"Bare" iron methoxide cation: A simple model to probe the mechanism of β-hydrogen transfer in organometallic compounds

Journal of the American Chemical Society

Volumn 118, Issue 21, 1996, Pages 5047-5055

  Fiedler, Andreas ^a   Schröder, Detlef ^a   Schwarz, Helmut ^a   Tjelta, Brenda L ^b   Armentrout, P B ^b  

^a TECHNISCHE UNIVERSITÄT BERLIN   (Germany)

^b UNIVERSITY OF UTAH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CALCULATIONS; ELECTRON ENERGY LEVELS; ELECTRONIC STRUCTURE; HYDROGEN; IONS; ISOMERIZATION; MASS SPECTROMETRY;

ACTIVATION BARRIERS; BOND DISSOCIATION ENERGY; HYDROGEN TRANSFER; IRON METHOXIDE CATIONS; QUINTET POTENTIAL ENERGY HYPERSURFACE;

ORGANOMETALLICS;

HYDROGEN; IRON DERIVATIVE; IRON METHOXIDE; ORGANOMETALLIC COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; GAS; ISOMERISM; MASS SPECTROMETRY; MODEL; PROTON TRANSPORT;

EID: 0030152598     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953039q     Document Type: Article

References (86)

1. Elschenbroich, C.; Salzer, A. Organometallchemie, Teubner: Stuttgart, 1989.
2. Bradley, D. C.; Mehrota, R. C.; Gaur, D. P. Metal Alkoxides, Academic Press: London, 1978.
3. (a) Meerwein, H.; Schmidt, R. Liebigs Ann. 1925, 444, 221.
4. (b) Verley, A. Bull. Soc. Chem. Fr. 1925, 37, 537.
5. (c) Ponndorf, W. Z. Angew. Chem. 1926, 39, 138.
6. (d) Oppenauer, R. V. Recl. Trav. Chim. 1937, 56, 137.
7. For a recent mechanistic study and numerous references, see: Blum, O.; Milstein, D. J. Am. Chem. Soc. 1995, 117, 4582.
8. Versluis, L.; Ziegler, T. J. Am. Chem. Soc. 1990, 112, 6763.
9. (a) Brookhart, M.; Lincoln, D. M.; Volpe, A. F., Jr.; Schmidt, G. F. Organometallics 1989, 8, 1212.
10. (b) Brookhart, M.; Lincoln, D. M.; Bennett, M. A.; Pelling, S. J. Am. Chem. Soc. 1990, 112, 2691.
11. (c) Brookhart, M.; Volpe, A. F., Jr.; Lincoln, D. M.; Horváth, I. T.; Millar, J. M. J. Am. Chem. Soc 1990, 112, 5634.
12. Versluis, L.; Ziegler, T.; Fan, L. Inorg. Chem. 1990, 29, 4530.
13. Eller, K.; Schwarz, H. Chem. Rev. 1991, 91, 1121.
14. Houriet, R.; Halle, L. F.; Beauchamp, J. L. Organometallics 1983, 2, 1818.
15. See, for example: (a) van Koppen, P. A. M.; Brodbelt-Lustig, J. F.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1990, 112, 5663. (b) Schröder, D.; Schwarz, H. J. Am. Chem. Soc. 1990, 112, 5947. (c) Schultz, R. H.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 729. (d) van Koppen, P. A. M.; Brodbelt-Lustig, J.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 2359. (e) Schröder, D.; Zummack, W.; Schwarz, H. J. Am. Chem. Soc. 1994, 116, 5857.
16. See, for example: (a) van Koppen, P. A. M.; Brodbelt-Lustig, J. F.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1990, 112, 5663. (b) Schröder, D.; Schwarz, H. J. Am. Chem. Soc. 1990, 112, 5947. (c) Schultz, R. H.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 729. (d) van Koppen, P. A. M.; Brodbelt-Lustig, J.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 2359. (e) Schröder, D.; Zummack, W.; Schwarz, H. J. Am. Chem. Soc. 1994, 116, 5857.
17. See, for example: (a) van Koppen, P. A. M.; Brodbelt-Lustig, J. F.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1990, 112, 5663. (b) Schröder, D.; Schwarz, H. J. Am. Chem. Soc. 1990, 112, 5947. (c) Schultz, R. H.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 729. (d) van Koppen, P. A. M.; Brodbelt-Lustig, J.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 2359. (e) Schröder, D.; Zummack, W.; Schwarz, H. J. Am. Chem. Soc. 1994, 116, 5857.
