The Structural Stability of Seven-Coordinate Divalent Cations in the First Transition Series Relevant to the Water-Exchange Reaction Mechanism

Bulletin of the Chemical Society of Japan

Volumn 71, Issue 8, 1998, Pages 1771-1779

  Tsutsui, Yuko ^a   Wasada, Hiroaki ^a,b   Funahashi, Shigenobu ^a  

^a NAGOYA UNIVERSITY   (Japan)

^b GIFU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000634242     PISSN: 00092673     EISSN: None     Source Type: Journal    
DOI: 10.1246/bcsj.71.1771     Document Type: Article

References (26)

1. C. N. Langford and H. B. Gray, "Ligand Substitution Processes," Benjamin Inc., New York (1966).
2. H. Ohtaki and T. Radnai, Chem. Rev., 93, 1157 (1993).
3. a) A. E. Merbach, Pure Appl. Chem., 59, 161 (1987);
4. b) R. van Eldik, T. Asano, and W. J. le Noble, Chem. Rev., 89, 549 (1989).
5. a) R. Åkesson, L. G. M. Pettersson, M. Sandström, P. E. M Siegbahn, and U. Wahlgren, J. Phys. Chem., 97, 3765 (1993);
6. b) R. Åkesson, L. G. M. Pettersson, M. Sandström, and U. Wahlgren, J. Am. Chem. Soc., 116, 8705 (1994);
7. c) S.-K. Kang, B. Lam, T. A. Albright, and J. F. O'Brien, New J. Chem., 15, 757 (1991).
8. a) Y. Tsutsui, H. Wasada, and S. Funahashi, Bull Chem. Soc. Jpn., 70, 1813 (1997);
9. b) Y. Tsutsui, H. Wasada, and S. Funahashi, Bull. Chem. Soc. Jpn., 71, 73 (1998).
10. a) F. P. Rotzinger, J. Am. Chem. Soc., 118, 6760 (1996);
11. b) F. P. Rotzinger, J. Am. Chem. Soc., 119, 5230 (1997);
12. c) M. Hartmann, T. Clark, and R. van Eldik, J. Am. Chem. Soc., 119, 7843 (1997).
13. A. J. H. Wachters, J. Chem. Phys., 52, 1033 (1970).
14. a) S. Huzinaga, J. Chem. Phys., 42, 1293 (1965);
15. b) T. H. Dunning, J. Chem. Phys., 53, 2823 (1970).
16. a) R. Åkesson, L. G. M. Pettersson, M. Sandström, and U. Wahlgren, J. Phys. Chem., 96, 10773 (1992);
17. b) R. Åkesson, L. G. M. Pettersson, M. Sandström, and U. Wahlgren, J. Am. Chem. Soc., 116, 8691 (1994).
18. S. F. Boys and F. Bernardii, Mol. Phys., 19, 553 (1970).
19. a) M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. G. Johnson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, and J. A. Pople, "Gaussian 92, Revision C," Gaussian Inc., Pittsburgh, PA (1992);
20. b) M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J, B, Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, "Gaussian 94, Revision C.3," Gaussian Inc., Pittsburgh, PA (1995).
21. a) Y. Tsutsui and H. Wasada, Chem. Lett., 1995, 517;
22. b) H. Wasada and Y. Tsutsui, Bull. Fac. General Educ., Gifu University, 33, 145 (1996).
23. a mechanism was experimentally accepted. The intrinsic reaction path leading down from the heptacoordination to the hexacoordination (hexaaqua vanadium(II) ion with a water molecule in the second coordination shell) showed that the heptacoordination is the transition state of the water-exchange reaction on the vanadium(II) ion; Furthermore, we evaluated the relation between the low imaginary frequency for the heptacoordination of cobalt(II) and the reaction path of the water-exchange reaction. The geometry optimization was performed with computing second derivatives of the potential surface. The atomic coordinates at the starting point were those of the heptacoordination slightly moved along the transition vector in proportion to its amplitude. The distance between the central cobalt atom and the leaving water molecule increased monotonously and the structure changed to the hexacoordination. These findings indicate that the heptacoordination is the transition state of the water-exchange reactions via the associative mechanism.
24. R. F. W. Bader, Can. J. Chem., 40, 1164 (1962).
25. A. E. Reed, R. B. Weinstock, and F. Weinhold, J. Chem. Phys., 83, 1164 (1985).
26. F. Basolo and R. G. Pearson, "Mechanisms of Inorganic Chemistry," 2nd ed, John Wiley & Sons, Inc., New York (1967).