Deuterium migration in {(1,4,7- triazacyclononane)Rh(alkyl)D[P(OMe)3]}+ evidence for mobility of rhodium along linear alkane chains in inferred rhodium-alkane complexes [10]

Journal of the American Chemical Society

Volumn 122, Issue 28, 2000, Pages 6783-6784

  Flood, Thomas C ^a   Janak, Kevin E ^a   Iimura, Masanori ^a   Zhen, Hongshi ^a  

^a UNIVERSITY OF SOUTHERN CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BINDING; COMPLEX FORMATION; ENERGY TRANSFER; LETTER; METAL BINDING; OXIDATION; REDUCTION;

EID: 0034686758     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000104+     Document Type: Letter

References (49)

1. Recent Reviews: (a) Arndsten, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154. (b) Hall, C.; Perutz, R. N. Chem. Rev. 1996, 96, 3125.
2. Recent Reviews: (a) Arndsten, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154. (b) Hall, C.; Perutz, R. N. Chem. Rev. 1996, 96, 3125.
3. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
4. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
5. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
6. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
7. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
8. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
9. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
10. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
11. Bergman and co-workers have provided leading work at first implicating and later studying alkane complexed intermediates: (a) Buchanan, J. M.; Stryker, J. M.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 1537. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Weiller, B. H.; Wasserman, E. P.; Bergman, R. G.; Moore, C. B.; Pimentel, G. C. J. Am. Chem. Soc. 1989, 111, 8288. (d) Wasserman, E. P.; Moore, C. B.; Bergman R. G. Science, 1992, 255, 315. (e) Bengali, A. A.; Schultz, R. H.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 9585. (f) Schultz, R. H.; Bengali, A. A.; Tauber, M. J.; Weiller, B. H.; Wasserman, E. P.; Kyle, K. R.; Moore, C. B.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7369. (g) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.; McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.; Bergman, R. G.; Harris, C. B. Science 1997, 278, 260. (h) Mobley, T. A.; Schade, C.; Bergman R. G. Organometallics 1998, 17, 3574. (i) Asbury, J. B.; Ghosh, H. N.; Yeston, J. S.; Bergman, R. G.; Lian, T. Organometallics 1998, 17, 3417.
12. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
13. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
14. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
15. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
16. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
17. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
18. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
19. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
20. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
21. Coordination complexes of intact alkanes have been postulated by other groups as well, usually based in part on an inverse isotope effect for alkane loss from alkyl hydrides: (a) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897. (b) Gould, G. L.; Heinekey, D. M. J. Am. Chem. Soc. 1989, 111, 5502. (c) Parkin, G.; Bercaw, J. E. Organometallics 1989, 8, 1172. (d) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647. (e) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 5961. (f) Jenkins, H. A.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 1997, 16, 1946. (g) Schafer, D. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (h) Gross, C. L.; Girolami, G. S. J. Am. Chem. Soc. 1998, 120, 6605. (i) Fekl, U.; Zahl, A.; van Eldik, R. Organometallics 1999, 18, 4156. (j) Wick, D. D.; Reynolds K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974.
22. Recent spectroscopic observations of alkane complexes: (a) At ambient temperature by time-resolved IR: Sun, X.-Z.; Grills, D. C.; Nikiforov, S. M.; Poliakoff, M.; George, M. W. J. Am. Chem. Soc. 1997, 119, 7521. (b) At -80 °C by NMR: Geftakis, S.; Ball, G. E. J. Am. Chem. Soc. 1998, 120, 9953.
23. Recent spectroscopic observations of alkane complexes: (a) At ambient temperature by time-resolved IR: Sun, X.-Z.; Grills, D. C.; Nikiforov, S. M.; Poliakoff, M.; George, M. W. J. Am. Chem. Soc. 1997, 119, 7521. (b) At -80 °C by NMR: Geftakis, S.; Ball, G. E. J. Am. Chem. Soc. 1998, 120, 9953.
24. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
25. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
26. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
27. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
28. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
29. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
30. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
