Reversing the Bond Length Alternation Order in Conjugated Polyenes by Substituent Effects.
bond alternations
bond lengths
complementary bonding analysis
polyenes
quantum crystallography
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
13 Mar 2023
13 Mar 2023
Historique:
received:
14
11
2022
pubmed:
15
12
2022
medline:
15
12
2022
entrez:
14
12
2022
Statut:
ppublish
Résumé
We have synthesised several push-pull substituted conjugated polyenes and determined their accurate C-C bond lengths and charge-density distributions by utilising quantum crystallographic techniques. In a series of alkene, dienes, and triene bearing two (trifluoromethyl)sulfonyl (triflyl) groups on the terminal carbon atom, unique reversal of the bond-length alternation (BLA) order has been observed. This is a pronounced aberration from the molecular structure predicted by the Lewis-structure-based neutral resonance structure. Such reversal of BLA order has not been observed in push-pull compounds bearing conventional electron-withdrawing groups such as carbonyl and cyano groups instead of triflyl groups. Bonding behaviour of both normal and reversed bond length alternating systems has been revealed by complementary bonding analysis using several bond descriptors based on the experimentally fitted wavefunctions.
Identifiants
pubmed: 36515459
doi: 10.1002/chem.202203538
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202203538Subventions
Organisme : Japan Society for the Promotion of Science
ID : 17K08224
Organisme : Japan Society for the Promotion of Science
ID : 20K06947
Organisme : Deutsche Forschungsgemeinschaft
ID : KL 3500/1-1
Informations de copyright
© 2022 Wiley-VCH GmbH.
Références
F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc. Perkin Trans. 2 1987, S1.
A. J. Kirby, I. V. Komarov, P. D. Wothers, N. Feeder, Angew. Chem. Int. Ed. 1998, 37, 785;
I. V. Komarov, S. Yanik, A. Yu. Ishchenko, J. E. Davies, J. M. Goodman, A. J. Kirby, J. Am. Chem. Soc. 2015, 137, 926;
K. Tani, B. M. Stolz, Nature 2006, 441, 731;
M. Liniger, D. G. Vander Velde, M. K. Takase, M. Shahgholi, B. M. Stoltz, J. Am. Chem. Soc. 2016, 138, 969.
For acyclic twisted amides, see; G. Meng, J. Zhang, M. Szostak, Chem. Rev. 2021, 121, 12746.
L. Pauling, The Nature of the Chemical Bond, Cornell University Press, NY, 1960.
E. D. Glendening, F. Weinhold, J. Comput. Chem. 1998, 19, 593.
C. R. Kemnitz, M. J. Loewen, J. Am. Chem. Soc. 2007, 129, 2521;
E. D. Glendening, J. A. Hrabal, J. Am. Chem. Soc. 1997, 119, 12940.
N. C. Craig, P. Groner, D. C. McKean, J. Phys. Chem. A 2006, 110, 7461.
T. Kupka, A. Buczek, M. A. Broda, M. Stachów, P. Tarnowsk, J. Mol. Model. 2016, 22, 101.
H. Yanai, T. Suzuki, F. Kleemiss, H. Fukaya, Y. Dobashi, L. A. Malaspina, S. Grabowsky, T. Matsumoto, Angew. Chem. Int. Ed. 2019, 58, 8839;
Angew. Chem. 2019, 131, 8931.
S. Grabowsky, P. Luger, J. Buschmann, T. Schneider, T. Schirmeister, A. N. Sobolev, D. Jayatilaka, Angew. Chem. Int. Ed. 2012, 51, 6776;
Angew. Chem. 2012, 124, 6880.
A. E. Reed, P. von Ragué Schleyer, J. Am. Chem. Soc. 1990, 112, 1434;
H. Yanai, Y. Takahashi, H. Fukaya, Y. Dobashi, T. Matsumoto, Chem. Commun. 2013, 49, 10091;
H. Yanai, P. Almendros, S. Takahashi, C. Lazaro-Milla, B. Alcaide, T. Matsumoto, Chem. Asian J. 2018, 13, 1956.
S. R. Marder, J. W. Perry, B. G. Tiemann, C. B. Gorman, S. Gilmour, S. L. Biddle, G. Bourhill, J. Am. Chem. Soc. 1993, 115, 2524.
