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New Hydroxylated Cyclic and Acyclic Silylenes Via DFT

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Abstract

We have scrutinized thirteen new derivatives of cyclic and acyclic silylenes and compared their structural and thermodynamic parameters, at M06-2X/6–311++G** level of theory. The cyclic three- and five-membered silylenes include (2-hydroxy)cyclopropasilylene-2-ene (1), (2,3-dihydroxy)cyclopropasilylene-2-ene (2), (2-hydroxy)cyclopentasilylene-2,4-diene (3), and (2,5-dihydroxy)cyclopentasilylene-2,4-diene (4). The acyclic isomers consist of hydroxypropa-2-silylene (1′), (1,3-dihydroxy)propa-2-silylene (2′), (2-hydroxy)penta-3-silylene (3′), (2-hydroxy)penta-3-silylene-1,4-diene (3″), (2,4-dihydroxy)penta-3-silylene (4′), and (2,4-dihydroxy)penta-3-silylene-1,4-diene (4″). In addition, keto forms of 3″ (3”K) and 4″ (4”K1 and 4”K2) along with protonated forms of silylenes (1H, 1’H, 2H, 2’H, 3H, 3’H, 3”H, 3”K-H, 4H, 4’H, 4”H, 4”K1-H, and 4”K2-H) are investigated for determining their proton affinities (PAs) and intramolecular hydrogen bondings (IHBs). The results show that 4′ shows the lowest singlet-triplet energy gap (ΔEs-t = −19.03 eV) and band gap (ΔEH-L = −2.01 eV) and the highest nucleophilicity (N = 4.02 eV), chemical potential (μ = −3.38 eV), and PA (382.85 kcal/mol) which correlates with its strongest IHB. Atoms in molecules (AIM) analysis represents the highest electron density (ρ(r) = 0.033) at bond critical point (BCP) of IHB in 4′. The natural bond orbital (NBO) analysis shows the highest value of second-order perturbation stabilization energy (E2 = 7.85 kcal/mol) for 4′ which is in consistent with the lowest bond length of IHB (1.84 Å). Furthermore, the infrared (IR) spectroscopy indicates the lowest vibrational frequency of O-H bond νOH(νOH= 3542.87 cm−1) which verifies the strong IHB of 4′. The overall order of the IHB strength is 4′ > 4” > 4’H > 4”H > 2’ > 2’H.

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References

  1. Jutzi P, Schubert U (2004) Silicon chemistry: from the atom to extended systems. Angew Chemie 43(23):2990

  2. Denk M, Lennon R, Hayashi R, West R, Belyakov AV, Verne HP, Haaland A, Wagner M, Metzler N (1994) Synthesis and Structure of a Stable Silylene. J Am Chem Soc 116(6):2691–2692

    Article  CAS  Google Scholar 

  3. Haaf M, Schmedake TA, West R (2000) Stable Silylenes. Acc Chem Res 33(10):704–714

    Article  CAS  Google Scholar 

  4. Hadlington TJ, Abdalla JAB, Tirfoin R, Aldridge S, Jones C (2016) Stabilization of a two-coordinate, acyclic diaminosilylene (ADASi): completion of the series of isolable diaminotetrylenes, :E(NR2)2(E = group 14 element). Chem Commun 52(8):1717–1720

    Article  CAS  Google Scholar 

  5. Schmedake TA, Haaf M, Paradise BJ, Millevolte AJ, Powell DR, West R (2001). J Organomet Chem 636(1):17–25

    Article  CAS  Google Scholar 

  6. Gehrhus B, Lappert MF (2001). J Organomet Chem 617:209–223

    Article  Google Scholar 

  7. Ayoubi-Chianeh M, Kassaee MZ (2019) Novel silicon super bases at DFT level of theory: effects of fused benzene rings on the basicity of 2,4,6-cycloheptatrienesilylene. Res Chem Intermed 45:4677–4691