18. See, for example: (a) van Koppen, P. A. M.; Brodbelt-Lustig, J. F.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1990, 112, 5663. (b) Schröder, D.; Schwarz, H. J. Am. Chem. Soc. 1990, 112, 5947. (c) Schultz, R. H.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 729. (d) van Koppen, P. A. M.; Brodbelt-Lustig, J.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 2359. (e) Schröder, D.; Zummack, W.; Schwarz, H. J. Am. Chem. Soc. 1994, 116, 5857.
19. See, for example: (a) van Koppen, P. A. M.; Brodbelt-Lustig, J. F.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1990, 112, 5663. (b) Schröder, D.; Schwarz, H. J. Am. Chem. Soc. 1990, 112, 5947. (c) Schultz, R. H.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 729. (d) van Koppen, P. A. M.; Brodbelt-Lustig, J.; Bowers, M. T.; Dearden, D. V.; Beauchamp, J. L.; Fisher, E. R.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 2359. (e) Schröder, D.; Zummack, W.; Schwarz, H. J. Am. Chem. Soc. 1994, 116, 5857.
20. (a) Czekay, G.; Drewello, T.; Schwarz, H. J. Am. Chem. Soc. 1989, 111, 4561.
21. (b) Czekay, G.; Drewello, T.; Eller, K.; Zummack, W.; Schwarz, H. Organometallics 1989, 8, 2439.
22. (a) Carlin, T. J.; Sallans, L.; Cassady, C. J.; Jacobson, D. B.; Freiser, B. S. J. Am. Chem. Soc. 1983, 105, 6320.
23. (b) Cassady, C. J.; Freiser, B. S.; McElvany, S. W.; Allison, J. J. Am. Chem. Soc. 1984, 106, 6125.
24. (c) Cassady, C. J.; Freiser, B. S. J. Am. Chem. Soc. 1985, 107, 1566.
25. Halle, L. F.; Klein, F. S.; Beauchamp, J. L. J. Am. Chem. Soc. 1984, 106, 2543.
26. Schröder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 910.
27. (a) Srinivas, R.; Sülzle, D.; Weiske, T.; Schwarz, H. Int. J. Mass Spectrom. Ion Professes 1991, 107, 368.
28. (b) Srinivas, R.; Sulzle, D.; Koch, W.; DePuy, C. H.; Schwarz, H. J. Am. Chem. Soc. 1991, 113, 5970.
29. Ervin, K. M.; Armentrout, P. B. J. Chem. Phys. 1985, 83, 166.
30. Schultz, R. H.; Armentrout, P. B. Int. J. Mass Spectrom. Ion Processes 1991, 107, 29.
31. (a) Eller, K.; Schwarz, H. Int. J. Mass Spectrom. Ion Processes 1989, 93, 243.
32. (b) Eller, K.; Zummack, W.; Schwarz, H. J. Am. Chem. Soc. 1990, 112, 621.
33. (a) For recent reviews, see: Goldberg, N.; Schwarz, H. Acc. Chem. Res. 1994, 27, 347. (b) Zagorevskii, D. V.; Holmes, J. L. Mass Spectrom. Rev. 1994, 13, 133.
34. (a) For recent reviews, see: Goldberg, N.; Schwarz, H. Acc. Chem. Res. 1994, 27, 347. (b) Zagorevskii, D. V.; Holmes, J. L. Mass Spectrom. Rev. 1994, 13, 133.
35. (a) Khan, F. A.; Clemmer, D. E.; Schultz, R. H.; Armentrout, P. B. J. Chem. Phys. 1993, 97, 7978.
36. (b) Dalleska, N. F.; Honma, K.; Armentrout, P. B. J. Am. Chem. Soc. 1993, 115, 12125.
37. (c) Dalleska, N. F.; Honma, K.; Sunderlin, L. S.; Armentrout, P. B. J. Am. Chem. Soc. 1994, 116, 3519.
38. (d) Tjelta, B. L.; Armentrout, P. B. J. Am. Chem. Soc. 1995, 117, 5531.
39. (a) Armentrout, P. B. In Advances in Gas Phase Ion Chemistry; Adams, N. G., Babcock, L. M., Eds.; JAI: Greenwich, 1992; Vol. 1, pp 83-119.
40. (b) Schultz, R. H.; Crellin, K. C.; Armentrout, P. B. J. Am. Chem. Soc. 1991, 113, 8590.
