Email this article Th e Study of Labile Silylene Reactions Using Matrix IR Spectroscopy
- Authors: Boganov S.E.1, Promyslov V.M.1, Krylova I.V.1, Shangin P.G.1, Syroeshkin M.A.1, Egorov M.P.1
-
Affiliations:
- N.D. Zelinsky Institute of Organic Chemistry, RAS
- Issue: Vol 122, No 2 (2024): THEMED SECTION: FUNDAMENTAL PRINCIPLES OF ORGANIC ELECTROCHEMISTRY, CREATION OF NEW FUNCTIONAL MATERIALS AND MATERIALS FOR MEDICINE
- Pages: 80-92
- Section: THEMED SECTION: FUNDAMENTAL SCIENTIFIC RESEARCH IN THE FIELD OF NATURAL SCIENCES
- URL: https://journals.rcsi.science/1605-8070/article/view/303452
- DOI: https://doi.org/10.22204/2410-4639-2024-122-02-80-92
- ID: 303452
Cite item
Full Text
Abstract
Using matrix IR spectroscopy, complexes of SiCl2 with CO2 and CO were stabilized in argon matrices at ~10 K and spectroscopically characterized. Complex Cl2Si•CO2 is the first experimentally detected complex of any silylenes with CO2. It is found that under matrix conditions, it exists in a photochemical equilibrium with the isomeric complex Cl2Si=O•CO, with the equilibrium being strongly shifted towards Cl2Si•CO2. The detected complex Cl2Si•CO with the coordination of the silylene to the C atom is the first unclassical complex of silylenes. The first complex with the silylene coordination to the O atom of CO, Cl2Si•OC, was also detected. Using matrix IR spectroscopy, photochemical transformations of one of the simplest labile silylenes, dimethoxysilylene, Si(OMe)2, were studied, all its conformers were revealed. It was confirmed that the only product of its photoisomerisation is labile methylmethoxysilanone, Me(MeO)Si=O. Potential energy surfaces of the studied systems were explored using quantum chemical calculations.
About the authors
Sergey E. Boganov
N.D. Zelinsky Institute of Organic Chemistry, RAS
Author for correspondence.
Email: bog@ioc.ac.ru
Russian Federation, 47 Leninsky Ave., Moscow, 119991, Russia
Vladimir M. Promyslov
N.D. Zelinsky Institute of Organic Chemistry, RAS
Email: vladimir-promyslov@yandex.ru
Russian Federation, 47 Leninsky Ave., Moscow, 119991, Russia
Irina V. Krylova
N.D. Zelinsky Institute of Organic Chemistry, RAS
Email: kiv@ioc.ac.ru
Russian Federation, 47 Leninsky Ave., Moscow, 119991, Russia
Pavel G. Shangin
N.D. Zelinsky Institute of Organic Chemistry, RAS
Email: shangin@ioc.ac.ru
Russian Federation, 47 Leninsky Ave., Moscow, 119991, Russia
Mikhail A. Syroeshkin
N.D. Zelinsky Institute of Organic Chemistry, RAS
Email: syroeshkin@ioc.ac.ru
Russian Federation, 47 Leninsky Ave., Moscow, 119991, Russia
Mikhail P. Egorov
N.D. Zelinsky Institute of Organic Chemistry, RAS
Email: mpe@ioc.ac.ru
Academician, Director
Russian Federation, 47 Leninsky Ave., Moscow, 119991, RussiaReferences
- T. Bally In Reactive Intermediate Chemistry, Eds R.A. Moss, M.S. Platz, M. Jones Jr., USA, New Jersey, Hoboken, John Wiley & Sons, 2004, pp. 795–845. doi: 10.1002/0471721492.ch17.
- R. Damrauer, R. Simon, A. Laporterie, G. Manuel, Y.T. Park, W.P. Weber J. Organomet. Chem., 1990, 391, 7. doi: 10.1016/0022-328X(90)80150-X.
- E.A. Tchernyshev, N.T. Komalenkova, S.A. Bashkirova, V.V. Sokolov Rus.J. Gen. Chem. [Zhurnal Obshchey Khimii], 1978, 48, 830 (in Russian).
- L.A. Curtiss, P.C. Redfern, K. Raghavachari J. Chem. Phys., 2007, 127, 124105. doi: 10.1063/1.2770701.
- 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 et. al. Gaussian 09, Revision D.01, USA, CT, Wallingford, Gaussian, Inc., 2013.
