Pi-interaction
In chemistry,
Types
[edit]The most common types of
- Metal–
π interactions: involves interaction of a metal and the face of aπ system, the metal can be a cation (known as cation–π interactions) or neutral - Polar–
π interactions: involves interaction of a polar molecule and quadrupole moment aπ system.
![](https://upload.wikimedia.org/wikipedia/commons/thumb/d/d2/Polar-pi.svg/220px-Polar-pi.svg.png)
- Aromatic–aromatic interactions (
π stacking): involves interactions of aromatic molecules with each other.- Arene–perfluoroarene interaction: electron-rich benzene ring interacts with electron-poor hexafluorobenzene.
![](https://upload.wikimedia.org/wikipedia/commons/thumb/b/b1/Areneperfluoroarene.svg/220px-Areneperfluoroarene.svg.png)
π donor–acceptor interactions: interaction between low energy empty orbital (acceptor) and a high-energy filled orbital (donor).
![](https://upload.wikimedia.org/wikipedia/commons/thumb/6/6b/Donoracceptor.svg/220px-Donoracceptor.svg.png)
- Anion–
π interactions: interaction of anion withπ system - Cation–
π interactions: interaction of a cation with aπ system - C–H–
π interactions: interaction of C-H withπ system: These interactions are well studied using experimental as well as computational techniques.[3][4][5]
Metal–π interactions
[edit]Metal–
Linear systems
[edit]Ethylene –
Allyl–
Cyclic systems
[edit]The specifics for binding of
Catalysis
[edit]The use of organometallic structures led by
- Heck reaction
- Hiyama coupling
- Kumada coupling
- Negishi coupling
- Petasis reaction
- Sonogashira coupling
- Suzuki reaction.
Another
Specific research
Due to reasons explained earlier in the article, the bonding between a nucleophilic olefin and an electrophilic palladium(II) leaves olefin susceptible to nucleophilic attack. This is true if the olefin is coordinated around Pd as the corner of a square planar complex or as the side of a cationic 18-electron Pd complex. In both cases electron donating groups on the olefin stabilize the complex, but anionic electron donors actually destabilized the complex in the case of the 18-electron Pd complex. The authors of this research proposed that when the olefin
![](https://upload.wikimedia.org/wikipedia/commons/thumb/8/85/Anion_pi_interaction.svg/170px-Anion_pi_interaction.svg.png)
Anion–π interactions
[edit]Anion and
The first X-ray crystal structure that depicted anion–
π -effects in biological systems
[edit]![](https://upload.wikimedia.org/wikipedia/commons/thumb/9/94/Debasis_image.gif/400px-Debasis_image.gif)
A great deal of circumstantial evidence places aromatic residues in the active site of a number of proteins that interact with cations but the presence of cation-
In supramolecular assembly
[edit]![](https://upload.wikimedia.org/wikipedia/commons/thumb/9/9a/24_fig._1.png/330px-24_fig._1.png)
concerns the direct interactions between two
References
[edit]- ^ Anslyn, E.V.; Dougherty, D.A. Modern Physical Organic Chemistry; University Science Books; Sausalito, CA, 2005 ISBN 1-891389-31-9
- ^ Meyer, EA; Castellano, RK; Diederich, F (2003). "Interactions with aromatic rings in chemical and biological recognition". Angewandte Chemie International Edition in English. 42 (11): 1210–50. doi:10.1002/anie.200390319. PMID 12645054.
- ^ K. Sundararajan; K. Sankaran; K.S. Viswanathan; A.D. Kulkarni; S.R. Gadre (2002). "H-
π Complexes of acetylene-ethylene: A matrix isolation and computational study". J. Phys. Chem. A. 106 (8): 1504. Bibcode:2002JPCA..106.1504S. doi:10.1021/jp012457g. - ^ Lu, Le; Hua, Ruimao (28 July 2021). "Dual XH–
π Interaction of Hexafluoroisopropanol with Arenes". Molecules. 26 (15): 4558. doi:10.3390/molecules26154558. PMC 8347120. PMID 34361719. - ^ K. Sundararajan; K.S. Viswanathan; A.D. Kulkarni; S.R. Gadre (2002). "H-
π Complexes of acetylene-benzene: A matrix isolation and computational study". J. Mol. Str. (Theochem). 613 (1–3): 209–222. Bibcode:2002JMoSt.613..209S. doi:10.1016/S0022-2860(02)00180-1. - ^ J. Rebek (2005). "Simultane Verkapselung: Moleküle unter sich". Angewandte Chemie. 117 (14): 2104–2115. Bibcode:2005AngCh.117.2104R. doi:10.1002/ange.200462839.
