Mechanistic and theoretical analysis of the oxidative addition of H2 to six-coordinate molybdenum and tungsten complexes M(PMe3)4X2 (M = Mo, W; X = F, Cl, Br, I): An inverse equilibrium isotope effect and an unprecedented halide dependence

Journal of the American Chemical Society

Volumn 121, Issue 49, 1999, Pages 11402-11417

  Hascall, Tony ^a   Rabinovich, Daniel ^a   Murphy, Vincent J ^a,b   Beachy, Michael D ^a   Friesner, Richard A ^a   Parkin, Gerard ^a  

^a Columbia University ^*  (United States)

^b SYMYX TECHNOLOGIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DEUTERIUM; HALIDE; METAL COMPLEX; MOLYBDENUM; TUNGSTEN;

ARTICLE; CHEMICAL BINDING; DISSOCIATION; ENERGY; MOLECULAR INTERACTION; OXIDATION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0033572870     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9920009     Document Type: Article

References (188)

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8. Murphy, V. J.; Rabinovich, D.; Hascall, T.; Klooster, W. T.; Koetzle, T. F.; Parkin, G. J. Am. Chem. Soc. 1998, 120, 4372-4387.
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10. 2, see: (a) Sharp, P. R. Ph.D. Thesis, Massachusetts Institute of Technology, 1980. (b) Sharp, P. R.; Frank, K. G. Inorg. Chem. 1985, 24, 1808-1813. (c) Chiu, K. W.; Lyons, D.; Wilkinson, G.; Thornton-Pett, M.; Hursthouse, M. B. Polyhedron 1983, 2, 803-810.
11. 2, see: (a) Sharp, P. R. Ph.D. Thesis, Massachusetts Institute of Technology, 1980. (b) Sharp, P. R.; Frank, K. G. Inorg. Chem. 1985, 24, 1808-1813. (c) Chiu, K. W.; Lyons, D.; Wilkinson, G.; Thornton-Pett, M.; Hursthouse, M. B. Polyhedron 1983, 2, 803-810.
12. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
13. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
14. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
15. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
16. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
17. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
18. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
19. For reviews on metal hydrides, see: (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH Publishers, Inc.: New York. 1991. (b) Transition Metal Hydrides; Muetterties, E. L., Ed.; Marcel Dekker, Inc.: New York, 1971. (c) Teller, R. G.; Bau, R. Struct. Bonding (Berlin) 1981, 44, 1-82. (d) Crabtree, R. H. In Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley: New York, 1994; Vol. 3, pp 1392-1400. (e) Hlatky, G. G.; Crabtree, R. H. Coord. Chem. Rev. 1985, 65, 1-48. (f) Moore, D. S.; Robinson, S. D. Chem. Soc. Rev. 1983, 12, 415-452. (g) Kuhlman, R. Coord. Chem. Rev. 1997, 167, 205-232. (h) Also see the special volume: Inorg. Chim. Acta 1997, 259, Nos. 1 and 2.
20. 2 at 80 °C with respect to reductive elimination was first noted by Sharp (ref 5b).
21. 2 has also been reported to exist as a diamagnetic cisisomer, but we have not observed such a species. See: Chiu, K. W.; Jones, R. A.; Wilkinson, G.; Galas, A. M. R.; Hursthouse, M. B.; Malik, K. M. A. J. Chem. Soc., Dalton Trans. 1981, 1204-1211.
22. Murphy, V. J.; Hascall, T.; Chen, J. Y.; Parkin, G. J. Am. Chem. Soc. 1996, 118, 7428-7429.
23. (aq) to give a bifluoride derivative. See ref 9.
24. b,d) compounds have been previously reported, (a) Carmona, E.; Marin, J. M.; Poveda, M. L.; Atwood, J. L.; Rogers, R. D. Polyhedron 1983, 2, 185-193. (b) Carmona, E.; Marin, J. M.; Poveda, M. L.; Rogers, R. D.; Atwood, J. L. J. Am. Chem. Soc. 1983, 105, 3014-3022. (c) Krueger, S. T.; Poli, R.; Rheingold, A. L.; Staley, D. L. Inorg. Chem. 1989, 28, 4599-4607. (d) Brookhart, M.; Cox, K.; Cloke, F. G. N.; Green, J. C.; Green, M. L. H.; Hare, P. M.; Bashkin, J.; Derome, A. E.; Grebenik, P. D. J. Chem. Soc., Dalton Trans. 1985, 423- 433.
25. b,d) compounds have been previously reported, (a) Carmona, E.; Marin, J. M.; Poveda, M. L.; Atwood, J. L.; Rogers, R. D. Polyhedron 1983, 2, 185-193. (b) Carmona, E.; Marin, J. M.; Poveda, M. L.; Rogers, R. D.; Atwood, J. L. J. Am. Chem. Soc. 1983, 105, 3014-3022. (c) Krueger, S. T.; Poli, R.; Rheingold, A. L.; Staley, D. L. Inorg. Chem. 1989, 28, 4599-4607. (d) Brookhart, M.; Cox, K.; Cloke, F. G. N.; Green, J. C.; Green, M. L. H.; Hare, P. M.; Bashkin, J.; Derome, A. E.; Grebenik, P. D. J. Chem. Soc., Dalton Trans. 1985, 423- 433.
26. b,d) compounds have been previously reported, (a) Carmona, E.; Marin, J. M.; Poveda, M. L.; Atwood, J. L.; Rogers, R. D. Polyhedron 1983, 2, 185-193. (b) Carmona, E.; Marin, J. M.; Poveda, M. L.; Rogers, R. D.; Atwood, J. L. J. Am. Chem. Soc. 1983, 105, 3014-3022. (c) Krueger, S. T.; Poli, R.; Rheingold, A. L.; Staley, D. L. Inorg. Chem. 1989, 28, 4599-4607. (d) Brookhart, M.; Cox, K.; Cloke, F. G. N.; Green, J. C.; Green, M. L. H.; Hare, P. M.; Bashkin, J.; Derome, A. E.; Grebenik, P. D. J. Chem. Soc., Dalton Trans. 1985, 423- 433.
