Abstract
The performance of modern density functional theory methods in predicting the geometry of a structurally complex titanocene bearing carboranyl σ-ligands is assessed. For comparison, ab initio Hartree—Fock calculations were carried out. The majority of the computational methods considered were shown to reproduce the experimentally obtained crystal structure of the compound with good accuracy. The electric dipole moment of the metal complex in the ground electronic state, as well as the composition and energies of its frontier molecular orbitals were evaluated.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Chem. Rev., Ed. J. A. Gladysz, 2000, 100 (Special issue: Frontiers in Metal-Catalyzed Polymerization).
Coord. Chem. Rev., Ed. H. G. Alt, 2006, 250, No. 1–2 (Special issue: Metallocene Complexes as Catalysts for Olefin Polymerization).
A. E. Shilov, Metal Complexes in Biomimetic Chemical Reactions, CRC Press, New York, 1997, 302 pp.
G. A. Abakumov, A. V. Piskunov, V. K. Cherkasov, I. L. Fedushkin, V. P. Ananikov, D. B. Eremin, E. G. Gordeev, I. P. Beletskaya, A. D. Averin, M. N. Bochkarev, A. A. Trifonov, U. M. Dzhemilev, V. A. D’yakonov, M. P. Egorov, A. N. Vereshchagin, M. A. Syroeshkin, V. V. Jouikov, A. M. Muzafarov, A. A. Anisimov, A. V. Arzumanyan, Yu. N. Kononevich, M. N. Temnikov, O. G. Sinyashin, Yu. H. Budnikova, A. R. Burilov, A. A. Karasik, V. F. Mironov, P. A. Storozhenko, G. I. Shcherbakova, B. A. Trofimov, S. V. Amosova, N. K. Gusarova, V. A. Potapov, V. B. Shur, V. V. Burlakov, V. S. Bogdanov, M. V. Andreev, Russ. Chem. Rev., 2018, 87, 393.
W. A. Wani, S. Prashar, S. Shreaz, S. Gomez-Ruis, Coord. Chem. Rev., 2016, 312, 67.
K. Strohfeldt, M. Tacke, Chem. Soc. Rev., 2008, 37, 1174.
H. Kunkely, A. Vogler, Inorg. Chim. Acta, 2004, 357, 4607.
A. F. Armstrong, J. F. Valliant, Dalton Trans., 2007, 4240.
M. G. Medvedev, I. S. Bushmarinov, J. Sun, J. P. Perdew, K. A. Lyssenko, Science, 2017, 355, 49.
P. Hirva, M. Haukka, M. Jakonen, M. A. Moreno, J. Mol. Model., 2008, 14, 171.
V. A. Karttunen, M. Linnolahti, T. A. Pakkanen, J. Maaranen, P. Pitkanen, Theor. Chem. Acc., 2007, 118, 899.
G. V. Loukova, A. A. Milov, V. P. Vasiliev, V. I. Minkin, Russ. Chem. Bull. (Int. Ed.), 2017, 66, 1325.
G. V. Loukova, A. A. Milov, V. P. Vasiliev, V. I. Minkin, High Energy Chem., 2018, 52, 384.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, J. E. Peralta, Jr., F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision D.01, Gaussian Inc., Wallingford CT, 2013.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, D. J. Fox, Gaussian 16, Revision B.01, Gaussian Inc., Wallingford CT, 2016.
A. D. J. Becke, J. Chem. Phys., 1993, 98, 5648.
G. V. Loukova, V. P. Vasiliev, A. A. Milov, V. A. Smirnov, V. I. Minkin, J. Photochem. Photobiol. A: Chem., 2016, 327, 6.
G. V. Loukova, A. A. Milov, V. P. Vasiliev, V. I. Minkin, Phys. Chem. Chem. Phys., 2016, 18, 17822.
G. V. Loukova, A. A. Milov, V. P. Vasiliev, V. I. Minkin, Dokl. Phys. Chem., 2016, 470, 133.
G. V. Loukova, A. A. Milov, V. P. Vasiliev, V. I. Minkin, High Energy Chem., 2017, 51, 333.
D. Rappoport, N. R. M. Crawford, F. Furche, K. Burke, in Computational Inorganic and Bioinorganic Chemistry, Eds E. I. Solomon, R. B. King, R. A. Scott, Wiley, Chichester, 2009, p. 159.
J. P. Perdew, A. Ruzsinszky, L. A. Constantin, J. Sun, G. I. Csonka, J. Chem. Theory Comput., 2009, 5, 902.
A. C. Tsipis, Coord. Chem Rev., 2014, 272, 1.
M. Korth, Angew. Chem., Int. Ed., 2017, 56, 5396.
G. V. Loukova, A. A. Milov, V. P. Vasiliev, Russ. Chem. Bull., 2018, 67, 2323.
C. H. Shin, Y. Han, M. H. Lee, Y. Do, J. Organomet. Chem., 2009, 694, 1623.
Author information
Authors and Affiliations
Corresponding author
Additional information
This work was financially supported by the Russian Foundation for Basic Research (Project No. 18-03-00359).
The study was carried out within the framework of the State Assignment (Project No. 0089-2019-0003, State Registration No. AAAA-A19-119070790003-7), the State Assignments of the Southern Scientific Center of the Russian Academy of Sciences (Project No. 01201354239) and the Southern Federal University (Project No. 1.5056.2017. VU), and also within the framework of the research plan of the Scientific and Educational Center on High Energy Chemistry at the Department of Chemistry, M. V. Lomonosov Moscow State University.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0218—0228, February, 2020.
Rights and permissions
About this article
Cite this article
Loukova, G.V., Milov, A.A., Vasiliev, V.P. et al. Modeling of the spatial and electronic structure and the dipole moment of titanocene dicarboranyl. Russ Chem Bull 69, 218–228 (2020). https://doi.org/10.1007/s11172-020-2749-z
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-020-2749-z