Solvent effects on BLA are considered to be an important factor for solvatochromism of polymethine dyes. See;
L. G. S. Brooker, G. H. Keyes, R. H. Sprague, R. H. VanDyke, E. VanLare, G. VanZandt, F. L. White, H. W. J. Cressman, S. G. Dent Jr., J. Am. Chem. Soc. 1951, 73, 5332;
S. Dähne, Science 1978, 199, 1163; Review, see:
A. V. Kulinich, A. A. Ishchenko, Russ. Chem. Rev. 2009, 78, 141.
H. Yanai, S. Egawa, T. Taguchi, Tetrahedron Lett. 2013, 54, 2160;
H. Yanai, S. Egawa, K. Yamada, J. Ono, M. Aoki, T. Matsumoto, T. Taguchi, Asian J. Org. Chem. 2014, 3, 556.
R. F. Coles, I. H. Skoog, U. S. Pat. 1976, 3 933 914;
I. H. Skoog, U. S. Pat. 1977, 4 018 810.
J. Sandström, Top. Stereochem. 1983, 14, 83;
E. Kleinpeter, J. Serb. Chem. Soc. 2006, 71, 1.
M. Woińska, S. Grabowsky, P. M. Dominiak, K. Woźniak, D. Jayatilaka, Sci. Adv. 2016, 2, e1600192.
D. Jayatilaka, B. Dittrich, Acta Crystallogr. Sect. A 2008, 64, 383;
S. C. Capelli, H.-B. Bürgi, B. Dittrich, S. Grabowsky, D. Jayatilaka, IUCrJ 2014, 1, 361 ; c) F. Kleemiss, O. V. Dolomanov, M. Bodensteiner, N. Peyerimhoff, L. Midgley, L. J. Bourhis, A. Genoni, L. A. Malaspina, D. Jayatilaka, J. L. Spencer, F. White, B. Grundkötter-Stock, S. Steinhauer, D. Lentz, H. Puschmann, S. Grabowsky, Chem. Sci. 2021, 12, 1675.
C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165.
Complementary Bonding Analysis (Ed.: S. Grabowsky), De Gruyter, Berlin, 2021.
M. Woińska, D. Jayatilaka, B. Dittrich, R. Flaig, P. Luger, K. Woźniak, P. M. Dominiak, S. Grabowsky, ChemPhysChem 2017, 18, 3334.
M. D. Gould, C. Taylor, S. K. Wolff, G. S. Chandler, D. Jayatilaka, Theor. Chem. Acc. 2008, 119, 275.
The Quantum Theory of Atoms in Molecules (Eds.: C. F. Matta, R. J. Boyd), Wiley-VCH, Weinheim, 2007;
R. F. W. Bader, Atoms in Molecules: A Quantum Theory, Oxford University Press, Oxford, 1990.
M. Kohout, Int. J. Quantum Chem. 2004, 97, 651;
M. Kohout, F. R. Wagner, Y. Grin, Theor. Chem. Acc. 2008, 119, 413.
S. Raub, G. Jansen, Theor. Chem. Acc. 2001, 106, 223.
F. Weinhold, C. R. Landis, Valency and Bonding: A Natural Bond Orbital Donor-Acceptor Perspective, Cambridge University Press, Cambridge, 2004.
Here, the total RGBI is used because in each bond, the ionic bond contribution is negligibly small and the total values are close to the covalent RGBI. Full details of RGBI analysis are shown in the Supporting Information.
In the case of non-push-pull diene 2 b, a lone electron pair ELI domain on C1 atom is not obtained and NELI of the C1−C2 bonding basin was notably large (3.553 e). See, Ref. [10].
H. Yanai, T. Yoshino, M. Fujita, H. Fukaya, A. Kotani, F. Kusu, T. Taguchi, Angew. Chem. Int. Ed. 2013, 52, 1560;
Angew. Chem. 2013, 125, 1600;
H. Yanai, R. Takahashi, Y. Takahashi, A. Kotani, H. Hakamata, T. Matsumoto, Chem. Eur. J. 2017, 23, 8203;
H. Yanai, S. Hoshikawa, Y. Moriiwa, A. Shoji, A. Yanagida, T. Matsumoto Angew. Chem. Int. Ed. 2021, 60, 5168;
Angew. Chem. 2021, 133, 5228.
R. J. Koshar, R. A. Mitsch, J. Org. Chem. 1973, 38, 3358;
L. Turowsky, K. Seppelt, Inorg. Chem. 1988, 27, 2135;
A. Hasegawa, T. Ishikawa, K. Ishihara, H. Yamamoto, Bull. Chem. Soc. Jpn. 2005, 78, 1401;
D. Höfler, R. Goddard, J. B. Lingnau, N. Nöthling, B. List, Angew. Chem. Int. Ed. 2018, 57, 8326;
Angew. Chem. 2018, 130, 8459.
F. Meyers, S. R. Marder, B. M. Pierce, J. L. Brédas, J. Am. Chem. Soc. 1994, 116, 10703;
S. R. Marder, C. B. Gorman, F. Meyers, J. W. Perry, G. Bourhill, J. L. Brédas, B. M. Pierce, Science 1994, 265, 632;
R. L. Gieseking, C. Risko, J.-L. Brédas, J. Phys. Chem. Lett. 2015, 6, 2158.