27. b,d) compounds have been previously reported, (a) Carmona, E.; Marin, J. M.; Poveda, M. L.; Atwood, J. L.; Rogers, R. D. Polyhedron 1983, 2, 185-193. (b) Carmona, E.; Marin, J. M.; Poveda, M. L.; Rogers, R. D.; Atwood, J. L. J. Am. Chem. Soc. 1983, 105, 3014-3022. (c) Krueger, S. T.; Poli, R.; Rheingold, A. L.; Staley, D. L. Inorg. Chem. 1989, 28, 4599-4607. (d) Brookhart, M.; Cox, K.; Cloke, F. G. N.; Green, J. C.; Green, M. L. H.; Hare, P. M.; Bashkin, J.; Derome, A. E.; Grebenik, P. D. J. Chem. Soc., Dalton Trans. 1985, 423-433.
28. b (a) Minas da Piedade, M.; Martino Simões, J. A. J. Organomet. Chem. 1996, 518, 167-180. (b) Reinaud, O.; Yap, G. P. A.; Rheingold, A. L.; Theopold, K. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2051-2052.
29. b (a) Minas da Piedade, M.; Martino Simões, J. A. J. Organomet. Chem. 1996, 518, 167- 180. (b) Reinaud, O.; Yap, G. P. A.; Rheingold, A. L.; Theopold, K. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2051-2052.
30. For rationalization of the use of this expression in determining bond energies, see ref 34 in the following: Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. Organometallics 1991, 10, 1875-1887.
31. -1. CRC Handbook of Chemistry und Physics, 70th ed.; Weast, R. C., Ed.; CRC Press: Boca Raton, FL, 1989-1990; p F-199.
32. For examples, see Table S1 in the Supporting Information.
33. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
34. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
35. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
36. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79-98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
37. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
38. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
39. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
40. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
41. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
42. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal-Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
43. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
44. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
45. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503-561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
46. For tabulations of bond energies, see; (a) Bonding Energetics in Organometallic Compounds; Marks, T. J. Ed.; ACS Symposium Series 428; American Chemical Society: Washington, DC, 1990. (b) Pearson, R. G. Chem. Rev. 1985, 85, 41-49. (c) Halpern, J. Inorg. Chim. Acta 1985, 100, 41-48. (d) Skinner, H. A.; Connor, J. A. Pure Appl. Chem. 1985, 57, 79- 98. (e) Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688. (f) Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110. (g) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (h) Wang, D.; Angelici, R. J. J. Am. Chem. Soc. 1996, 118, 935-942. (i) Eisenberg, D. C.; Norton, J. R. Isr. J. Chem. 1991, 31, 55-66. (j) Pilcher, G.; Skinner, H. A. In The Chemistry of the Metal- Carbon Bond; Hartley, F. R., Patai, S., Eds.; Wiley: New York, 1982; Vol. 1, Chapter 2, pp 43-90. (k) Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928. (l) King, W. A.; Di Bella, S.; Gulino, A.; Lanza, G.; Fragala, I. L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 355-366. (m) Hoff, C. D. Prog. Inorg. Chem. 1992, 40, 503- 561. (f) Energetics of Organometallic Species; Martinho Simões, J. A., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992.
47. 2 (E = O, S, Se, Te), see: (a) Cotton, F. A.; Feng, X. Inorg. Chem. 1996, 35, 4921-4925. (b) Kim, W.-S.; Kaltsoyannis, N. Inorg. Chem. 1998, 37, 674-678. (c) Kaltsoyannis, N. J. Chem. Soc., Dalton Trans. 1994, 1391-1400.
48. 2 (E = O, S, Se, Te), see: (a) Cotton, F. A.; Feng, X. Inorg. Chem. 1996, 35, 4921-4925. (b) Kim, W.-S.; Kaltsoyannis, N. Inorg. Chem. 1998, 37, 674-678. (c) Kaltsoyannis, N. J. Chem. Soc., Dalton Trans. 1994, 1391-1400.
49. 2 (E = O, S, Se, Te), see: (a) Cotton, F. A.; Feng, X. Inorg. Chem. 1996, 35, 4921-4925. (b) Kim, W.-S.; Kaltsoyannis, N. Inorg. Chem. 1998, 37, 674-678. (c) Kaltsoyannis, N. J. Chem. Soc., Dalton Trans. 1994, 1391-1400.
50. Jaguar 3.5, Schrodinger, Inc., Portland, OR, 1998.
51. The differences between ΔH° and ΔE are those at 25 °C.
52. Jacobsen, H.; Berke, H. Chem. Eur. J. 1997, 3, 881-886.
53. 2 from a metal center follow a similar trend, with the barriers being greater for the heavier metal. See, for example: Halpern, J.; Cai, L.; Desrosiers, P. J.; Lin, Z. J. Chem. Soc., Dalton Trans. 1991, 717-723.
54. M-C bond energies also increase upon descending a transition metal group. See, for example: Mancuso, C.; Halpern, J. J. Organomet. Chem. 1992, 428, C8-C11.
55. Dias, A. R.; Martinho Simões, J. A. Polyhedron 1988, 7, 1531-1544.
56. (a) Ohanessian, G.; Goddard, W. A., III. Acc. Chem. Res. 1990, 23, 386-392.
57. (b) Landis, C. R.; Firman, T. K.; Root, D. M.; Cleveland, T. J. Am. Chem. Soc. 1998, 120, 1842-1854.
58. Vaska, L.; Werneke, M. F. Ann. N.Y. Acad. Sci. 1971, 172, 546-562.
59. It should be noted that the Vaska system had also been studied by Strohmeier, who obtained results that are not in accord with Vaska's. See: Strohmeier, W.; Müller, F. J. Z. Naturforsch. 1969, 24b, 931-932.
60. (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. Inorg. Chem. 1993, 32, 495-496.
61. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130.
62. Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry, 5th ed.; Wiley: New York, 1988; p 1191.
63. (a) Collman, J. P. Acc. Chem. Res. 1968, 1, 136-141.
