Tetra-tert-butyl-s-indacene is a Bond-Localized C2h Structure and a Challenge for Computational Chemistry
Dr. Lucas J. Karas
Department of Chemistry, University of Houston, Houston, TX 77204 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Said Jalife
Department of Chemistry, University of Houston, Houston, TX 77204 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Renan V. Viesser
Department of Chemistry, University of Houston, Houston, TX 77204 USA
Search for more papers by this authorJoão V. Soares
Department of Chemistry, University of Houston, Houston, TX 77204 USA
Search for more papers by this authorCorresponding Author
Prof. Michael M. Haley
Department of Chemistry & Biochemistry and the Materials Science Institute, University of Oregon, Eugene, OR 97403-1253 USA
Search for more papers by this authorCorresponding Author
Prof. Judy I. Wu
Department of Chemistry, University of Houston, Houston, TX 77204 USA
Search for more papers by this authorDr. Lucas J. Karas
Department of Chemistry, University of Houston, Houston, TX 77204 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Said Jalife
Department of Chemistry, University of Houston, Houston, TX 77204 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Renan V. Viesser
Department of Chemistry, University of Houston, Houston, TX 77204 USA
Search for more papers by this authorJoão V. Soares
Department of Chemistry, University of Houston, Houston, TX 77204 USA
Search for more papers by this authorCorresponding Author
Prof. Michael M. Haley
Department of Chemistry & Biochemistry and the Materials Science Institute, University of Oregon, Eugene, OR 97403-1253 USA
Search for more papers by this authorCorresponding Author
Prof. Judy I. Wu
Department of Chemistry, University of Houston, Houston, TX 77204 USA
Search for more papers by this authorGraphical Abstract
The structure of tetra-tert-butyl-s-indacene is a computational challenge. Highly correlated methods and popular DFT functionals predict a bond-delocalized D2h symmetry, but excellent agreement between experimental and computed proton chemical shifts suggests a true C2h geometry.
Abstract
Whether tetra-tert-butyl-s-indacene is a symmetric D2h structure or a bond-alternating C2h structure remains a standing puzzle. Close agreement between experimental and computed proton chemical shifts based on minima structures optimized at the M06-2X, ωB97X-D, and M11 levels confirm a bond-localized C2h symmetry, which is consistent with the expected strong antiaromaticity of TtB-s-indacene.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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References
- 1K. Hafner, Pure Appl. Chem. 1982, 54, 939–956.
- 2K. Hafner, B. Stowasser, H.-P. Krimmer, S. Fischer, M. C. Böhm, H. J. Lindner, Angew. Chem. Int. Ed. 1986, 25, 630–632.
- 3E. Heilbronner, Z.-Z. Yang, Angew. Chem. Int. Ed. 1987, 26, 360–362.
- 4J. D. Dunitz, C. Krüger, H. Irngartinger, E. F. Maverick, Y. Wang, M. Nixdorf, Angew. Chem. Int. Ed. 1988, 27, 387–389.
- 5C. Gellini, G. Cardini, P. R. Salvi, G. Marconi, K. Hafner, J. Phys. Chem. 1993, 97, 1286–1293.
- 6R. H. Hertwig, M. C. Holthausen, W. Koch, Z. B. Maksić, Angew. Chem. Int. Ed. 1994, 33, 1192–1194.
- 7R. R. Hertwig, M. C. Holthausen, W. Koch, Z. B. Maksí, Int. J. Quantum Chem. 1995, 54, 147–159.
- 8M. Nendel, B. Goldfuss, K. N. Houk, K. Hafner, J. Mol. Struct. 1999, 461–462, 23–28.
- 9L. Moroni, C. Gellini, P. R. Salvi, J. Mol. Struct. 2004, 677, 1–5.
- 10K. Hafner, K. H. Häfner, C. König, M. Kreuder, G. Ploss, G. Schulz, E. Sturm, K. H. Vöpel, Angew. Chem. Int. Ed. 1963, 2, 123–134.
10.1002/anie.196301231 Google Scholar
- 11T. Nakajima, T. Saijo, H. Yamaguchi, Tetrahedron 1964, 20, 2119–2124.
- 12R. D. Brown, J. Chem. Soc. 1951, 2391–2394.
- 13M. Bühl, P. v. R. Schleyer, J. Am. Chem. Soc. 1992, 114, 477–491.
- 14C. S. Wannere, K. W. Sattelmeyer, H. F. Schaefer, III, P. v R. Schleyer, Angew. Chem. Int. Ed. 2004, 43, 4200–4206.
- 15C. H. Choi, M. Kertesz, J. Chem. Phys. 1998, 108, 6681–6688.
- 16K. K. Baldridge, J. S. Siegel, Angew. Chem. Int. Ed. 1997, 36, 745–748.
- 17R. Gershoni-Poranne, A. Stanger, Chem. Eur. J. 2014, 20, 5673–5688.
- 18H. M. Sulzbach, P. v. R. Schleyer, H. Jiao, Y. Xie, H. F. Schaefer, III, J. Am. Chem. Soc. 1995, 117, 1369–1373.
