Platinum catalysts for the high-yield oxidation of methane to a methanol derivative

Science

Volumn 280, Issue 5363, 1998, Pages 560-564

  Periana, Roy A ^a   Taube, Douglas J ^a   Gamble, Scott ^a   Taube, Henry ^a   Satoh, Takashi ^a   Fujii, Hiroshi ^a  

^a NZ Legacy LLC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

METHANE; METHANOL; PLATINUM;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; HYDROGEN BOND; LOW TEMPERATURE PROCEDURES; METAL BINDING; OXIDATION; OXIDATION REDUCTION REACTION; PRIORITY JOURNAL; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0032562776     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.280.5363.560     Document Type: Article

References (33)

1. For developments in this area see Oil Gas J. 95 (no. 16), 16 (1997); U.S. Patents 4,833,170; 4,973,453; 4,686,238; 5,628,931; 5,658,497; 5,653,916; 5,639,401; 5,645,613; 5,621,155; 5,620,670; 5,543,437; 5,506,272; 5,504,118; 5,500,449; and 5,324,335.
2. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
3. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
4. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
5. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
6. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
7. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
8. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
9. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
10. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
11. B. A. Arndtsen, R. G., Bergman, T. A. Mobley, T. H. Peterson, Acc. Chem. Res. 28, 154 (1995); J. A. Davies, P. L. Watson, J. F. Liebman, A. Greenberg, Eds., Selective Hydrocarbon Activation (Wiley-VCH, New York, 1990); C. L. Hill, Activation and Functionalization of Alkanes (Wiley-Interscience, New York, 1989); A. Sen, Acc. Chem. Res. 21, 421 (1988); A. E. Shilov and E. I. Karasevich, Catal. Met. Complexes 17, 87 (1994); J. Sommer and J. Bukala, Acc. Chem. Res. 26, 370 (1993); M. Ephritikhine, Industrial Applications of Homogeneous Catalysis, M. F. Petit, Ed. (Reidel, Dordrecht, Netherlands, 1988), pp. 257-275; K. M. Waltz and J. F. Hartwig, Science 277, 211 (1997); K. I. Goldberg and D. D. Wick, J. Am. Chem. Soc. 119, 10235 (1997); S. E. Bromberg et al., Science 278, 260 (1997).
12. A. E. Shilov, Activation of Saturated Hydrocarbons by Transition Metal Complexes (Reidel, Dordrecht, Netherlands, 1984).
13. The oxidation of butane to maleic anhydride or acetic acid, propane to acrylonitrile, or isobutane to t-butyl hydroperoxide are atypical, free-radical - based alkane autooxidation reactions that proceed in reasonable selectivities and yields (>10% per pass) because either the products are uniquely stable, as in the case of maleic anhydride, acetic acid, and acrylonitrile, or in the case of isobutane, the reactivity of the tertiary C-H bond is significantly higher than those in the products.
14. 4]final) × 100 % yield ≡ (% conversion) × (% selectivity)
15. R. A. Periana et al., Science 259, 340 (1993); U.S. Patents 5,233,113 and 5,306,855.
16. "C-H activation" is used to describe a process where substitution of a stronger C-H bond (375 to 440 kJ/mol) occurs to produce a weaker metal-carbon bond (210 to 335 kJ/mol).
17. P. M. Henry, Palladium Catalyzed Oxidation of Hydrocarbons, (Reidel, Dordrecht, Netherlands, 1980).
18. Turnover frequency = [(mol of product produced)/ (mol of added catalysts)] per second; Turnover number = [(mol of product produced)/(mol of added catalysts)] when reaction is stopped.
19. 3OH) analyses allowed >90 to 95% mass balance on methane.
20. Oxidation of the Pt(II) center to Pt(IV) occurs as evidenced by changes in the solution NMR spectra. Free ligand is generated, but no reaction at the C-H bonds is observed.
21. -1) were values obtained over the integrated reaction time.
22. The catalyst was still active after 500 turnovers. The reaction was stopped at this point. The actual number of turnovers before the regeneration would be required has not been determined.
23. 4 used in the calculations.
24. M. W. Holtcamp, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 119, 848 (1997) and references therein.
25. 4 containing 1 under typical reaction conditions over a 30-min period.
26. Assuming the microscopic reverse of the C-H activation step, protonolysis of the methyl Pt bond is significantly more rapid than the C-H activation step.
27. 2.
28. If H/D exchange is occurring with these oxidation states the rates must be at least three orders of magnitude slower than with Pt(II).
29. C. Hall and R. N. Perutz, Chem. Rev. 96, 3125 (1996); J. J. Schneider, Angew. Chem. Int. Ed. Engl. 35, 1068 (1996) and references therein. Methane complexes are now generally accepted intermediates in C-H activation reactions. To date, extensive indirect data have been obtained to support the intermediacy of such species. However, none have been isolated and characterized.
30. C. Hall and R. N. Perutz, Chem. Rev. 96, 3125 (1996); J. J. Schneider, Angew. Chem. Int. Ed. Engl. 35, 1068 (1996) and references therein. Methane complexes are now generally accepted intermediates in C-H activation reactions. To date, extensive indirect data have been obtained to support the intermediacy of such species. However, none have been isolated and characterized.
31. 2 formation). In this case, we can estimate that the rate C-H activation of methane is at least 100 times greater than that of methyl bisulfate (13). No methane formation is observed in these reactions indicating that the oxidation of methane to methyl bisulfate occurs irreversible as expected.
32. Similar scrambling had been observed by Shilov (3) who proposed a carbene-hydride intermediate to explain the results.
33. Catalytica Advanced Technologies Inc., a wholly owned subsidiary of Catalytica Inc., acknowledges participation in this program by Syntroleum Corp.; Techmocisco Inc., a wholly owned subsidiary of Mitsubishi Oil Co., Ltd.; Petro-Canada; and the U.S. Department of Commerce, National Institutes of Standards and Technology.