64. (b) Collman, J. P.; Roper, W. R. Adv. Organomet. Chem. 1968, 7, 53-94.
65. b (a) Crabtree, R. H.; Quirk, J. M. J. Organomet. Chem. 1980, 199, 99-106. (b) Saillard, J.-Y.; Hoffmann, R. J. Am. Chem. Soc. 1984, 106, 2006-2026.
66. b (a) Crabtree, R. H.; Quirk, J. M. J. Organomet. Chem. 1980, 199, 99-106. (b) Saillard, J.-Y.; Hoffmann, R. J. Am. Chem. Soc. 1984, 106, 2006-2026.
67. 2. See ref 25.
68. (a) Deeming, A. J.; Shaw, B. L. J. Chem. Soc. (A) 1969, 1802-1804.
69. (b) van Doom, J. A.; Masters, C. van der Woude, C. J. Chem. Soc., Dalton Trans. 1978, 1213-1220.
70. 2(CO)X (X = Cl, Br, I) becomes more favored in the sequence Cl < Br < I. See ref 32.
71. (a) Caulton, K. G. New J. Chem. 1994, 18, 25-41.
72. (b) Caulton, K. G. Chemtracts - Inorg. Chem. 1993, 5, 170-172.
73. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
74. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
75. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
76. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
77. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796-3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
78. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
79. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
80. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
81. i indicate that the ease of oxidation increases in the sequence I < Br < Cl. (a) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1993, 115, 7267-7274. (b) Rottink, M. K.; Angelici, R. J. J. Am. Chem. Soc. 1992, 114, 8296-8298. (c) Doherty, N. M.; Hoffman, N. W. Chem. Rev. 1991, 91, 553-573. (d) Agbossou, S. K.; Roger, C.; Igau, A.; Gladysz, J. A. Inorg. Chem. 1992, 31, 419-424. (e) Pomp, C.; Wieghardt, K. Inorg. Chem. 1988, 27, 3796- 3804. (f) Procopio, L. J.; Carroll, P. J.; Berry, D. H. J. Am. Chem. Soc. 1994, 116, 177-185. (g) Lukens, W. W., Jr.; Smith, M. R., III; Andersen, R. A. J. Am. Chem. Soc. 1996, 118, 1719-1728. (h) Hunter, J. A.; Lindsell, W. E. McCullough, K. J.; Parr, R. A.; Scholes, M. L. J. Chem. Soc., Datlon Trans. 1990, 2145-2153. (i) Asaro, M. F.; Cooper, S. R.; Cooper, N. J. J. Am. Chem. Soc. 1986, 108, 5187-5193.
82. 2(CO)X: 1957 (F), 1965 (Cl), 1966 (Br), and 1967 (I). See: Vaska, L.; Peone, J., Jr. J. Chem. Soc., Chem. Commun. 1971, 418-419.
83. Goldman and Krogh-Jespersen have offered another suggestion to account for the observed variation of ν(CO) stretching frequencies in the Vaska system. Specifically, they have attributed the observed ν(CO) trend to the greater electrostatic field strength of the lighter halides, which raises the energy of the Ir d orbitals and, as a consequence, promotes π-back-bonding to CO. See ref 27b.
84. 2, would promote oxidative addition by stabilizing the 18-electron product. See ref 27b.
85. c (a) Reference 34a. (b) Dahlenburg, L.; Höck, N.; Berke, H. Chem. Ber. 1988, 121, 2083-2093. (c) Cowan, R. L.; Trogler, W. C. J. Am. Chem. Soc. 1989, 111, 4750-4761.
86. 2 is coplanar with the
87. c (a) Reference 34a. (b) Dahlenburg, L.; Höck, N.; Berke, H. Chem. Ber. 1988, 121, 2083-2093. (c) Cowan, R. L.; Trogler, W. C. J. Am. Chem. Soc. 1989, 111, 4750-4761.
88. The overlap of filled orbitals results in a repulsive interaction because the antibonding orbital is destabilized to a greater extent than the bonding orbital is stabilized. For example, the overlap of two identical orbitals results in a bonding orbital that is stabilized by an energy Δ/(1 + S), while the antibonding combination is destabilized by Δ/(1 - S), where Δ is the interaction energy and S is the overlap integral. See: Albright, T. A.; Burdett, J. K.; Whangbo, M.-H. Orbital Interactions in Chemistry; Wiley; New York, 1985.
89. 2 follows the opposite trend, with Cl having the lower barrier since π-donation promotes elimination. (a) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. J. Phys. Chem. 1993, 97, 5890-5896. (b) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214.
90. 2 follows the opposite trend, with Cl having the lower barrier since π-donation promotes elimination. (a) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. J. Phys. Chem. 1993, 97, 5890- 5896. (b) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214.
91. 2. See: Bruce, M. R. M.; Kenter, A.; Tyler, D. R. J. Am. Chem. Soc. 1984, 106, 639-644.
92. See. for example: (a) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; Wiley-Interscience: New York, 1988. (b) Trnka, T. M.; Parkin, G. Polyhedron 1997, 16, 1031-1045. (c) Parkin, G. Prog. Inorg. Chem. 1998, 47, 1-165.
93. See. for example: (a) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; Wiley-Interscience: New York, 1988. (b) Trnka, T. M.; Parkin, G. Polyhedron 1997, 16, 1031-1045. (c) Parkin, G. Prog. Inorg. Chem. 1998, 47, 1-165.
94. See. for example: (a) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; Wiley-Interscience: New York, 1988. (b) Trnka, T. M.; Parkin, G. Polyhedron 1997, 16, 1031-1045. (c) Parkin, G. Prog. Inorg. Chem. 1998, 47, 1-165.
95. Mayer, J. M. Comments Inorg. Chem. 1988, 8, 125-135.
96. 2]. See, for example, ref 43a.
97. xy orbital.
98. 2 fragment as compared to that for a bent geometry (see Figures 4 and 5).
99. (a) Reference 4.
100. (b) Green, M. L. H.; Parkin, G.; Chen, M.; Prout, K. J. Chem. Soc., Dalton Trans. 1986, 2227-2236.
101. -1.
