Investigation of the reactivity of Pt phosphinito and molybdocene nitrile hydration catalysts with cyanohydrins

Inorganic Chemistry

Volumn 48, Issue 16, 2009, Pages 7828-7837

  Ahmed, Takiya J ^a   Fox, Brandy R ^a   Knapp, Spring Melody M ^a   Yelle, Robert B ^a   Juliette, J Jerrick ^b   Tyler, David R ^a  

^a UNIVERSITY OF OREGON   (United States)

^b DOW CHEMICAL COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYANOHYDRIN; NITRILE; PLATINUM COMPLEX; WATER;

ARTICLE; CATALYSIS; CHEMISTRY; ELECTRON; QUANTUM THEORY;

CATALYSIS; ELECTRONS; NITRILES; ORGANOPLATINUM COMPOUNDS; QUANTUM THEORY; WATER;

EID: 68949097266     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic900734d     Document Type: Article

References (35)

1. Green, M. M.; Wittcoff, H. A. Organic Chemistry Principles and Industrial Practice; Wiley-VCH: Weinheim, 2003; p 137.
2. Wilczynski, R.; Juliette, J. J. In Kirk-Othmer Encyclopedia of Chemical Technology, 5th ed.; Wiley: Hoboken, NJ, 2006; Vol. 16, p 227.
3. Several noteworthy acid-free synthetic methods for the hydration of cyanohydrins utilizing boron, metal oxides, and nitrile hydratase enzymes as mediators have been disclosed in patents and in the literature. These methods are summarized in the Supporting Information.
4. Kukushkin, V. Y.; Pombeiro, A. J. L. Inorg. Chim. Acta 2005, 358, 1.
5. Ghaffar, T.; Parkins, A. W. Tetrahedron Lett. 1995, 36, 8657.
6. Ghaffar, T.; Parkins, A. W. J. Mol. Catal. A: Chem. 2000, 160, 249.
7. Parkins, A. W.; Ghaffar, T. PCT Intl. Patent Appl. WO 9630379, 1996.
8. Cobley, C. J.; Van den Heuvel, M.; Abbadi, A.; De Vries, J. G. Tetrahedron Lett. 2000, 41, 2467.
9. Jiang, X.-b.; Minnaard, A. J.; Feringa, B. L.; De Vries, J. G. J. Org. Chem. 2004, 69, 2327.
10. Breno, K. L.; Pluth, M. D.; Tyler, D. R. Organometallics 2003, 22, 1203.
11. Ahmed, T. J.; Zakharov, L. N.; Tyler, D. R. Organometallics 2007, 26, 5179.
12. Ahmed, T. J.; Tyler, D. R. Organometallics 2008, 27, 2608.
13. Ren, J. G.; Tomita, H.; Minato, M.; Osakada, K.; Ito, T. Chem. Lett. 1994, 637.
14. Osprian, I.; Fechter, M. H.; Griengl, H. J. Mol. Catal. B: Enzymatic 2003, 24-25, 89.
15. Schuchardt, K. L. D., B. T.; Black, G. D. A Problem-Solving Environment's Evolution Toward Grid Services and a Web Architecture. In Concurrency and Computation: Practice and Experience, Ecce; Wiley Inter Science: Hoboken, NJ, 2002; Vol. 14, pp 1221-1239.
16. Black, G.; Daily, 1; Didier, T.; Elsethagen, T.; Feller, D.; Gracio, D.; Hackler, M.; Havre, S.; Jones, D.; Jurrus, E.; Keller, T.; Lansing, C.; Matsumoto, S.; Palmer, B.; Peterson, M.; Schuchardt, K.; Stephan, E.; Taylor, H.; Thomas, G.; Vorpagel, E.; Windus, T. A Problem Solving Environment for Computational Chemistry, 3.2; Ecce: 2004.
17. Kendall, R. A.; Apra, E.; Bernholdt, D. E.; Bylaska, E. J.; Dupuis, M.; Fann, G. I.; Harrison, R. J.; Ju, J.; Nichols, J. A.; Nieplocha, J.; Straatsma, T. P.; Windus, T. L.; Wong, A. T. Comput. Phys. Commun. 2000, 128, 260.
18. Bylaska, E. J.; de Jong, W. A.; Kowalski, K.; Straatsma, T. P.; Valiev, M.; Wang, D.; Aprà, E.; Windus, T. L.; Hirata, S.; Hackler, M. T.; Zhao, Y.; Fan, P.-D.; Harrison, R. J.; Dupuis, M.; Smith, D. M. A.; Nieplocha, J.; Tipparaju, V.; Krishnan, M.; Auer, A. A.; Nooijen, M.; Brown, E.; Cisneros, G.; Fann, G. I.; Friichtl, H.; Garza, J.; Hirao, K.; Kendall, R.; Nichols, J. A.; Tsemekhman, K.; Wolinski, K.; Anchell, J.; Bernholdt, D.; Hess, P. A.; Jaffe, J.; Johnson, B.; Ju, J.; Kobayashi, R.; Kutteh, R.; Lin, Z.; Littlefield, R.; Long, X.; Meng, B.; Wong, T. A.; Zhang, Z. NW Chem 2006.
19. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
20. Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650.
21. Andrae, D.; Haeussermann, U.; Dolg, M.; Stoll, H.; Preuss, H. Theor Chim Acta 1991, 78, 247.
22. Martin, J. M. L.; Sundermann, A. J. Chem. Phys. 2001, 114, 3408.
23. Becke, A. D. Phys. Rev. A 1988, 38, 3098.
24. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
25. Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
26. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
27. Klamt, A.; Schueuermann, G. J. Chem. Soc, Perkin Trans. 2 1993, 799.
28. Stefanovich, E. V.; Truong, T. N. Chem. Phys. Lett. 1995, 244, 65.
29. Prior studies showed that H/D exchange in alcohols occurs by a mechanism involving coordination through the oxygen atom, followed by β-hydride elimination. (See Balzarek, C.; Weakley, T. J. R.; Tyler, D. R. J. Am. Chem. Soc. 2000, 722, 9427.) However, beta-hydride elimination is not possible from coordinated ACH because it is a tertiary alcohol.
30. 31
31. For the reactions carried out at 43 °C, nitriles containing electron-withdrawing groups displayed pseudo-first order kinetics. In contrast, pseudo-zero-order kinetics were observed for electron-donating nitriles, indicating a change in the rate-determining step. This inconsistency precluded generation of a Hammett plot. Kinetic traces for each substrate are available in the Supporting Information.
32. This value was the rate after 30 min of reaction.
33. Unfortunately, rate data could not be obtained for the 2-methox-yisobutyronitrile. However, the reaction of ∼0.50 M 2-methoxyisobutyro-nitrile did proceed to completion.
34. 2O)2H}] is described in more detail in a following section.
35. Schlesinger, G.; Miller, S. L. J. Am. Chem. Soc. 1973, 95, 3729.