41. Freiser, B. S. Talanta 1985, 32, 687.
42. (a) Burnier, R. C.; Cody, R. B.; Freiser, B. S. J. Am. Chem. Soc. 1982, 104, 7436.
43. (b) Freiser, B. S.; Cody, R. B. Int. J. Mass Spectrom. Ion Phys. 1982, 41, 199.
44. Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
45. (a) Wachters, A. J. H. J. Chem. Phys. 1970, 52, 1033.
46. (b) Hay, P. J. J. Chem. Phys. 1977, 66, 4377.
47. Dunning, T. H.; Hay, P. J. In Modern Theoretical Chemistry; Schaefer, H. F., Ed.; Plenum Press: New York, 1977; Vol. II.
48. GAUSSIAN 92/DFT, Revision F.2, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Wong, M. W.; Foresman, J. B.; Robb, M. A.; Head-Gordon, M.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A.; GAUSSIAN Inc.: Pittsburgh, PA, 1993.
49. For a detailed discussion of the theoretical aspects of this approach, see: (a) Holthausen, M. C.; Heinemann, C.; Cornehl, H. H.; Koch, W.; Schwarz, H. J. Chem. Phys. 1995, 102, 4931. (b) Also see: Holthausen, M. C.; Mohr, M.; Koch, W. Chem. Phys. Lett. 1995, 240, 245.
50. For a detailed discussion of the theoretical aspects of this approach, see: (a) Holthausen, M. C.; Heinemann, C.; Cornehl, H. H.; Koch, W.; Schwarz, H. J. Chem. Phys. 1995, 102, 4931. (b) Also see: Holthausen, M. C.; Mohr, M.; Koch, W. Chem. Phys. Lett. 1995, 240, 245.
51. Holthausen, M. C.; Fiedler, A.; Schwarz, H.; Koch. W, Angew. Chem. 1995, 34, 2282.
52. Morokuma, K.; Ahlrichs, R. Personal communications.
53. + isomers, see: Schröder, D.; Fiedler, A.; Hrušák, J.; Schwarz, H. J. Am. Chem. Soc. 1992, 114, 1215.
54. Schröder, D. Ph.D. Thesis, Technische Universität Berlin D83, 1993.
55. (a) Schalley, C. A.; Wesendrup, R.; Schröder, D.; Weiske, T.; Schwarz, H. J. Am. Chem. Soc. 1995, 117, 7711.
56. (b) Wesendrup, R.; Schalley, C. A.; Schröder, D.; Schwarz, H. Chem. Eur. J. 1995, 1, 608.
57. (a) Relevant thermochemical data were taken from: Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Gas Phase Ion and Neutral Thermochemistry. J. Phys. Chem. Ref. Data, Suppl. 1 1988, 17. (b) An accurate value of IE(Fe) = 7.90 eV was taken from: Sugar, J.; Corliss, C. J. Phys. Chem. Ref. Data Suppl. 2 1985, 14.
58. (a) Relevant thermochemical data were taken from: Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Gas Phase Ion and Neutral Thermochemistry. J. Phys. Chem. Ref. Data, Suppl. 1 1988, 17. (b) An accurate value of IE(Fe) = 7.90 eV was taken from: Sugar, J.; Corliss, C. J. Phys. Chem. Ref. Data Suppl. 2 1985, 14.
59. Additional thermochemical information on organometallic ions was taken from: Armentrout, P. B.; Kickel, B. L. In Organometallic Ion Chemistry; Freiser, B. S., Ed.; Kluwer: Dordrecht, 1995; pp 1-45.
60. 3I to form eventually 5. However, within experimental error, all CID spectra were indistinguishable from that shown in Figure 1a. Consequently, either 3-5 were not formed at all or they rapidly isomerize to 1 and/or 2 under CI conditions.
61. Schröder, D.; Sülzle, D.; Hrušák, J.; Bohme, D. K.; Schwarz, H. Int. J. Mass Spectrom. Ion Processes 1991, 110, 145.
62. Burgers, P. C.; Holmes, J. L. Org. Mass Spectrom. 1984, 19, 452.
63. Schultz, R. H.; Armentrout, P. B. J. Phys. Chem. 1993, 97, 596.