102. e (a) Badger, R. M. J. Chem. Phys. 1934, 2, 128-131. (b) Badger, R. M. J. Chem. Phys. 1935, 3, 710-714. (c) Herschbach, D. R.; Laurie, V. W. J. Chem. Phys. 1961, 35, 458-463. (d) Pauling, L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY. 1960; p 231. (e) Christen, D.; Gupta, O. D.; Kadel, J.; Kirchmeier, R. L.; Mack, H. G.; Oberhammer, H.; Shreeve, J. M. J. Am. Chem. Soc. 1991, 113, 9131- 9135.
103. e (a) Badger, R. M. J. Chem. Phys. 1934, 2, 128-131. (b) Badger, R. M. J. Chem. Phys. 1935, 3, 710-714. (c) Herschbach, D. R.; Laurie, V. W. J. Chem. Phys. 1961, 35, 458-463. (d) Pauling, L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY. 1960; p 231. (e) Christen, D.; Gupta, O. D.; Kadel, J.; Kirchmeier, R. L.; Mack, H. G.; Oberhammer, H.; Shreeve, J. M. J. Am. Chem. Soc. 1991, 113, 9131- 9135.
104. e (a) Badger, R. M. J. Chem. Phys. 1934, 2, 128-131. (b) Badger, R. M. J. Chem. Phys. 1935, 3, 710-714. (c) Herschbach, D. R.; Laurie, V. W. J. Chem. Phys. 1961, 35, 458-463. (d) Pauling, L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY. 1960; p 231. (e) Christen, D.; Gupta, O. D.; Kadel, J.; Kirchmeier, R. L.; Mack, H. G.; Oberhammer, H.; Shreeve, J. M. J. Am. Chem. Soc. 1991, 113, 9131- 9135.
105. e (a) Badger, R. M. J. Chem. Phys. 1934, 2, 128-131. (b) Badger, R. M. J. Chem. Phys. 1935, 3, 710-714. (c) Herschbach, D. R.; Laurie, V. W. J. Chem. Phys. 1961, 35, 458-463. (d) Pauling, L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY. 1960; p 231. (e) Christen, D.; Gupta, O. D.; Kadel, J.; Kirchmeier, R. L.; Mack, H. G.; Oberhammer, H.; Shreeve, J. M. J. Am. Chem. Soc. 1991, 113, 9131- 9135.
106. e (a) Badger, R. M. J. Chem. Phys. 1934, 2, 128-131. (b) Badger, R. M. J. Chem. Phys. 1935, 3, 710-714. (c) Herschbach, D. R.; Laurie, V. W. J. Chem. Phys. 1961, 35, 458-463. (d) Pauling, L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY. 1960; p 231. (e) Christen, D.; Gupta, O. D.; Kadel, J.; Kirchmeier, R. L.; Mack, H. G.; Oberhammer, H.; Shreeve, J. M. J. Am. Chem. Soc. 1991, 113, 9131-9135.
107. See, for example: (a) Ernst, R. D.; Freeman, J. W.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Nuber, B.; Ziegler, M. L. J. Am. Chem. Soc. 1995, 117, 5075-5081. (b) Tudela, D. J. Chem. Educ. 1996, 73, A297. (c) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219. (d) Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. (e) Bowmaker, G. A.; Schmidbaur, H.; Krüger, S.; Rösch, N. Inorg. Chem. 1997, 36, 1754-1757. (f) McKean, D. C.; Torto, I.; Morrison, A. R. J. Phys. Chem. 1982, 86, 307-309. (g) Vollhardt, K. P. C.; Cammack, J. K.; Matzger, A. J.; Bauer, A.; Capps, K. B.; Hoff, C. D. Inorg. Chem. 1999, 38, 2624-2631.
108. See, for example: (a) Ernst, R. D.; Freeman, J. W.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Nuber, B.; Ziegler, M. L. J. Am. Chem. Soc. 1995, 117, 5075-5081. (b) Tudela, D. J. Chem. Educ. 1996, 73, A297. (c) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219. (d) Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. (e) Bowmaker, G. A.; Schmidbaur, H.; Krüger, S.; Rösch, N. Inorg. Chem. 1997, 36, 1754-1757. (f) McKean, D. C.; Torto, I.; Morrison, A. R. J. Phys. Chem. 1982, 86, 307-309. (g) Vollhardt, K. P. C.; Cammack, J. K.; Matzger, A. J.; Bauer, A.; Capps, K. B.; Hoff, C. D. Inorg. Chem. 1999, 38, 2624-2631.
109. See, for example: (a) Ernst, R. D.; Freeman, J. W.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Nuber, B.; Ziegler, M. L. J. Am. Chem. Soc. 1995, 117, 5075-5081. (b) Tudela, D. J. Chem. Educ. 1996, 73, A297. (c) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219. (d) Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. (e) Bowmaker, G. A.; Schmidbaur, H.; Krüger, S.; Rösch, N. Inorg. Chem. 1997, 36, 1754-1757. (f) McKean, D. C.; Torto, I.; Morrison, A. R. J. Phys. Chem. 1982, 86, 307-309. (g) Vollhardt, K. P. C.; Cammack, J. K.; Matzger, A. J.; Bauer, A.; Capps, K. B.; Hoff, C. D. Inorg. Chem. 1999, 38, 2624-2631.
110. See, for example: (a) Ernst, R. D.; Freeman, J. W.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Nuber, B.; Ziegler, M. L. J. Am. Chem. Soc. 1995, 117, 5075-5081. (b) Tudela, D. J. Chem. Educ. 1996, 73, A297. (c) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219. (d) Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. (e) Bowmaker, G. A.; Schmidbaur, H.; Krüger, S.; Rösch, N. Inorg. Chem. 1997, 36, 1754-1757. (f) McKean, D. C.; Torto, I.; Morrison, A. R. J. Phys. Chem. 1982, 86, 307-309. (g) Vollhardt, K. P. C.; Cammack, J. K.; Matzger, A. J.; Bauer, A.; Capps, K. B.; Hoff, C. D. Inorg. Chem. 1999, 38, 2624-2631.
