Browse > Article
http://dx.doi.org/10.5012/bkcs.2011.32.8.3003

Oxidation of Benzyl Alcohols with Extraordinarily High Kinetic Isotope Effects  

Jo, Myeong-Ran (Department of Chemistry, Dongguk University)
Seok, Won-K. (Department of Chemistry, Dongguk University)
Publication Information
Bulletin of the Korean Chemical Society / v.32, no.spc8, 2011 , pp. 3003-3008 More about this Journal
Abstract
Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.
Keywords
Ru oxo complex; Mechanisms; High kinetic isotope effects;
Citations & Related Records
Times Cited By KSCI : 1  (Citation Analysis)
연도 인용수 순위
1 Kreevoy, M. M.; Kotchevar, A. T. J. Am. Chem. Soc. 1990, 112, 3579.   DOI
2 Lee, I.-S. H.; Chow, K.-H.; Kreevoy, M. M. J. Am. Chem. Soc. 2002, 124, 7735.
3 Sutin, N. Acc. Chem. Res. 1982, 15, 275.   DOI
4 Anderson, S. N.; Cooksey, C. J.; Holton, S. G.; Johnson, M. D. J. Am. Chem. Soc. 1980, 102, 2312.   DOI
5 Bryant, J. R.; Mayer, J. M. J. Am. Chem. Soc. 2003, 125, 10351.   DOI
6 Lam, W. W. Y.; Yiu, S.- M.; Yiu, D. T. Y.; Lau, T.-C.; Yip, W.-P.; Che, C.-M. Inorg. Chem. 2003, 42, 8011.   DOI
7 Mezer, A.; Friedman, R.; Noivirt, O.; Nachliel, E.; Gutman, M. J. Phys. Chem. B 2005, 109, 11379.   DOI
8 Jeong, Y. J.; Kang, Y.; Han, A.-R.; Lee, Y.-M.; Kotani, H.; Fukuzumi, S.; Nam, W. Angew. Chem. Int. Ed. 2008, 47, 7321.   DOI
9 Gratzel, M. Acc. Chem. Res. 2000, 33, 269.   DOI
10 Wang, M.; Liu, J.; Cevey-Ha, N.; Moon, S.-J.; Liska, P.; Humphry-Baker, R.; Moser, J.-E.; Gratzel, C.; Wang, P.; Zakeeruddin, S.; Gratzel, M. Nano Today 2010, 5, 169.   DOI
11 Hornstein, B. J.; Dattelbaum, D. M.; Schoonover, J. R.; Meyer, T. J. Inorg. Chem. 2007, 46, 8139.   DOI
12 Liu, L.; Yu, M.; Wayland, B. B.; Fu, X. Chem. Commun. 2010, 46, 6353   DOI
13 Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory Chemicals, 3rd ed.; Pergamon Press: New York, 1988.
14 Seok, W. K.; Gupta, A. K.; Roh, S.-J.; Lee, W.; Han, S.-H. Bull. Korean Chem. Soc. 2007, 28, 1311.   DOI
15 Moore, J. W.; Pearson, R. G. Kinetics and Mechanisms, 3rd ed.; John Wiley & Sons: New York, 1981; p 71.
16 Bales, B. C.; Brown, P.; Dehestani, A.; Mayer, J. M. J. Am. Chem. Soc. 2005, 127, 2822.   DOI   ScienceOn
17 Seok, W. K.; Meyer, T. J. Inorg. Chem. 2005, 44, 3931.   DOI
18 Dobson, J. C.; Helms, J. H.; Doppelt, P.; Sullivan, B. P.; Hatfield, W. E.; Meyer, T. J. Inorg. Chem. 1989, 28, 2200.   DOI
19 Roecker, L.; Meyer, T. J. J. Am. Chem. Soc. 1987, 109, 746.   DOI
20 Thompson, M. S.; Meyer, T. J. J. Am. Chem. Soc. 1982, 104, 4106.   DOI
21 Binstead, R. A.; McGuire, M. E.; Dovletoglou, A.; Seok, W. K.; Meyer, T. J. J. Am. Chem. Soc. 1992, 114, 173.   DOI
22 Binstead, R. A.; Moyer, B. A.; Samuels, G. J.; Meyer, T. J. J. Am. Chem. Soc. 1981, 103, 2897.   DOI
23 Gong, J. I.; Mullins, C. B. Acc. Chem. Res. 2009, 42, 1063.   DOI
24 Hu, L.; Cao, X.; Yang, J.; Li, M.; Hong, H.; Xu, Q.; Ge, J.; Wang, L.; Lu, J.; Chen, L.; Hu, H. Chem. Commun. 2011, 47, 1303   DOI
25 Meyer, T. J.; Huynh, M. H. V. Inorg. Chem. 2003, 42, 8140.   DOI
26 Zhang, J.; Liang, J.-L.; Sun, X.-R.; Zhou, H.-B.; Zhu, N.-Y.; Chan, P. W. H.; Che, C.-M. Inorg. Chem. 2005, 44, 3942.   DOI
27 Chen, Z.; Concepcion, J. J.; Hu, X.; Yang, W.; Hoertz, P. G.; Meyer, T. J. Proc. Nat. Acad. Sci. 2010, 107, 7225.   DOI
28 Waidmann, C. R.; Zhou, X.; Tsai, E. A.; Kaminsky, W.; Hrovat, D. A.; Borden, W. T.; Mayer, J. M. J. Am. Chem. Soc. 2009, 131, 4729.   DOI
29 Karmee, S. K.; Greiner, L.; Kraynov, A.; Muller, T. E.; Niemeijer, B.; Leitner, W. Chem. Commun. 2010, 46, 6705.   DOI
30 Wasylenko, D. J.; Ganesamoorthy, C.; Koivisto, B. D.; Henderson, M. A.; Berlinguette, C. P. Inorg. Chem. 2010, 49, 2202.   DOI