64. Calculated from heats of formation given by: Gurvich, L. V.; Veyts, I. V.; Alcock, C. B. Thermodynamic Properties of Individual Substances, 4th ed.; Hemisphere: New York, 1989; Vol. 1, Part 2. Chase, M. W., Jr.; Davies, C. A.; Downey, J. R., Jr.; Frurip, D. J.; McDonald, R. A.; Syverud, A. N. J. Phys. Chem. Ref. Data 1985, 14, Suppl. No. 1 (JANAF Tables).
65. Calculated from heats of formation given by: Gurvich, L. V.; Veyts, I. V.; Alcock, C. B. Thermodynamic Properties of Individual Substances, 4th ed.; Hemisphere: New York, 1989; Vol. 1, Part 2. Chase, M. W., Jr.; Davies, C. A.; Downey, J. R., Jr.; Frurip, D. J.; McDonald, R. A.; Syverud, A. N. J. Phys. Chem. Ref. Data 1985, 14, Suppl. No. 1 (JANAF Tables).
66. 0 by using values in: Wagman D. D.; Evans, W. H.; Parker, V. B.; Schumm, R. H.; Halow, I.; Bailey, S. M.; Churney, K. L.; Nuttall, R. L. J. Phys. Chem. Ref. Data 1982, 11, 1.
67. 0 by using values in: Wagman D. D.; Evans, W. H.; Parker, V. B.; Schumm, R. H.; Halow, I.; Bailey, S. M.; Churney, K. L.; Nuttall, R. L. J. Phys. Chem. Ref. Data 1982, 11, 1.
68. 2) = 33.4 and 33.0 kcal/ mol, respectively, see: (a) Schröder, D.; Schwarz, H. J. Organomet. Chem. 1995, 504, 123. (b) Tjelta, B. L.; Armentrout, P. B. Unpublished results.
69. 2) = 33.4 and 33.0 kcal/ mol, respectively, see: (a) Schröder, D.; Schwarz, H. J. Organomet. Chem. 1995, 504, 123. (b) Tjelta, B. L.; Armentrout, P. B. Unpublished results.
70. +-Cl) = 84 kcal/mol; see: (a) Fisher, E. R.; Schultz, R. H.; Armentrout, P. B. J. Phys. Chem. 1989, 93, 7382. (b) Schröder, D.; Hrušák, J.; Schwarz, H. Ber. Bunsenges. Phys. Chem. 1993, 97, 1086.
71. +-Cl) = 84 kcal/mol; see: (a) Fisher, E. R.; Schultz, R. H.; Armentrout, P. B. J. Phys. Chem. 1989, 93, 7382. (b) Schröder, D.; Hrušák, J.; Schwarz, H. Ber. Bunsenges. Phys. Chem. 1993, 97, 1086.
72. Blum, O.; Stöckigt, D.; Schröder, D.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1992, 31, 603.
73. -1, respectively.
74. 1 symmetry in order to avoid problems encountered at higher symmetries.
75. O-C-H = 111°.
76. Ziegler, T.; Li, J. Can. J. Chem. 1994, 72, 783
77. (a) Langhoff, S. R.; Bauschlicher, C. W., Jr. Annu. Rev. Phys. Chem. 1988, 39, 181.
78. (b) Sodupe, M.; Lluch, J. M.; Oliva, A.; Illas, F.; Rubio, J. J. Chem. Phys. 1989, 90, 6436.
79. (c) McKee, M. L. J. Am. Chem. Soc. 1990, 112, 2601.
80. (d) Ohanessian, G.; Goddard, W. A., III Acc. Chem. Res. 1990, 23, 386.
81. Fe-H = 1.58 Å.
82. 2v symmetry. However, for the most accurate grid, these deviations are within the convergence thresholds of the optimization.
83. 3A) using the Becke3LYP-optimized geometries. These CCSD(T) calculations were also performed with GAUSSIAN92/DFT and the same basis sets were used, except for one additional f-function (three-term fit to a Slater-type orbital) for iron. At this level of theory, the energy difference between the high- and the low-spin TS is even higher, 15 kcal/mol as compared to 8 kcal/mol with Becke3LYP. In view of the limited accuracy of both approaches, this qualitative agreement justifies the use of the economic hybrid method.
84. (a) Fiedler, A.; Schröder, D.; Shaik, S.; Schwarz, H. J. Am. Chem. Soc. 1994, 116, 10734.
85. (b) Shaik, S.; Danovich, D.; Fiedler, A.; Schröder, D.; Schwarz, H. Helv. Chim. Acta 1995, 78, 1393.
86. Becker, H.; Schröder, D.; Zummack, W.; Schwarz, H. J. Am. Chem. Soc. 1994, 116, 1096.