- S. Yadav, S. Saha, S.S. Sen ChemCatChem, 2016, 8, 486. doi: 10.1002/cctc.201501015.
- X. Liu, X.-Q. Xiao, Z. Xu, X. Yang, Z. Li, Z. Dong, C. Yan, G. Lai, M. Kira Organometallics, 2014, 33, 5434. doi: 10.1021/om500736h.
- D. Wendel, A. Porzelt, F.A.D. Herz, D. Sarkar, C. Jandl, S. Inoue, B. Rieger J. Am. Chem. Soc., 2017, 139, 8134. doi: 10.1021/jacs.7b05136.
- A.V. Protchenko, P. Vasko, D.C.H. Do, J. Hicks, M.Á. Fuentes, C. Jones, S. Aldridge Angew. Chem. Int. Ed., 2019, 58(6), 1808. doi: 10.1002/anie.201812675.
- R. Becerra, J.P. Cannady, R. Walsh J. Phys. Chem. A, 2002, 106, 4922. doi: 10.1021/jp020091h.
- A.V. Lalov, S.E. Boganov, V.I. Faustov, M.P. Egorov, O.M. Nefedov Russ. Chem. Bull., 2003, 52, 526. doi: 10.1023/A:1023973815486.
- S.E. Boganov, V.M. Promyslov, P.G. Shangin, M.A. Syroeshkin, M.P. Egorov Mendeleev Commun., 2021, 31, 149. doi: 10.1016/j.mencom.2021.03.002.
- B.D. Ruzsicska, A. Jodhan, I. Safarik, O.P. Strausz, T.N. Bell Chem. Phys. Lett., 1985, 113, 67. doi: 10.1016/0009-2614(85)85012-0.
- H. Schnöckel Z. Anorg. Allg. Chem., 1980, 460, 37. doi: 10.1002/zaac.19804600104.
- Y. Xiong, S. Yao, T. Szilvási, A. Ruzicka, M. Driess Chem. Commun., 2020, 56, 747. doi: 10.1039/c9cc08680c.
- G. Maier, H.P. Reisenauer, H. Egenolf Organometallics, 1999, 18, 2155. doi: 10.1021/om981025y.
- C.A. Arrington, J.T. Petty, S.E. Payne, W.C.K. Haskins J. Am. Chem. Soc., 1988, 110, 6240. doi: 10.1021/ja00226a046.
- M.A. Pearsall, R. West J. Am. Chem. Soc., 1988, 110, 7228. doi: 10.1021/ja00229a055.
- H. Bornemann, W. Sander J. Organomet. Chem., 2002, 641, 156. doi: 10.1016/S0022-328X(01)01363-8.
- M. Tacke, C. Klein, D.J. Stufkens, A. Oskam, P. Jutzi, E.A. Bunte Z. Anorg. Allg. Chem., 1993, 619, 865. doi: 10.1002/zaac.19936190510.
- C. Ganesamoorthy, J. Schoening, C. Wölper, L. Song, P.R. Schreiner, S. Schulz Nat. Chem., 2020, 12, 608. doi: 10.1038/s41557-020-0456-x.
- D. Reiter, R. Holzner, A. Porzelt, P. Frisch, S. Inoue Nat. Chem., 2020, 12, 1131. doi: 10.1038/s41557-020-00555-4.
- A.J. Lupinetti, S.H. Strauss, G. Frenking Prog. Inorg. Chem., 2001, 49, 1. doi: 10.1002/9780470166512.ch1.
- S.E Boganov, V.M. Promyslov, A.V. Lalov, M.A. Syroeshkin, M.P. Egorov Russ. Chem. Bull., 2021, 70, 1084. doi: 10.1007/s11172-021-3188-1.
- A.J. Lupinetti, S. Fau, G. Frenking, S.H. Strauss J. Phys. Chem. A, 1997, 101, 9551. doi: 10.1021/jp972657l.
- G. Maier, H.P. Reisenauer, K. Schöttler, U. Wessolek-Kraus J. Organomet. Chem., 1989, 366, 25. doi: 10.1016/0022-328X(89)87312-7.
- A. Patyk. W. Sander, J. Gauss, D. Cremer Angew. Chem., Int. Ed. Engl., 1989, 28, 898. doi: 10.1002/anie.198908981.
- G.O. Braathen, A. Gatial, P. Klaboe, J. Nielsen J. Mol. Struct., 1990, 218, 67. doi: 10.1016/0022-2860(90)80245-F.
Supplementary files