- ^ J. Rebek (2005). "Simultaneous Encapsulation: Molecules Held at Close Range". Angewandte Chemie International Edition. 44 (14): 2068–2078. doi:10.1002/anie.200462839. PMID 15761888.
- ^ S. Grimme (2004). "Accurate description of van der Waals complexes by density functional theory including empirical corrections". Journal of Computational Chemistry. 25 (12): 1463–73. doi:10.1002/jcc.20078. PMID 15224390. S2CID 6968902.
- ^ a b c d Miessler, G.A.; Tarr, D.A. Inorganic Chemistry. Pearson Education, Inc. 2010 ISBN 0-13-612866-1
- ^ Laszlo, K.; Czako, B. Strategic Applications of Named Reactions in Organic Synthesis, Elsevier Academic Press, ISBN 0-12-429785-4
- ^ Zhou, Yongbo; Xi, Zhenxing; Chen, Wanzhi; Wang, Daqi (2008). "Dinickel(II) Complexes of Bis(N-heterocyclic carbene) Ligands Containing [Ni2(
μ -OH)] Cores as Highly Efficient Catalysts for the Coupling of Aryl Chlorides". Organometallics. 27 (22): 5911. doi:10.1021/om800711g. - ^ Miki, Kunio; Shiotani, Osamu; Kai, Yasushi; Kasai, Nobutami; Kanatani, Hideki; Kurosawa, Hideo (1983). "Comparative x-ray crystallographic and thermodynamic studies of substituted styrene complexes of palladium(II) containing the .eta.5-cyclopentadienyl ligand. Appreciation of olefin–palladium(II) .pi. Interaction in the 18-electron complex". Organometallics. 2 (5): 585. doi:10.1021/om00077a003.
- ^ Schottel, Brandi L.; Chifotides, Helen T.; Dunbar, Kim R. (2008). "Anion-
π interactions". Chemical Society Reviews. 37 (1): 68–83. doi:10.1039/b614208g. PMID 18197334. - ^ Ballester P. "Anions and pi–Aromatic Systems. Do they interact attractively?" Recognition of Anions. Structure and Bonding Series, 129 (2008) 127-174 Berlin. Springer Verlag
- ^ Gamez, Patrick; Mooibroek, Tiddo J.; Teat, Simon J.; Reedijk, Jan (2007). "Anion Binding Involving
π -Acidic Heteroaromatic Rings". Accounts of Chemical Research. 40 (6): 435–44. doi:10.1021/ar7000099. PMID 17439191. - ^ Demeshko, Serhiy; Dechert, Sebastian; Meyer, Franc (2004). "Anion−
π Interactions in a Carousel Copper(II)−Triazine Complex". Journal of the American Chemical Society. 126 (14): 4508–9. doi:10.1021/ja049458h. PMID 15070355. - ^ Maeda, Hiromitsu; Osuka, Atsuhiro; Furuta, Hiroyuki (2004). "Anion Binding Properties of N-Confused Porphyrins at the Peripheral Nitrogen". Journal of Inclusion Phenomena. 49: 33–36. doi:10.1023/B:JIPH.0000031110.42096.d3. S2CID 95180509.
- ^ Dougherty, D. A. (1996). "Cation-pi Interactions in Chemistry and Biology: A New View of Benzene, Phe, Tyr, and Trp". Science. 271 (5246): 163–8. Bibcode:1996Sci...271..163D. doi:10.1126/science.271.5246.163. PMID 8539615. S2CID 9436105.
- ^ Kumpf, R.; Dougherty, D. (1993). "A mechanism for ion selectivity in potassium channels: computational studies of cation-pi interactions". Science. 261 (5129): 1708–10. Bibcode:1993Sci...261.1708K. doi:10.1126/science.8378771. PMID 8378771.