111. See, for example: (a) Ernst, R. D.; Freeman, J. W.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Nuber, B.; Ziegler, M. L. J. Am. Chem. Soc. 1995, 117, 5075-5081. (b) Tudela, D. J. Chem. Educ. 1996, 73, A297. (c) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219. (d) Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. (e) Bowmaker, G. A.; Schmidbaur, H.; Krüger, S.; Rösch, N. Inorg. Chem. 1997, 36, 1754-1757. (f) McKean, D. C.; Torto, I.; Morrison, A. R. J. Phys. Chem. 1982, 86, 307-309. (g) Vollhardt, K. P. C.; Cammack, J. K.; Matzger, A. J.; Bauer, A.; Capps, K. B.; Hoff, C. D. Inorg. Chem. 1999, 38, 2624-2631.
112. See, for example: (a) Ernst, R. D.; Freeman, J. W.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Nuber, B.; Ziegler, M. L. J. Am. Chem. Soc. 1995, 117, 5075-5081. (b) Tudela, D. J. Chem. Educ. 1996, 73, A297. (c) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219. (d) Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. (e) Bowmaker, G. A.; Schmidbaur, H.; Krüger, S.; Rösch, N. Inorg. Chem. 1997, 36, 1754-1757. (f) McKean, D. C.; Torto, I.; Morrison, A. R. J. Phys. Chem. 1982, 86, 307-309. (g) Vollhardt, K. P. C.; Cammack, J. K.; Matzger, A. J.; Bauer, A.; Capps, K. B.; Hoff, C. D. Inorg. Chem. 1999, 38, 2624-2631.
113. See, for example: (a) Ernst, R. D.; Freeman, J. W.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Nuber, B.; Ziegler, M. L. J. Am. Chem. Soc. 1995, 117, 5075-5081. (b) Tudela, D. J. Chem. Educ. 1996, 73, A297. (c) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214-4219. (d) Mayer, P. M.; Glukhovtsev, M. N.; Gauld, J. W.; Radom, L. J. Am. Chem. Soc. 1997, 119, 12889-12895. (e) Bowmaker, G. A.; Schmidbaur, H.; Krüger, S.; Rösch, N. Inorg. Chem. 1997, 36, 1754-1757. (f) McKean, D. C.; Torto, I.; Morrison, A. R. J. Phys. Chem. 1982, 86, 307-309. (g) Vollhardt, K. P. C.; Cammack, J. K.; Matzger, A. J.; Bauer, A.; Capps, K. B.; Hoff, C. D. Inorg. Chem. 1999, 38, 2624-2631.
114. For an example of the influence of selective π-interactions stabilizing unusual oxo complexes, see: Bursten, B. E.; Cayton, R. H. Organometallics 1987, 6, 2004-2005.
115. -1.
116. Zietlow, T. C.; Hopkins, M. D.; Gray, H. B. J. Am. Chem. Soc. 1986, 108, 8266-8267.
117. For theoretical calculations on this system, see: Clot, E.; Eisenstein, O. J. Phys. Chem. A 1998, 102, 3592-3598.
118. (a) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362.
119. (b) Lee, D. W.; Jensen, C. M. J. Am. Chem. Soc. 1996, 118, 8749-8750.
120. 2 to the iodide complex in alkane solvent with respect to that for the chloride and bromide has been suggested to indicate preferential alkane coordination to the five-coordinate iodide (ref 57).
121. Le-Husebo, T.; Jensen, C. M. Inorg. Chem. 1993, 32, 3797-3798.
122. 2 ratios are 0.56 (Cl), 0.91 (Br), and 1.67 (I).
123. -1 for the chloride derivative]. See: Eckert, J.; Jensen, C. M.; Koetzle, T. F.; Husebo, T. L.; Nicol, J.; Wu, P. J. Am. Chem. Soc. 1995, 117, 7271-7272.
124. 2)X systems may be associated with the equilibrium constant data having being measured over a relatively small temperature range.
125. 2(CO)Cl has been reported: Werneke, M. F. Ph.D Thesis, Clarkson College of Technology, Potsdam, NY, 1971.
126. For reviews of isotope effects in reactions of transition metal hydrides, see: (a) Bullock, R. M. In Transition Metal Hydrides; Dedieu, A., Ed.; VCH: New York, 1992; pp 263-307. (b) Rosenberg, E. Polyhedron 1991, 8, 383-405.
127. For reviews of isotope effects in reactions of transition metal hydrides, see: (a) Bullock, R. M. In Transition Metal Hydrides; Dedieu, A., Ed.; VCH: New York, 1992; pp 263-307. (b) Rosenberg, E. Polyhedron 1991, 8, 383-405.
128. Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636.
129. 2, these values also are a composite of primary and secondary effects. However, for this particular system, the primary and secondary isotope contributions were estimated to be 0.73 and 0.74, respectively, on the basis of IR calculations for the primary effect. See ref 64.
130. (a) Packett, D. L.; Trogler, W. C. J. Am. Chem. Soc. 1986, 108, 5036-5038.
131. (b) Packett, D. L.; Trogler, W. C. Inorg. Chem. 1988, 27, 1768-1775.
132. (c) Howarth, O. W.; McAteer, C. H.; Moore, P.; Morris, G. E. J. Chem. Soc., Dalton Trans. 1984, 1171-1180.
133. (d) Reference 1a, p 331.
134. g It is, therefore, evident that the factors which influence the preference for deuterium (or tritium) to occupy either a hydride or dihydrogen site are complex. (a) Luo, X-L.; Crabtree, R. H. J. Am. Chem. Soc. 1990, 112, 6912-6918. (b) Haward, M. T.; George, M. W.; Hamley, P.; Poliakoff, M. J. Chem. Soc., Chem. Commun. 1991, 1101-1103. (c) Packett, D. L.; Trogler, W. C. Inorg. Chem. 1988, 27, 1768-1775. (d) Heinekey, D. M.; Oldham, W. J., Jr. J. Am. Chem. Soc. 1994, 116, 3137- 3138. (e) Oldham, W. J., Jr.; Hinkle, A. S.; Heinekey, D. M. J. Am. Chem. Soc. 1997, 119, 11028-11036. (f) Henderson, R. A.; Oglieve, K. E. J. Chem. Soc., Dalton Trans. 1993, 3431-3439.