    Article  CAS  Google Scholar 

  8. Ayoubi-Chianeh M, Kassaee MZ, Ashenagar S, Cummings PT (2019) J Phys Org Chem 32(8):e3956

  9. Ayoubi-Chianeh M, Kassaee MZ 2019 J Phys Org Chem 32(10):e3988

  10. Cote DR, Van Nguyen S, Stamper AK, Armbrust DS, Tobben D, Conti RA, Lee GY (1999). IBM J Res Dev 43(1.2):5–38

    Article  CAS  Google Scholar 

  11. Heaven MW, Metha GF, Buntine MA (2001). J Phys Chem A 105(7):1185–1196

    Article  CAS  Google Scholar 

  12. Tamao K, Kobayashi M, Matsuo T, Furukawa S, Tsuji H (2012) The first observation of electroluminescence from di(2-naphthyl)disilene, an Si Si double bond-containing π-conjugated compound. Chem Commun 48(7):1030–1032

    Article  CAS  Google Scholar 

  13. Schwartz RL, Davico GE, Ramond TM, Lineberger WC (1999). J Phys Chem A 103(41):8213–8221

    Article  CAS  Google Scholar 

  14. Luke BT, Pople JA, Krogh-Jespersen M-B, Apeloig Y, Karni M, Chandrasekhar J, Schleyer P v R (1986). J Am Chem Soc 108(2):270–284

    Article  CAS  Google Scholar 

  15. Kalcher J, Sax AF (1992) Singlet-triplet splittings and electron affinities of some substituted silylenes. J Mol Struct Theochem 253:287–302

    Article  Google Scholar 

  16. Krogh-Jespersen K (1985) Structural and energetic features of fully substituted silylenes, disilenes, and silylsilylenes (SiX2, X2SiSiX2, and XSiSiX3; X = lithium, methyl, and fluorine). J Am Chem Soc 107(3):537–543

    Article  CAS  Google Scholar 

  17. Yoshida M, Tamaoki N (2002) DFT Study on Triplet Ground State Silylenes Revisited: The Quest for the Triplet Silylene Must Go On. Organometallics 21(13):2587–2589

    Article  CAS  Google Scholar 

  18. Asay M, Inoue S, Driess M (2011) Aromatic Ylide-Stabilized Carbocyclic Silylene. Angew Chemie Int Ed 50(41):9589–9592

    Article  CAS  Google Scholar 

  19. Oláh J, Veszprémi T, De Proft F, Geerlings P (2007). J Phys Chem A 111(42):10815–10823

    Article  Google Scholar 

  20. Rekken BD, Brown TM, Fettinger JC, Tuononen HM, Power PP (2012) Isolation of a Stable, Acyclic, Two-Coordinate Silylene. J Am Chem Soc 134(15):6504–6507

    Article  CAS  Google Scholar 

  21. Biswas AK, Lo R, Ganguly B (2013). J Phys Chem. A 117(14):3109–3117

    Article  CAS  Google Scholar 

  22. Kosa M, Karni M, Apeloig Y (2004) How to Design Linear Allenic-Type Trisilaallenes and Trigermaallenes. J Am Chem Soc 126(34):10544–10545

    Article  CAS  Google Scholar 

  23. Apeloig Y, Pauncz R, Karni M, West R, Steiner W, Chapman D (2003) Why Is Methylene a Ground State Triplet while Silylene Is a Ground State Singlet?†. Organometallics 22(16):3250–3256

    Article  CAS  Google Scholar 

  24. Belzner J, Dehnert U, Ihmels H (2001) Reactions of a cyclotrisilane with styrene derivatives and diarylacetylenes—evidence for nucleophilic silylenes. Tetrahedron 57(3):511–517

    Article  CAS  Google Scholar 

  25. Dubois I, Herzberg G, Verma RD (1967). J Chem Phys 47(10):4262–4263

    Article  CAS  Google Scholar 

  26. Ayoubi-Chianeh M, Kassaee KZ (2020) J Chinese Chem Soc 67(9):1544–1551

  27. Ayoubi-Chianeh M, Kassaee MZ n.d. J Phys Org Chem e4074

  28. Öztürk N, Özdemir T, Alpaslan YB, Gokce H, Alpaslan G (2018). Bilge Int J Sci Technol Res 2(1):56–73