31. Theoretical calculations of alkane complexes: (a) Ziegler, T.; Tschinke, V.; Fan, L.; Becke, A. D. J. Am. Chem. Soc. 1989, 111, 9177. (b) Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 10557. (c) Song, J.; Hall, M. B. Organometallics 1993, 12, 3118. (d) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 6883. (e) Cundari, T. R. Organometallics 1993, 12, 1998. (f) Margl, P.; Ziegler, T.; Bloechl, P. E. J. Am. Chem. Soc. 1995, 117, 12625. (g) Zaric, S.; Hall, M. B. J. Phys. Chem. 1997, 101, 4646. (h) Martin, R. L. J. Am. Chem. Soc. 1999, 121, 9459.
32. Informally, 1,4,7-triazacyclononane (tacn) = Cn, and 1,4,7-trimethyl-(tacn) = Cn*. Previously we used the standard abbreviation "tacn", and called 1,4,7-trimethyl(tacn) "Cn." Given that tacn is tractable in organometallic systems, the new abbreviations are more analogous to Cp/Cp* and Tp/Tp*.
33. Zhou, R.; Wang, C.; Hu, Y.; Flood, T. C. Organometallics 1997, 16, 434.
34. 3)(CN-t-Bu) has been reported to be first order in benzene concentration (ref 3j).
35. The rate of exchange of the Rh-D on to the α-carbon is very sensitive to the extent of exposure to ambient light, so all work with the alkyl hydrides was done with careful exclusion of light.
36. 1H peak at δ 0.9 to 1.1 ppm which is quite broad since the α-protons are coupled to Rh, P, two β-H, and each other (diastereotopic with slightly different δ). All the other alkyl chain protons for all the rhodium alkyls are contained in a broad envelope at δ 1.2 to 1.4 ppm.
37. +), and for [Rh](D)(hexyl), [Rh](H)(hexyl-α-d), [Rh](H)(hexyl-ω-d), and [Rh](H)(Ph) in the α → ω scrambling reaction in neat benzene were fitted to kinetic models based on Scheme 1 using the iterative kinetics program "Gear", copyright 1995 by F. J. Weigert. (a) Stabler R. N.; Chesick, J. Int. J. Kinet. 1978, 10, 461. (b) Weigert, F. J. Comput. Chem. 1987, 11, 273.
38. +), and for [Rh](D)(hexyl), [Rh](H)(hexyl-α-d), [Rh](H)(hexyl-ω- d), and [Rh](H)(Ph) in the α → ω scrambling reaction in neat benzene were fitted to kinetic models based on Scheme 1 using the iterative kinetics program "Gear", copyright 1995 by F. J. Weigert. (a) Stabler R. N.; Chesick, J. Int. J. Kinet. 1978, 10, 461. (b) Weigert, F. J. Comput. Chem. 1987, 11, 273.
39. 2H NMR analysis.
40. 6 two dominant as-yet-unidentified, rhodium-containing products are formed, but the reaction is not clean. About 18% of methyl hydride (based on total rhodium) is present at 2 half-lives of butyl hydride disappearance.
41. 13C spectra of our Rh-(H)(n-R) complexes.
42. 3), see ref 2b.
43. Nitrogen-dissociated intermediates have been invoked for Tp*Rh(H)-(R)(L) systems: L = CO, ref 2 g; L = CN-t-Bu, ref 3j.
44. 8 species (refs 17a,d-f). (a) Shinomoto, R. S.; Desrosiers, P. J.; Harper, T. G. P.; Flood, T. C. J. Am. Chem. Soc. 1990, 112, 704. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) References 2g and 3e. (d) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1991, 113, 6492. (e) Harper, T. G. P.; Desrosiers, P. J.; Flood, T. C. Organometallics 1990, 9, 2523. (f) Reference 2b.
45. 8 species (refs 17a,d-f). (a) Shinomoto, R. S.; Desrosiers, P. J.; Harper, T. G. P.; Flood, T. C. J. Am. Chem. Soc. 1990, 112, 704. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) References 2g and 3e. (d) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1991, 113, 6492. (e) Harper, T. G. P.; Desrosiers, P. J.; Flood, T. C. Organometallics 1990, 9, 2523. (f) Reference 2b.
46. 8 species (refs 17a,d-f). (a) Shinomoto, R. S.; Desrosiers, P. J.; Harper, T. G. P.; Flood, T. C. J. Am. Chem. Soc. 1990, 112, 704. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) References 2g and 3e. (d) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1991, 113, 6492. (e) Harper, T. G. P.; Desrosiers, P. J.; Flood, T. C. Organometallics 1990, 9, 2523. (f) Reference 2b.
47. 8 species (refs 17a,d-f). (a) Shinomoto, R. S.; Desrosiers, P. J.; Harper, T. G. P.; Flood, T. C. J. Am. Chem. Soc. 1990, 112, 704. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) References 2g and 3e. (d) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1991, 113, 6492. (e) Harper, T. G. P.; Desrosiers, P. J.; Flood, T. C. Organometallics 1990, 9, 2523. (f) Reference 2b.
48. 8 species (refs 17a,d-f). (a) Shinomoto, R. S.; Desrosiers, P. J.; Harper, T. G. P.; Flood, T. C. J. Am. Chem. Soc. 1990, 112, 704. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) References 2g and 3e. (d) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1991, 113, 6492. (e) Harper, T. G. P.; Desrosiers, P. J.; Flood, T. C. Organometallics 1990, 9, 2523. (f) Reference 2b.
49. 8 species (refs 17a,d-f). (a) Shinomoto, R. S.; Desrosiers, P. J.; Harper, T. G. P.; Flood, T. C. J. Am. Chem. Soc. 1990, 112, 704. (b) Goldberg, K. I.; Yan, J. Y.; Breitung, E. M. J. Am. Chem. Soc. 1995, 117, 6889. (c) References 2g and 3e. (d) Hartwig, J. F.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1991, 113, 6492. (e) Harper, T. G. P.; Desrosiers, P. J.; Flood, T. C. Organometallics 1990, 9, 2523. (f) Reference 2b.