osadchiy, D.Y. et al. Molecular structure and conformations of 1-phenyl-1-silacyclohexane from gas-phase electron diffraction and quantum chemical calculations. Struct Chem 25, 1677–1685 (2014). https://doi.org/10.1007/s11224-014-0444-0

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Keywords

  • 1-Phenyl-1-silacyclohexane
  • Molecular structure
  • Conformational analysis
  • DFT and MP2 calculations