    Article  Google Scholar 

  29. Alvareda E, Denis PA, Iribarne F, Paulino M (2016) Bond dissociation energies and enthalpies of formation of flavonoids: A G4 and M06-2X investigation. Comput Theor Chem 1091:18–23

    Article  CAS  Google Scholar 

  30. Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su S (1993). J Comput Chem 14(11):1347–1363

    Article  CAS  Google Scholar 

  31. Schmidt MW, Gordon MS (2017) J Phys Chem A 121(41):8003–8011

  32. Bryantsev VS, Diallo MS, van Duin ACT, Goddard III WA (2009) Evaluation of B3LYP, X3LYP, and M06-Class Density Functionals for Predicting the Binding Energies of Neutral, Protonated, and Deprotonated Water Clusters. J Chem Theory Comput 5(4):1016–1026

    Article  CAS  Google Scholar 

  33. Zhao Y, Truhlar DG (2008). Theor Chem Accounts Theory Comput Model (Theoretica Chim Acta) 120(1):215–241

    Article  CAS  Google Scholar 

  34. Walker M, Harvey AJA, Sen A, Dessent CEH (2013). J Phys Chem A 117(47):12590–12600

    Article  CAS  Google Scholar 

  35. Domingo LR, Chamorro E, Pérez P (2008). J Org Chem 73(12):4615–4624

    Article  CAS  Google Scholar 

  36. Yang W, Parr RG (1985) Hardness, softness, and the fukui function in the electronic theory of metals and catalysis. Proc Natl Acad Sci 82(20):6723–6726

    Article  CAS  Google Scholar 

  37. Sheela NR, Muthu S, Sampathkrishnan S (2014) Spectrochim. Acta Part A Mol Biomol Spectrosc 120:237–251

    Article  CAS  Google Scholar 

  38. Chandra A, Uchimaru T (2002) The O-H Bond Dissociation Energies of Substituted Phenols and Proton Affinities of Substituted Phenoxide Ions: A DFT Study. Int J Mol Sci 3(4):407–422

    Article  CAS  Google Scholar 

  39. Biegler-König F, Schönbohm J (2002). J Comput Chem 23(15):1489–1494

    Article  Google Scholar 

  40. Kumar PSV, Raghavendra V, Subramanian V (2016). J Chem Sci 128(10):1527–1536

    Article  CAS  Google Scholar 

  41. Gordon MS (1985) Potential-energy surfaces in singlet and triplet silylene. Chem Phys Lett 114(4):348–352

    Article  CAS  Google Scholar 

  42. Bader RFW (2005) The Quantum Mechanical Basis of Conceptual Chemistry. Monatshefte für Chemie/Chemical Mon 136(6):819–854

    Article  CAS  Google Scholar 

  43. Bader RFW (1991) A quantum theory of molecular structure and its applications. Chem Rev 91(5):893–928

    Article  CAS  Google Scholar 

  44. Yang Q, Yang H, Ding X, Xue W, Sun S (2020) The effect of adsorption and grafting on the acidity of [(HSO3)C3C1im]+[Cl]− on the surface of (SiO2)4O2H4 clusters. J Mol Graph Model 96:107528

    Article  CAS  Google Scholar 

  45. Weinhold F, Landis CR, Glendening ED (2016) What is NBO analysis and how is it useful? Int Rev Phys Chem 35(3):399–440

    Article  CAS  Google Scholar 

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Acknowledgements

We gratefully appreciate Tarbiat Modares University for financial support.

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  1. Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran

    Mojgan Ayoubi-Chianeh & Mohamad Z. Kassaee

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  1. Mojgan Ayoubi-Chianeh
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  2. Mohamad Z. Kassaee
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Correspondence to Mohamad Z. Kassaee.

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Ayoubi-Chianeh, M., Kassaee, M.Z. New Hydroxylated Cyclic and Acyclic Silylenes Via DFT. Silicon 13, 3385–3397 (2021). https://doi.org/10.1007/s12633-020-00750-5

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