135. g It is, therefore, evident that the factors which influence the preference for deuterium (or tritium) to occupy either a hydride or dihydrogen site are complex. (a) Luo, X-L.; Crabtree, R. H. J. Am. Chem. Soc. 1990, 112, 6912-6918. (b) Haward, M. T.; George, M. W.; Hamley, P.; Poliakoff, M. J. Chem. Soc., Chem. Commun. 1991, 1101-1103. (c) Packett, D. L.; Trogler, W. C. Inorg. Chem. 1988, 27, 1768-1775. (d) Heinekey, D. M.; Oldham, W. J., Jr. J. Am. Chem. Soc. 1994, 116, 3137- 3138. (e) Oldham, W. J., Jr.; Hinkle, A. S.; Heinekey, D. M. J. Am. Chem. Soc. 1997, 119, 11028-11036. (f) Henderson, R. A.; Oglieve, K. E. J. Chem. Soc., Dalton Trans. 1993, 3431-3439.
136. g It is, therefore, evident that the factors which influence the preference for deuterium (or tritium) to occupy either a hydride or dihydrogen site are complex. (a) Luo, X-L.; Crabtree, R. H. J. Am. Chem. Soc. 1990, 112, 6912-6918. (b) Haward, M. T.; George, M. W.; Hamley, P.; Poliakoff, M. J. Chem. Soc., Chem. Commun. 1991, 1101-1103. (c) Packett, D. L.; Trogler, W. C. Inorg. Chem. 1988, 27, 1768-1775. (d) Heinekey, D. M.; Oldham, W. J., Jr. J. Am. Chem. Soc. 1994, 116, 3137- 3138. (e) Oldham, W. J., Jr.; Hinkle, A. S.; Heinekey, D. M. J. Am. Chem. Soc. 1997, 119, 11028-11036. (f) Henderson, R. A.; Oglieve, K. E. J. Chem. Soc., Dalton Trans. 1993, 3431-3439.
137. g It is, therefore, evident that the factors which influence the preference for deuterium (or tritium) to occupy either a hydride or dihydrogen site are complex. (a) Luo, X-L.; Crabtree, R. H. J. Am. Chem. Soc. 1990, 112, 6912-6918. (b) Haward, M. T.; George, M. W.; Hamley, P.; Poliakoff, M. J. Chem. Soc., Chem. Commun. 1991, 1101-1103. (c) Packett, D. L.; Trogler, W. C. Inorg. Chem. 1988, 27, 1768-1775. (d) Heinekey, D. M.; Oldham, W. J., Jr. J. Am. Chem. Soc. 1994, 116, 3137-3138. (e) Oldham, W. J., Jr.; Hinkle, A. S.; Heinekey, D. M. J. Am. Chem. Soc. 1997, 119, 11028-11036. (f) Henderson, R. A.; Oglieve, K. E. J. Chem. Soc., Dalton Trans. 1993, 3431-3439.
138. g It is, therefore, evident that the factors which influence the preference for deuterium (or tritium) to occupy either a hydride or dihydrogen site are complex. (a) Luo, X-L.; Crabtree, R. H. J. Am. Chem. Soc. 1990, 112, 6912-6918. (b) Haward, M. T.; George, M. W.; Hamley, P.; Poliakoff, M. J. Chem. Soc., Chem. Commun. 1991, 1101-1103. (c) Packett, D. L.; Trogler, W. C. Inorg. Chem. 1988, 27, 1768-1775. (d) Heinekey, D. M.; Oldham, W. J., Jr. J. Am. Chem. Soc. 1994, 116, 3137- 3138. (e) Oldham, W. J., Jr.; Hinkle, A. S.; Heinekey, D. M. J. Am. Chem. Soc. 1997, 119, 11028-11036. (f) Henderson, R. A.; Oglieve, K. E. J. Chem. Soc., Dalton Trans. 1993, 3431-3439.
139. g It is, therefore, evident that the factors which influence the preference for deuterium (or tritium) to occupy either a hydride or dihydrogen site are complex. (a) Luo, X-L.; Crabtree, R. H. J. Am. Chem. Soc. 1990, 112, 6912-6918. (b) Haward, M. T.; George, M. W.; Hamley, P.; Poliakoff, M. J. Chem. Soc., Chem. Commun. 1991, 1101-1103. (c) Packett, D. L.; Trogler, W. C. Inorg. Chem. 1988, 27, 1768-1775. (d) Heinekey, D. M.; Oldham, W. J., Jr. J. Am. Chem. Soc. 1994, 116, 3137- 3138. (e) Oldham, W. J., Jr.; Hinkle, A. S.; Heinekey, D. M. J. Am. Chem. Soc. 1997, 119, 11028-11036. (f) Henderson, R. A.; Oglieve, K. E. J. Chem. Soc., Dalton Trans. 1993, 3431-3439.
140. (g) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
141. 6, the deutendes are more stable. See: (a) Wiswall, R. H., Jr.; Reilly, J. I. Inorg. Chem. 1972, 11, 1691-1696. (b) Luo, W.; Clewley, J. D.; Flanagan, T. B. J. Phys. Chem. 1990, 93, 6710-6722.
142. 6, the deutendes are more stable. See: (a) Wiswall, R. H., Jr.; Reilly, J. I. Inorg. Chem. 1972, 11, 1691-1696. (b) Luo, W.; Clewley, J. D.; Flanagan, T. B. J. Phys. Chem. 1990, 93, 6710-6722.
143. 2, which has recently been reported to exhibit a normal equilibrium isotope effect. See ref 51g.
144. Wooley, H. W.; Scott, R. B.; Brickwedde, F. G. J. Res. Nat. Bur. Stand. 1948, 41, 379-475.
145. Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023.
146. McLennan, D. J. In Isotopes in Organic Chemistry; Buncel, E., Lee, C. C., Eds.; Elsevier: New York, 1987; Vol 7, Chapter 6, pp 393-480.
