Density functional theory calculations on 19-electron organometallic complexes: The Mn(CO)5Cl- anion. The difference between unpaired electron density and spin density due to spin polarization

Organometallics

Volumn 17, Issue 18, 1998, Pages 4060-4064

  Braden, Dale A ^a   Tyler, David R ^a  

^a UNIVERSITY OF OREGON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000362208     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980325c     Document Type: Article

References (45)

1. Braden, D. A.; Tyler, D. R. J. Am. Chem. Soc. 1998, 120, 942-947.
2. Tyler, D. R. Acc. Chem. Res. 1991, 24, 325-331.
3. Geiger, W. E. Acc. Chem. Res. 1995, 28, 351-357.
4. Symons, M. C. R.; Bratt, S. W. J. Chem. Soc., Dalton Trans. 1979, 1739-1743.
5. Drago, R. S. Physical Methods for Chemists, 2nd ed.; Saunders: Philadelphia, 1992; pp 374-376.
6. Anderson, O. P.; Fieldhouse, S. A.; Forbes, C. E.; Symons, M. C. R. J. Chem. Soc., Dalton Trans. 1976, 1329-1336.
7. Lionel, T.; Morton, J. R.; Preston, K. F. Chem. Phys. Lett. 1981, 81, 17-20.
8. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision D.4; Gaussian, Inc.: Pittsburgh, PA, 1995.
9. 0 is the Bohr radius.
10. Lide, D. R., Ed. CRC Handbook of Chemistry and Physics, 77th ed.; CRC: Boca Raton, 1997; pp 9:85-87.
11. The basis set was obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 1.0 (http:// www.emsl.pnl.gov: 2080/forms/ basisform.html), as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory, which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, WA 99352, and funded by the U.S. Department of Energy. The Pacific Northwest Laboratory is a multiprogram laboratory operated by Battelle Memorial Institute for the U.S. Department of Energy under contract DE-AC06-76RLO1830. Contact David Feller, Karen Schuchardt, or Don Jones for further information.
12. Schäfer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829-5835.
13. Ehlers, A. W.; Böhme, M.; Dapprich, S.; Gobbi, A.; Höllwarth, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Freaking, G. Chem. Phys. Lett. 1993, 208, 111-114.
14. The authors are grateful to Dr. Björn Roos and Dr. Kristin Pierloot for providing the necessary exponents and coefficients for this basis set.
15. Pierloot, K.; Dumez, B.; Widmark, P.-O.; Roos, B. O. Theor. Chim. Acte 1995, 90, 87-114.
16. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
17. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
18. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
19. Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623-11627.
20. Perdew, J. P.; Wang, Y. Phys. Rev. B 1992, 45, 13244-13249.
21. 4v structure. Because of the existence of a lower symmetry structure of nearly identical energy, the observed hfc tensor should be nonaxial.
22. Symons, M. C. R.; Wyatt, J.; Peake, B. M.; Simpson, J.; Robinson, B. H. J. Chem. Soc., Dalton Trans. 1982, 2037-2039.
23. This wide range of bond dissociation energies is represented by only four compounds. See: Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987; p 240.
24. Using the data from ref 6, the isotropic hfc values would be 25.9 and 0 G, respectively.
25. The reasons for this choice are somewhat vague. They are based either on the reasonableness of calculated orbital populations for 1 or by comparison to hyperfine data for molecular halogen anions. See refs 6 and 7.
26. Adamo, C.; Barone, V.; Fortunelli, A. J. Chem. Phys. 1995, 102, 384.
27. Eriksson, L. Mol. Phys. 1997, 91, 827-833.
28. Nguyen, M. T.; Creve, S.; Eriksson, L. A.; Vanquickenborne, L. G. Mol. Phys. 1997, 91, 537-550.
29. Eriksson, L. A.; Malkina, O. L.; Malkin, V. G.; Salahub, D. R. J. Chem. Phys. 1996, 100, 5066.
30. Pople, J. A.; Gill, P. M. W.; Handy, N. C. Int. J. Quantum Chem. 1995, 56, 303.
31. Becke, A. J. Chem. Phys. 1997, 107, 8554-8560.
32. Csonka, G. I.; Nguyen, N. A.; Kolossvary, I. J. Comput. Chem. 1997, 18, 1534-1545.
33. Gritsenko, O. V.; Van Leeuwen, R.; Baerends, E. J. Int. J. Quantum Chem.: Quantum Chem. Symp. 1996, 30, 163-172.
34. Adamson, R. D.; Gill, P. M. W.; Pople, J. A. Chem. Phys. