Sulfonium Cation in the Service of π-Acid Catalysis.
Electrophilic Catalysis
Ligand Design
Sulfonium Cations
π-Acid Catalysis
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
27 Nov 2023
27 Nov 2023
Historique:
received:
06
10
2023
pubmed:
27
11
2023
medline:
27
11
2023
entrez:
27
11
2023
Statut:
aheadofprint
Résumé
While still rare, cationic ligands offer much promise as tunable electron-withdrawing ligands for π-acid catalysis. Recently, we introduced pincer-type sulfonium cations into the list of available strongly π-acidic ancillary ligands. However, the M-S bond in sulfonium complexes of these ligands was found highly labile, precluding their catalytic applications. Herein we demonstrate that this obstacle can be overcome by increasing the rigidity of the sulfonium pincer scaffold. X-ray analyses confirm that despite bearing a formal positive charge, the sulfur atom of this newly designed sulfonium ligand maintains its coordination to the Pt(II)-center, while DFT calculations indicate that by doing so it strongly enhances the electrophilic character of the metal. Kinetic studies carried out on three model cycloisomerization reactions prove that such a tris-cationic sulfonium-Pt(II) complex is highly reactive, compared to its thioether-based analogue. This proof-of-concept study presents the first example of employing sulfonium-based ligands in homogeneous catalysis.
Identifiants
pubmed: 38009835
doi: 10.1002/anie.202314997
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202314997Subventions
Organisme : Israel Science Foundation
ID : 2079/22
Informations de copyright
© 2023 Wiley-VCH GmbH.
Références
Z. Li, C. Brouwer, C. He, Chem. Rev. 2008, 108, 3239-3265;
A. S. K. Hashmi, Chem. Rev. 2007, 107, 3180-3211;
E. Jiménez-Núñez, A. M. Echavarren, Chem. Rev. 2008, 108, 3326-3350;
A. Furstner, Acc. Chem. Res. 2014, 47, 925-938.
D. J. Gorin, F. D. Toste, Nature 2007, 446, 395-403;
D. J. Gorin, B. D. Sherry, F. D. Toste, Chem. Rev. 2008, 108, 3351-3378;
R. Dorel, A. M. Echavarren, Chem. Rev. 2015, 115, 9028-9072;
J. L. Mascareñas, I. Varela, F. López, Acc. Chem. Res. 2019, 52, 465-479.
F. Inagaki, C. Matsumoto, Y. Okada, N. Maruyama, C. Mukai, Angew. Chem. Int. Ed. 2015, 54, 818-822;
M. Sircoglou, S. Bontemps, M. Mercy, N. Saffon, M. Takahashi, G. Bouhadir, L. Maron, D. Bourissou, Angew. Chem. Int. Ed. 2007, 46, 8583-8586.
H. Yang, F. P. Gabbaï, J. Am. Chem. Soc. 2015, 137, 13425-13432;
D. You, F. P. Gabbaï, J. Am. Chem. Soc. 2017, 139, 6843-6846;
S. Sen, I.-S. Ke, F. P. Gabbaï, Organometallics 2017, 36, 4224-4230;
D. You, H. Yang, S. Sen, F. P. Gabbaï, J. Am. Chem. Soc. 2018, 140, 9644-9651.
L. C. Wilkins, Y. Kim, E. D. Litle, F. P. Gabbai, Angew. Chem. Int. Ed. 2019, 58, 18266-18270;
D. Litle, L. C. Wilkins, F. P. Gabbaï, Chem. Sci. 2021, 12, 3929-3936;
M. J. Karimi, E. D. Litle, F. P. Gabbaï, Isr. J. Chem. 2022, e202200036;
Y. Lo, F. P. Gabbaï, Angew. Chem. Int. Ed. 2019, 58, 10194-10197.
H. Buhl, C. Ganter, Chem. Commun. 2013, 49, 5417-5419;
P. Brüggemann, M. Wahl, S. Schwengers, H. Buhl, C. Ganter, Organometallics 2018, 37, 4276-4286.
J. Petuskova, M. Patil, S. Holle, C. W. Lehmann, W. Thiel, M. Alcarazo, J. Am. Chem. Soc. 2011, 133, 20758-20760;
J. Carreras, M. Patil, W. Thiel, M. Alcarazo, J. Am. Chem. Soc. 2012, 134, 16753-16758;
J. Carreras, G. Gopakumar, L. Gu, A. Gimeno, P. Linowski, J. Petuskova, W. Thiel, M. Alcarazo, J. Am. Chem. Soc. 2013, 135, 18815-18823;
M. Alcarazo, Chem. Eur. J. 2014, 20, 7868-7877.
R. D. Adams, C. Blankenship, B. E. Segmueller, M. Shiralian, J. Am. Chem. Soc. 1983, 105, 4319-4326;
T. Yoshida, T. Adachi, K. Sato, K. Baba, T. Kanokogi, J. Chem. Soc. Chem. Commun. 1993, 1511-1513.
R. Li, N. Barel, V. Subramaniyan, O. Cohen, F. Tibika, Y. Tulchinsky, Chem. Sci. 2022, 13, 4770-4778;
R. Li, N. Barel, V. Subramaniyan, R. Hoffman, F. Tibika, Y. Tulchinsky, Organometallics 2023, 42, 246-258.
V. Subramaniyan, F. Tibika, Y. Tulchinsky, Inorg. Chem. 2023, 62, 123-136.
Deposition numbers 2265127, 2265128 and 2265130 for [4](OTf), [5](SbF6)2, and [6](BF4)3 contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.
L. Bonnafoux, L. Ernst, F. R. Leroux, F. Colober, Eur. J. Inorg. Chem. 2011, 3387-3397;
J. J. Race, M. J. Webb, T. M. Boyd, A. S. Weller, Eur. J. Inorg. Chem. 2022, e202200174.
To obtain a Pt(II) complex of the new sulfonium ligand [4](OTf) we initially employed a protocol previously utilized for Pt(II) complexes of ligands I and II, i.e. via the preparation of PtX2 intermediates (X=Me or Cl) reference 9. However, as the rigid thioxanthone backbone was unable to acquire the a cis-κ2-P,P coordination mode, no such products could be obtained with either (COD)PtCl2 or (COD)PtMe2.
Ligand [4](BF4) was prepared by double ion exchange from [4](OTf), as shown on Scheme and explained in SI, for avoiding counterion-mixed products.
D. J. H. Emslie, L. E. Harrington, H. A. Jenkins, C. M. Robertson, J. F. Britten, Organometallics 2008, 27, 5317-5325;
L. M. Suess, J. C. Peters, Organometallics 2012, 31, 5213-5222;
S.-Y. Siah, P−H. Leung, K. F. Mok, Polyhedron 1994, 13, 3253-3255.
Y. Tulchinsky, S. Kozuch, P. Saha, M. Botoshansky, L. J. W. Shimonb, M. Gandelman, Chem. Sci. 2014, 5, 1305-1311;
R. Tonner, Foxler, B. Neumuller, W. Petz, G. Frenking, Angew. Chem. Int. Ed. 2006, 45, 8038-8042;
J. F. Wishart, A. Bino, H. Taube, Inorg. Chem. 1986, 25, 3318-3321.
K. Takeuchi, H. Taniguchi, I. Tanigawa, S. Tsujimoto, T. Matsuo, H. Tanaka, K. Yoshizawa, F. Ozawa, Angew. Chem. Int. Ed. 2016, 55, 15347-15350;
H. Kameo, Y. Tanaka, Y. Shimoyama, D. Izumi, H. Matsuzaka, Y. Nakajima, P. Lavedan, A. L. Gac, D. Bourissou, Angew. Chem. Int. Ed. 2023, 62, e202301509;
H. Braunschweig, K. Gruss, K. Radacki, Angew. Chem. Int. Ed. 2007, 46, 7782-7784.
T.-P. Lin, F. P. Gabbaï, J. Am. Chem. Soc. 2012, 134, 12230-12238.
D. You, J. E. Smith, S. Sen, F. P. Gabbaï, Organometallics 2020, 39, 4169-4173.
T. Ziegler, A. Rauk, Inorg. Chem. 1979, 18, 1755-1759;
T. Ziegler, A. Rauk, Theor. Chim. Acta 1977, 46, 1-10.
M. Mitoraj, A. Michalak, Organometallics 2007, 26, 6576-6580;
A. Michalak, M. Mitoraj, T. Ziegler, J. Phys. Chem. A 2008, 112, 1933-1939;
M. Mitoraj, A. Michalak, J. Mol. Model. 2007, 13, 347-355;
M. Mitoraj, A. Michalak, J. Mol. Model. 2008, 14, 681-687;
M. Mitoraj, H. Zhu, A. Michalak, T. Ziegler, Int. J. Quantum Chem. 2009, 109, 3379-3386.