Protonated Alcohols Are Examples of Complete Charge-Shift Bonds

Journal Article · Wed Oct 15 00:00:00 EDT 2014 · Journal of Organic Chemistry

DOI:https://doi.org/10.1021/jo501549q· OSTI ID:1385890

Anderson, Peter ^[1]; Petit, Alban ^[1]; Ho, Junming ^[2]; Mitoraj, Mariusz Pawel ^[3]; Coote, Michelle L. ^[2]; Danovich, David ^[4]; Shaik, Sason ^[4]; Braïda, Benoît ^[5]; Ess, Daniel H. ^[1]

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1. Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States
2. Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia
3. Faculty of Chemistry, Jagiellonian University, ul. Ingardena 3, 30-060 Krakow, Poland
4. Institute of Chemistry and the Lise-Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
5. Sorbonne Universités, UPMC Univ Paris 06, UMR 7616, LCT F-75005, Paris, France; CNRS, UMR 7616, LCT F-75005, Paris, France

Accurate gas-phase and solution-phase valence bond calculations reveal that protonation of the hydroxyl group of aliphatic alcohols transforms the C–O bond from a principally covalent bond to a complete charge-shift bond with principally “no-bond” character. All bonding in this charge-shift bond is due to resonance between covalent and ionic structures, which is a different bonding mechanism from that of traditional covalent bonds. Until now, charge-shift bonds have been previously identified in inorganic compounds or in exotic organic compounds. This work showcases that charge-shift bonds can occur in common organic species.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• DOE Contract Number: SC0001298
• OSTI ID: 1385890
• Journal Information: Journal of Organic Chemistry, Vol. 79, Issue 21; Related Information: CCHF partners with University of Virginia (lead); Brigham Young University; California Institute of Technology; Colorado School of Mines; University of Maryland; University of North Carolina, Chapel Hill; University of North Texas; Princeton University; The Scripps Research Institute; Yale University; ISSN 0022-3263
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

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