Thumbnail
Access Restriction
Open

Author Scott, S. L. ♦ Bakac, A. ♦ Espenson, J. H.
Sponsorship USDOE
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CHEMISTRY ♦ ALDEHYDES ♦ OXIDATION ♦ CHROMIUM COMPLEXES ♦ REDUCTION ♦ ALCOHOLS ♦ CARBOXYLIC ACIDS ♦ REACTION INTERMEDIATES ♦ CATIONS ♦ CHEMICAL REACTION KINETICS ♦ ACTIVATION ENERGY
Abstract Four methods have been developed to prepare aquachromium (IV), which is believed to be an oxo ion, CrO{sup 2+}. It readily converts Ph{sub 3}P to Ph{sub 3}PO (k = 2.1 x 10{sup 3} L mol{sup -1} s{sup -1}) at 25 {degrees}C in 85% CH{sub 3}CN/H{sub 2}O (0.10 M HClO{sub 4}). The reactions used to form CrO{sup 2+} are those between Cr{sup 2+} and (a) O{sub 2} (b) anaerobic CrO{sub 2}{sup 2+}, (c) anaerobic CrOOCr{sup 4+}, and (d) anaerobic Tl(III). The CrO{sup 2+} has a half-life of 30 s in acidic solution at room temperature and will oxidize alcohols, aldehydes, and certain carboxylates as well as diethyl ether. The second-order rate constants (L mol{sup -1} s{sup -1}) in acidic solution ({mu} = 1.0 M HClO{sub 4}/LiClO{sub 4}, 25 {degrees}C) are as follows: CH{sub 3}OH, 52; CD{sub 3}OH, 15; C{sub 2}H{sub 5}OH, 88; C{sub 2}D{sub 5}OH, 41; (CH{sub 3}){sub 2}CHOH, 12.0; (CD{sub 3}){sub 2}CDOH, 4.6; CH{sub 2}=CHCH{sub 2}OH, 101; CH{sub 3}(CH{sub 2}){sub 2}CH{sub 2}OH, 44; (C{sub 2}H{sub 5})(CH{sub 3})CHOH, 41; (CH{sub 3}){sub 3}CCH{sub 2}OH, 39; C{sub 6}H{sub 5}CH{sub 2}OH, 56; (C{sub 6}H{sub 5})(CH{sub 3})CHOH, 30; (C{sub 6}H{sub 5}){sub 2}CHOH, 10.5; p-CH{sub 3}OC{sub 6}H{sub 4}CH{sub 2}OH, 71; p-CH{sub 3}C{sub 6}H{sub 4}CH{sub 2}OH, 66; p-CF{sub 3}C{sub 6}H{sub 4}CH{sub 2}OH, 60; c-C{sub 4}H{sub 7}OH, 44; c-C{sub 5}H{sub 9}OH, 31; HCHO-H{sub 2}O, 92; (CH{sub 3}){sub 3}CCHO, 37; HCO{sub 2}H, 11.6; HCO{sub 2}{sup -}, 6.9x10{sup 3}; HC{sub 2}O{sub 4}{sup -}, 2.2x10{sup 3}; (C{sub 2}H{sub 5}){sub 2}O, 4.5. Activation parameters were also determined for selected reactions. 48 refs., 10 figs., 3 tabs.
ISSN 00027863
Educational Use Research
Learning Resource Type Article
Publisher Date 1992-05-20
Publisher Place United States
Journal Journal of the American Chemical Society
Volume Number 114
Issue Number 11


Open content in new tab

   Open content in new tab