147. D. See ref 72.
148. -1. See: Herzberg, G. Molecular Spectra and Molecular Structure; Van Nostrand Reinhold Co.: New York, 1950; Vol. 1, pp 532-533.
149. It is, however, important to consider bending modes in evaluating secondary isotope effects.
150. b-c (a) Polyakova, V. B.; Borisov, A. P.; Makhaev, V. D.; Semenenko, K. D. Koord. Khim. 1980, 6, 743-752. (b) Girling, R. B.; Grebenik, P.; Perutz, R. N. Inorg. Chem. 1986, 25, 31-36. (c) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 1998, 291-300. (d) Reference 67g. (e) Jonas, V.; Thiel, W. J. Chem. Phys. 1996, 105, 3636-3648. (f) Egdell, W. F.; Fisher, J. W.; Asato, G.; Risen, W. M., Jr. Inorg. Chem. 1969, 8, 1103-1108. (g) Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719-727.
151. b-c (a) Polyakova, V. B.; Borisov, A. P.; Makhaev, V. D.; Semenenko, K. D. Koord. Khim. 1980, 6, 743-752. (b) Girling, R. B.; Grebenik, P.; Perutz, R. N. Inorg. Chem. 1986, 25, 31-36. (c) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 1998, 291-300. (d) Reference 67g. (e) Jonas, V.; Thiel, W. J. Chem. Phys. 1996, 105, 3636-3648. (f) Egdell, W. F.; Fisher, J. W.; Asato, G.; Risen, W. M., Jr. Inorg. Chem. 1969, 8, 1103-1108. (g) Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719-727.
152. b-c (a) Polyakova, V. B.; Borisov, A. P.; Makhaev, V. D.; Semenenko, K. D. Koord. Khim. 1980, 6, 743-752. (b) Girling, R. B.; Grebenik, P.; Perutz, R. N. Inorg. Chem. 1986, 25, 31-36. (c) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 1998, 291-300. (d) Reference 67g. (e) Jonas, V.; Thiel, W. J. Chem. Phys. 1996, 105, 3636-3648. (f) Egdell, W. F.; Fisher, J. W.; Asato, G.; Risen, W. M., Jr. Inorg. Chem. 1969, 8, 1103-1108. (g) Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719-727.
153. b-c (a) Polyakova, V. B.; Borisov, A. P.; Makhaev, V. D.; Semenenko, K. D. Koord. Khim. 1980, 6, 743-752. (b) Girling, R. B.; Grebenik, P.; Perutz, R. N. Inorg. Chem. 1986, 25, 31-36. (c) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 1998, 291-300. (d) Reference 67g. (e) Jonas, V.; Thiel, W. J. Chem. Phys. 1996, 105, 3636-3648. (f) Egdell, W. F.; Fisher, J. W.; Asato, G.; Risen, W. M., Jr. Inorg. Chem. 1969, 8, 1103-1108. (g) Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719-727.
154. b-c (a) Polyakova, V. B.; Borisov, A. P.; Makhaev, V. D.; Semenenko, K. D. Koord. Khim. 1980, 6, 743-752. (b) Girling, R. B.; Grebenik, P.; Perutz, R. N. Inorg. Chem. 1986, 25, 31-36. (c) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 1998, 291-300. (d) Reference 67g. (e) Jonas, V.; Thiel, W. J. Chem. Phys. 1996, 105, 3636-3648. (f) Egdell, W. F.; Fisher, J. W.; Asato, G.; Risen, W. M., Jr. Inorg. Chem. 1969, 8, 1103-1108. (g) Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719-727.
155. b-c (a) Polyakova, V. B.; Borisov, A. P.; Makhaev, V. D.; Semenenko, K. D. Koord. Khim. 1980, 6, 743-752. (b) Girling, R. B.; Grebenik, P.; Perutz, R. N. Inorg. Chem. 1986, 25, 31-36. (c) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 1998, 291-300. (d) Reference 67g. (e) Jonas, V.; Thiel, W. J. Chem. Phys. 1996, 105, 3636-3648. (f) Egdell, W. F.; Fisher, J. W.; Asato, G.; Risen, W. M., Jr. Inorg. Chem. 1969, 8, 1103-1108. (g) Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719-727.
156. b-c (a) Polyakova, V. B.; Borisov, A. P.; Makhaev, V. D.; Semenenko, K. D. Koord. Khim. 1980, 6, 743-752. (b) Girling, R. B.; Grebenik, P.; Perutz, R. N. Inorg. Chem. 1986, 25, 31-36. (c) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 1998, 291-300. (d) Reference 67g. (e) Jonas, V.; Thiel, W. J. Chem. Phys. 1996, 105, 3636-3648. (f) Egdell, W. F.; Fisher, J. W.; Asato, G.; Risen, W. M., Jr. Inorg. Chem. 1969, 8, 1103-1108. (g) Sweany, R. L.; Russell, F. N. Organometallics 1988, 7, 719-727.
157. 2.
158. -1.
159. 2] = 35.31 eu
160. For example, the deuterium equilibrium isotope effect for oxidative addition of Me-H versus Me-D is calculated tu be normal since the reactant and product have the same number of isotope-sensitive modes and C-H bonds are stronger than M-H bonds. See: Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023.
161. 2]. See ref 80.
162. 2.
163. MMI. EXC, and ZPE terms were determined from the calculated vibrational frequencies using a program provided by Dr. Bruce Bender.
164. 3 (see text).
165. For a listing of oxidative addition and reductive elimination reactions that involve either direct addition or elimination, or a mechanism involving initial dissociation or addition of a ligand, see Table S6 in the Supporting Information. (86) (a) Halpern, J.; Wong, C. S. J. Chem. Soc., Chem. Commun. 1973, 629-630. (b) Halpern, J.; Okamoto, T.; Zakhariev, A. J. Mol. Catal. 1976, 2, 65-68. (c) Halpern, J. Inorg. Chim. Acta 1981, 50, 11-19.
