Rh(0) nanoclusters in benzene hydrogenation catalysis: Kinetic and mechanistic evidence that a putative [(C8H17)3NCH3]+[RhCl4]- ion- pair catalyst is actually a distribution of Cl- and [(C8H17)3NCH3]+ stabilized Rh(0) nanoclusters

Journal of the American Chemical Society

Volumn 120, Issue 23, 1998, Pages 5653-5666

  Weddle, Katherine S ^a   Aiken III, John D ^a   Finke, Richard G ^a  

^a Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTHRACENE; BENZENE; CHLORIDE ION; NAPHTHALENE; RHODIUM;

ARTICLE; CATALYSIS; CATALYST; HYDROGENATION;

EID: 0032540691     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja973045h     Document Type: Article

References (117)

1. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
2. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
3. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
4. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
5. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
6. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
7. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
8. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
9. A literature search (Chemical Abstracts Service; CA file) of benzene(w)hydrogenation reveals 974 references, including 231 patents, while a literature search of selective(w)benzene(w)hydrogenation reveals only 50 references (an incomplete search, since we already have in our files more than 50 papers concerned with selectivity in benzene hydrogenation). Lead references follow: (a) Struijk, J.; d'Angremond, M.; Lucas-de Regt, W. J. M.; Scholten, J. J. F. Appl. Catal. A: General 1992, 83, 263. (b) Struijk, J.; Moene, R.; van der Kamp, T.; Scholten, J. J. F., Appl. Catal. A: General 1992, 89, 77. (c) Struijk, J.; Scholten, J. J. F. Appl. Catal. A: General 1992, 82, 277. (d) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1980, 30, 677. (e) Struijk, J.; Scholten, J. J. F. Appl. Catal. 1990, 62, 151. (f) Van der Steen, P. J.; Scholten, J. J. F. Appl. Catal. 1990, 58, 291. (g) Odenbrand, C. U. I.; Andersson, S. L. T. J. Chem. Technol. Biotechnol. 1982, 32, 691 (h) Don, J. A.; Scholten, J. J. F. Faraday Discuss., Chem. Soc. 1982, 72, 145. (i) Odenbrand, C. U. I.; Lundin, S. T. J. Chem. Technol. Biotechnol. 1981, 31, 660.
10. 2n.o
11. (b) Mitsui, O.; Fukuoka, Y. U.S. Patent 4,678,861, 1987, to Asahi Kasei Kogyo Kabushiki Kaisha.
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24. (o) G. W. Parshall notes: "The hydrogenation of benzene to cyclohexene has been a major target of industrial research because the oxidation of cyclohexene to adipic acid may proceed more cleanly than the current cyclohexane oxidation." Parshall, G. W.; Ittel, S. D. Homogeneous Catalysis, John Wiley & Sons: New York, 1992; pp 180-183.
25. (p) We note that a plant for commercial, selective hydrogenation of benzene to cyclohexene was brought on line by Asahi in 1990: Chem. Eng. 1990, 97(10), 25.
26. Aiken, J. D., III; Lin, Y.; Finke, R. G. J. Mol. Catal. 1996, 114, 29.
27. Yin, L.; Finke, R. G. J. Am. Chem. Soc. 1994, 116, 8335.
28. (a) Watzky, M. A.; Finke, R. G. J. Am. Chem. Soc. 1997, 119, 10382.
29. (b) Watzky, M. A.; Aiken, J. D., III, Widegren, J.; Finke, R. G. Chem. Mater. Submitted ("A New Kinetic Method to Follow Transition-Metal Nanocluster Formation Based on Catalytic Activity and the Pseudoelementary Step Concept").
30. (a) Aiken, J. D., III; Finke, R. G. Experiments in progress.
31. (b) Aiken, J. D., III; Finke, R. G. Experiments in progress.
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33. Aiken, J. D., Ill; Finke, R. G. Unpublished results.
34. 8c
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38. (b) Jones, R. A.; Seeberger, M. H. J. Chem. Soc., Chem. Commun. 1985, 373. Note the induction periods and dark catalyst colors described therein.
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41. 31P NMR (e.g., ≥ ca. 90% catalyst recovery), ≥ 90% rate still after 18 catalyst recycles, Table 1), and use of Collman's three-phase test].
42. 11 - not an inappropriate suggestion, since one does not prove a mechanism, but only disproves alternative mechanisms.
43. (a) Januszklewicz, K. R.; Alper, H. Organomelallics, 1983, 2, 1055.
44. (b) Note that these authors were aware that the actual catalyst had not been identified, specifically stating on p 1056 of their paper that, "Finally, we are not certain whether the phase-transfer process described herein involves a soluble or insoluble rhodium catalyst".
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56. 4-6,11
57. 3 to make Multeities' Co-based arene hydrogenation catalyst reproducible.
58. 3 formation on p 590.
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61. -2400 Nanoclusters: Synthesis, Characterization and Hydrogenation Catalysis, submitted. (f) Edlund, D. J. Ph.D. Thesis, University of Oregon, 1987.
