Electron-Withdrawing Trifluoromethyl Groups in Combination with Hydrogen Bonds in Polyols: Brønsted Acids, Hydrogen-Bond Catalysts, and Anion Receptors

Journal Article · Wed Jun 26 04:00:00 EDT 2013 · Journal of the American Chemical Society, 135(25):9525-9530

DOI:https://doi.org/10.1021/ja4036384· OSTI ID:1091476

Shokri, Alireza; Wang, Xue B.; Kass, Steven R.

Electron withdrawing trifluoromethyl groups were characterized in combination with hydrogen bond interactions in three polyols (i.e., CF3CH(OH)CH2CH(OH)CF3, 1; (CF3)2C(OH)C(OH)(CF3)2, 2; ((CF3)2C(OH)CH2)2CHOH, 3) by pKa measurements in DMSO and H2O, negative ion photoelectron spectroscopy and binding constant determinations with Cl–. Their catalytic behavior in several reactions were also examined and compared to a BrØnsted acid (HOAc) and a commonly employed thiourea ((3,5-(CF3)3C6H3NH)2CS). The combination of inductive stabilization and hydrogen bonds was found to afford potent acids which are effective catalysts. It also appears that hydrogen bonds can transmit the inductive effect over distance even in an aqueous environment, and this has far reaching implications.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1091476
• Report Number(s): PNNL-SA-96131; 42590; 44678; KC0301020
• Journal Information: Journal of the American Chemical Society, 135(25):9525-9530, Journal Name: Journal of the American Chemical Society, 135(25):9525-9530
• Country of Publication: United States
• Language: English

Related Subjects

Environmental Molecular Sciences Laboratory