Abstract
Singlet-triplet energy differences in Arduengo-type carbenes XC2HN2C compared and contrasted with their sila, germa, stana and plumba analogues; at B3LYP/6-311++G** level of theory. Free Gibbs energy differences between triplet (t) and singlet (s) states (ΔG(t–s)) change in the following order: plumbylenes > stannylenes > germylenes > silylenes > carbenes. The singlet states in XC2HN2C are generally more stable when the electron withdrawing groups such as–F was used at β-position. However, the singlet states in XC2N2HM (M = Si, Ge, Sn, and Pb) are generally more stable when the withdrawing groups such as–F was placed. The puckering energy is investigated for each the singlet and triplet states. The DFT calculations found the linear correlation to size of the group 14 divalent element (M), the ∠N–M–N angle, and the Δ(LUMO–HOMO) of XC2HN2M.
Similar content being viewed by others
References
A. J. Arduengo, R. L. Harlow, and M. Kline, J. Am. Chem. Soc. 113, 361 (1991).
P. S. Skell and R. C. Woodworth, J. Am. Chem. Soc. 78, 4496 (1956).
D. Bourissou, O. Guerret, F. P. Gabbai, and G. Bertrand, Chem. Rev. 100, 39 (2000).
W. E. Parham, F. C. Loew, and E. E. Schweizer, J. Org. Chem. 24, 1900 (1959).
W. H. Atwell and D. R. Weyenberg, J. Am. Chem. Soc. 90, 3438 (1968).
Y. Apeloig, R. Pauncz, M. Karni, R. West, W. Steiner, and D. Chapman, Organometallics 22, 3250 (2003).
C. L. Collins, R. D. Davy, and H. F. Schaefer, Chem. Phys. Lett. 171, 259 (1990).
M. Denk, R. Lennon, R. Hayashi, R. West, A. V. Belyakov, H. P. Verne, A. Haaland, and N. Metzler, J. Am. Chem. Soc. 116, 2691 (1994).
W. A. Herrmann, M. Denk, J. Behm, W. Scherer, F.-R. Klingan, H. Bock, B. Solouki, and M. Wagner, Angew. Chem. 31, 1485 (1992).
N. Tokitoh, H. Suzuki, R. Okazaki, and K. Ogawa, J. Am. Chem. Soc. 115, 10428 (1993).
M. Z. Kassaee, S. Arshadi, M. Acedy, and E. Vessally, J. Organomet. Chem. 690, 3427 (2005).
E. Vessally, Heteroat. Chem. 19, 245 (2008).
E. Vessally, M. Nikoorazm, and A. Ramazani, Chin. J. Inorg. Chem. 24, 631 (2008).
E. Vessally, A. Rezaei, N. Chalyavi, and M. Nikoorazm, Russ. J. J. Phys. Chem. 81, 1821 (2007).
E. Vessally, A. Rezaei, N. Chalyavi, and M. Nikoorazm, J. Chin. Chem. Soc. 54, 1583 (2007).
E. Vessally, Phosphorus Sulfur Silicon Relat. Elem. 184, 1805 (2009).
E. Vessally, M. Abbasian, A. Ramazani, and A. R. Poor Heravi, Phosphorus Sulfur Silicon Relat. Elem. 185, 705 (2010).
E. Vessally, M. Nikoorazm, F. Esmaili, and E. Fereyduni, J. Organomet. Chem. 696, 932 (2011).
A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Znkrzewski, G. A. Montgomery, R. E. Startmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, et al., Gaussian 98, Revision A.6 (Gaussian Inc., Pittsburgh PA, 1998).
M. M. Francl, W. J. Pietro, W. J. Hehre, J. S. Binkley, M. S. Gordon, D. J. DeFrees, and J. A. Pople, J. Chem. Phys. 77, 3654 (1982).
M. J. Frisch, J. A. Pople, and J. S. Binkley, J. Chem. Phys. 80, 3265 (1984).
Y. Apeloig, R. Pauncz, M. Karni, R. West, W. Steiner, and D. Chapman, Organometallics 22, 3250 (2003).
C. Gonzalez, A. Restrepo-Cossio, M. Márquez, K. B. Wiberg, and M. D. Rosa, J. Phys. Chem. A 102, 2732 (1998).
Author information
Authors and Affiliations
Corresponding author
Additional information
The article is published in the original.
Rights and permissions
About this article
Cite this article
Vessally, E., Dehbandi, B. & Ahmadi, E. Singlet–triplet energy differences in divalent five membered cyclic conjugated Arduengo-type carbenes XC2HN2M (M = C, Si, Ge, Sn, and Pb; X = F, Cl, Br, and I). Russ. J. Phys. Chem. 90, 1849–1858 (2016). https://doi.org/10.1134/S0036024416090302
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0036024416090302