- 19H. M. Sulzbach, H. F. Schaefer, III, W. Klopper, H. P. Lüthi, J. Am. Chem. Soc. 1996, 118, 3519–3520.
- 20R. A. King, T. D. Crawford, J. F. Stanton, H. F. Schaefer, III, J. Am. Chem. Soc. 1999, 121, 10788–10793.
- 21I. Casademont-Reig, R. Guerrero-Avilés, E. Ramos-Cordoba, M. Torrent-Sucarrat, E. Matito, Angew. Chem. Int. Ed. 2021, 60, 24080–24088.
- 22J.-R. Deng, D. Bradley, M. Jirásek, H. L. Anderson, M. D. Peeks, Angew. Chem. Int. Ed. 2022, 61, e202201231.
- 23I. Casademont-Reig, L. Soriano-Agueda, E. Ramos-Cordoba, M. Torrent-Sucarrat, E. Matito, Angew. Chem. Int. Ed. 2022, 61, e202206836.
- 24M. D. Peeks, T. D. W. Claridge, H. L. Anderson, Nature 2017, 541, 200–203.
- 25P. Mori-Sánchez, A. J. Cohen, W. Yang, Phys. Rev. Lett. 2008, 100, 146401.
- 26S.-J. Jhang, J. Pandidurai, C.-P. Chu, H. Miyoshi, Y. Takahara, M. Miki, H. Sotome, H. Miyasaka, S. Chatterjee, R. Ozawa, Y. Ie, I. Hisaki, C.-L. Tsai, Y.-J. Cheng, Y. Tobe, J. Am. Chem. Soc. 2023, 145, 4716–4729.
- 27J. E. Barker, T. W. Price, L. J. Karas, R. Kishi, S. N. MacMillan, L. N. Zakharov, C. J. Gómez-García, J. I. Wu, M. Nakano, M. M. Haley, Angew. Chem. Int. Ed. 2021, 60, 22385–22392.
- 28K. Hafner, H. U. Süss, Angew. Chem. Int. Ed. 1973, 12, 575–577.
- 29T. Gazdag, P. J. Mayer, P. P. Kalapos, T. Holczbauer, O. El Bakouri, G. London, ACS Omega 2022, 7, 8336–8349.
- 30P. J. Mayer, G. London, Org. Lett. 2023, 25, 42–46.
- 31T. Xu, Y. Han, Z. Shen, X. Hou, Q. Jiang, W. Zeng, P. W. Ng, C. Chi, J. Am. Chem. Soc. 2021, 143, 20562–20568.
- 32National Institute of Advanced Industrial Science and Technology, SDBSWeb, 2023, https://sdbs.db.aist.go.jp.
- 33T. Nishinaga, T. Ohmae, K. Aita, M. Takase, M. Iyoda, T. Arai, Y. Kunugi, Chem. Commun. 2013, 49, 5354–5356.
- 34C. Liu, S. Xu, W. Zhu, X. Zhu, W. Hu, Z. Li, Z. Wang, Chem. Eur. J. 2015, 21, 17016–17022.
- 35C. K. Frederickson, B. D. Rose, M. M. Haley, Acc. Chem. Res. 2017, 50, 977–987.
- 36Z. Jin, Z.-F. Yao, K. P. Barker, J. Pei, Y. Xia, Angew. Chem. Int. Ed. 2019, 58, 2034–2039.
- 37J. Wang, M. Chu, J.-X. Fan, T.-K. Lau, A.-M. Ren, X. Lu, Q. Miao, J. Am. Chem. Soc. 2019, 141, 3589–3596.
- 38C. K. Frederickson, L. N. Zakharov, M. M. Haley, J. Am. Chem. Soc. 2016, 138, 16827–16838.
- 39J. J. Dressler, M. M. Haley, J. Phys. Org. Chem. 2020, 33, e4114.
- 40T. Kawase, J.-i. Nishida, Chem. Rec. 2015, 15, 1045–1059.
- 41B. Esser, J. S. Wössner, M. Hermann, Synlett 2022, 33, 737–753.
- 42T. Kawase, T. Fujiwara, C. Kitamura, A. Konishi, Y. Hirao, K. Matsumoto, H. Kurata, T. Kubo, S. Shinamura, H. Mori, E. Miyazaki, K. Takimiya, Angew. Chem. Int. Ed. 2010, 49, 7728–7732.
- 43J. L. Marshall, K. Uchida, C. K. Frederickson, C. Schütt, A. M. Zeidell, K. P. Goetz, T. W. Finn, K. Jarolimek, L. N. Zakharov, C. Risko, R. Herges, O. D. Jurchescu, M. M. Haley, Chem. Sci. 2016, 7, 5547–5558.
- 44A. M. Zeidell, L. Jennings, C. K. Frederickson, Q. Ai, J. J. Dressler, L. N. Zakharov, C. Risko, M. M. Haley, O. D. Jurchescu, Chem. Mater. 2019, 31, 6962–6970.
- 45R. Breslow, F. W. Foss Jr, J. Phys. Condens. Matter 2008, 20, 374104.
- 46T. A. Su, M. Neupane, M. L. Steigerwald, L. Venkataraman, C. Nuckolls, Nat. Rev. Mater. 2016, 1, 16002.