166. For a listing of oxidative addition and reductive elimination reactions that involve either direct addition or elimination, or a mechanism involving initial dissociation or addition of a ligand, see Table S6 in the Supporting Information. (86) (a) Halpern, J.; Wong, C. S. J. Chem. Soc., Chem. Commun. 1973, 629-630. (b) Halpern, J.; Okamoto, T.; Zakhariev, A. J. Mol. Catal. 1976, 2, 65-68. (c) Halpern, J. Inorg. Chim. Acta 1981, 50, 11-19.
167. For a listing of oxidative addition and reductive elimination reactions that involve either direct addition or elimination, or a mechanism involving initial dissociation or addition of a ligand, see Table S6 in the Supporting Information. (86) (a) Halpern, J.; Wong, C. S. J. Chem. Soc., Chem. Commun. 1973, 629-630. (b) Halpern, J.; Okamoto, T.; Zakhariev, A. J. Mol. Catal. 1976, 2, 65-68. (c) Halpern, J. Inorg. Chim. Acta 1981, 50, 11-19.
168. (a) Heinekey, D. M.; Oldham, W. J., Jr. Chem. Rev. 1993, 93, 913-926.
169. (b) Crabtree, R. H. Acc. Chem. Res. 1990, 23, 95-101.
170. (c) Jessop, P. G.; Morris, R. H. Coord. Chem. Rev. 1992, 121, 155-284.
171. (d) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805.
172. (e) Kubas, G. J. Ace. Chem. Res. 1988, 21, 120-128.
173. Kinetic deuterium isotope effects for a three-centered transition state are greatest for a symmetric transition state and decrease for transition states that are either product-like or reactant-like; indeed, calculations indicate that the isotope effect could become inverse (<1) in certain situations. See: (a) Bigeleisen, J. Pure Appl. Chem. 1964, 8, 217-222. (b) Melander, L. Acta Chem. Scand. 1971, 25, 3821-3826. (c) More O'Ferrall, R. A. J. Chem. Soc. (B) 1970, 787-790. (d) Bigeleisen, J.; Wolfsberg, M. Adv. Chem. Phys. 1958, 1, 15-76.
174. Kinetic deuterium isotope effects for a three-centered transition state are greatest for a symmetric transition state and decrease for transition states that are either product-like or reactant-like; indeed, calculations indicate that the isotope effect could become inverse (<1) in certain situations. See: (a) Bigeleisen, J. Pure Appl. Chem. 1964, 8, 217-222. (b) Melander, L. Acta Chem. Scand. 1971, 25, 3821-3826. (c) More O'Ferrall, R. A. J. Chem. Soc. (B) 1970, 787-790. (d) Bigeleisen, J.; Wolfsberg, M. Adv. Chem. Phys. 1958, 1, 15-76.
175. Kinetic deuterium isotope effects for a three-centered transition state are greatest for a symmetric transition state and decrease for transition states that are either product-like or reactant-like; indeed, calculations indicate that the isotope effect could become inverse (<1) in certain situations. See: (a) Bigeleisen, J. Pure Appl. Chem. 1964, 8, 217-222. (b) Melander, L. Acta Chem. Scand. 1971, 25, 3821-3826. (c) More O'Ferrall, R. A. J. Chem. Soc. (B) 1970, 787-790. (d) Bigeleisen, J.; Wolfsberg, M. Adv. Chem. Phys. 1958, 1, 15-76.
176. Kinetic deuterium isotope effects for a three-centered transition state are greatest for a symmetric transition state and decrease for transition states that are either product-like or reactant-like; indeed, calculations indicate that the isotope effect could become inverse (<1) in certain situations. See: (a) Bigeleisen, J. Pure Appl. Chem. 1964, 8, 217-222. (b) Melander, L. Acta Chem. Scand. 1971, 25, 3821-3826. (c) More O'Ferrall, R. A. J. Chem. Soc. (B) 1970, 787-790. (d) Bigeleisen, J.; Wolfsberg, M. Adv. Chem. Phys. 1958, 1, 15-76.
177. + is known to be characterized by both normal and inverse kinetic isotope effects. See: Cheng, T.-Y.; Bullock, R. M. J. Am. Chem. Soc. 1999, 121, 3150-3155.
178. b (a) Zhou, P.; Vitale, A. A.; San Filippo, J., Jr.; Saunders, W. H., Jr. J. Am. Chem. Soc. 1985, 107, 8049-8054. (b) Reference 41b.
179. b (a) Zhou, P.; Vitale, A. A.; San Filippo, J., Jr.; Saunders, W. H., Jr. J. Am. Chem. Soc. 1985, 107, 8049-8054. (b) Reference 41b.
180. (a) McNally, J. P.; Leong, V. S.; Cooper, N. J. In Experimental Organometallic Chemistry; Wayda, A. L., Darensbourg, M. Y., Eds.; American Chemical Society: Washington, DC, 1987; chapter 2, pp 6-23.
181. (b) Burger, B. J.; Bercaw, J. E. In Experimental Organometallic Chemistry; Wayda, A. L., Darensbourg, M. Y., Eds.; American Chemical Society: Washington, DC, 1987; Chapter 4, pp 79-98.
182. Lyons, D.; Wilkinson, G.; Thornton-Pett, M.; Hursthouse, M. B. J. Chem. Soc., Dalton Trans. 1984, 695-700.
183. Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219.
184. In x = -5.5284 - 813.90(T/K). See: Clever, H. L. Hydrogen and Deuterium. In Solubility Data Series, Young, C. L., Ed.; Pergamon Press: Oxford, 1981; Volume 5/6, p 159.
185. In x = -5.7399 - 743.44/(T/K). See: Clever, H. L. Hydrogen and Deuterium. In Solubility Data Series, Young, C. L., Ed.; Pergamon Press: Oxford, 1981; Volume 5/6, p 287.
186. 3 methyl groups. For consistency, all calculations were performed for a common rotameric structure.
187. Frenking, G.; Pidun, U. J. Chem. Soc., Dalton Trans. 1997, 1653-1662.
188. W-I bond lengths (Å): BLYP, 3.040, 3.106; B3LYP, 3.014, 3.067; LMP2, 3.003, 3.037; expt, 2.903, 2.922.