62. -2400 Nanoclusters: Synthesis, Characterization and Hydrogenation Catalysis, submitted. (f) Edlund, D. J. Ph.D. Thesis, University of Oregon, 1987.
63. -2400 Nanoclusters: Synthesis, Characterization and Hydrogenation Catalysis, submitted. (f) Edlund, D. J. Ph.D. Thesis, University of Oregon, 1987.
64. -2400 Nanoclusters: Synthesis, Characterization and Hydrogenation Catalysis, submitted. (f) Edlund, D. J. Ph.D. Thesis, University of Oregon, 1987.
65. -2400 Nanoclusters: Synthesis, Characterization and Hydrogenation Catalysis, submitted. (f) Edlund, D. J. Ph.D. Thesis, University of Oregon, 1987.
66. -1 from a first-order plot (as the literature study describes their system as following first-order kinetics). We found that the data had a better fit to an autocatalytic growth curve, Figure 4, and expect, therefore, that the rate reported in the literature study has no rigorous meaning because the data were fit to the wrong mechanism.
67. 460, respectively.
68. 5b and references therein.
69. (a) Bönnemann, H.; Brijoux, W.; Brinkmann, R.; Dinjus, E.; Fretzen, R.; Joussen, T.; Korall, B. J. Mol. Catal. 1992, 74, 323.
70. (b) See also ref 16a.
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72. 561 cluster. Therefore, the surface number of Rh atoms decreases from ca. 52% to ca. 26% (i.e., a 2-fold drop in the number of surface Rh atoms) on going from a 47 Å to a 21 Å cluster.
73. (b) Teo, B. K.; Sloane, N. J. A. Inorg. Chem. 1985, 24, 4545.
74. 9c). Since the curves show an induction period and are sigmoidal (i.e., as shown by the fit of the literature data in Figure 4 herein), but since their autocatalytic nature was not appreciated previously, they could not have been properly analyzed previously and, hence, any focus attempting to further analyze the prior claim of highly reproducible kinetics is probably a misguided effort.
75. 9c nor the present, study.
76. 2(H)(Ph) surface intermediates) which can then lead to D-incorporation into the unreacted benzene. (a) Moyes, R. B.; Wells, P. B. Adv. Catal. 1973, 23, 121. (b) Van Hardeveld, R.; Hartog, F. Adv. Catal. 1972, 22, 75. (c) Siegel, S. Adv. Catal. 1966, 16, 123. (d) Rooney, J. J.; Webb, G. J. Catal. 1964, 3, 488. (e) Bond, G. C. Catalysis by Metals; Academic Press: New York, 1962; pp 316-319.
77. 2(H)(Ph) surface intermediates) which can then lead to D-incorporation into the unreacted benzene. (a) Moyes, R. B.; Wells, P. B. Adv. Catal. 1973, 23, 121. (b) Van Hardeveld, R.; Hartog, F. Adv. Catal. 1972, 22, 75. (c) Siegel, S. Adv. Catal. 1966, 16, 123. (d) Rooney, J. J.; Webb, G. J. Catal. 1964, 3, 488. (e) Bond, G. C. Catalysis by Metals; Academic Press: New York, 1962; pp 316-319.
78. 2(H)(Ph) surface intermediates) which can then lead to D-incorporation into the unreacted benzene. (a) Moyes, R. B.; Wells, P. B. Adv. Catal. 1973, 23, 121. (b) Van Hardeveld, R.; Hartog, F. Adv. Catal. 1972, 22, 75. (c) Siegel, S. Adv. Catal. 1966, 16, 123. (d) Rooney, J. J.; Webb, G. J. Catal. 1964, 3, 488. (e) Bond, G. C. Catalysis by Metals; Academic Press: New York, 1962; pp 316-319.
79. 2(H)(Ph) surface intermediates) which can then lead to D-incorporation into the unreacted benzene. (a) Moyes, R. B.; Wells, P. B. Adv. Catal. 1973, 23, 121. (b) Van Hardeveld, R.; Hartog, F. Adv. Catal. 1972, 22, 75. (c) Siegel, S. Adv. Catal. 1966, 16, 123. (d) Rooney, J. J.; Webb, G. J. Catal. 1964, 3, 488. (e) Bond, G. C. Catalysis by Metals; Academic Press: New York, 1962; pp 316-319.
80. 2(H)(Ph) surface intermediates) which can then lead to D-incorporation into the unreacted benzene. (a) Moyes, R. B.; Wells, P. B. Adv. Catal. 1973, 23, 121. (b) Van Hardeveld, R.; Hartog, F. Adv. Catal. 1972, 22, 75. (c) Siegel, S. Adv. Catal. 1966, 16, 123. (d) Rooney, J. J.; Webb, G. J. Catal. 1964, 3, 488. (e) Bond, G. C. Catalysis by Metals; Academic Press: New York, 1962; pp 316-319.
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84. 12).
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87. 22c
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90. Anton, D. R.; Crabtree, R. H. Organometallics 1983, 2, 855.
91. 18b (ii) dct is no longer commercially available, and, most importantly (iii) in light of the strong evidence uncovered for Rh(0) nanocluster catalysis, the testing of a "homogeneous" catalyst poison such as dct on Rh(0) nanoclusters is no longer sensible or cost-effective.
92. (b) Crabtree, R. H. Private communication.
93. 4) is between 0 and 8 Hz.
94. 4) are much less than those observed for Rh(III) hydrides, the latter usually falling in the range of 15-30 Hz.
95. Bradley, J. In Colloids and Clusters: From Theory to Applications; Schmid, G., Ed.; VCH Publishers: New York, 1994; see pp 515-522.
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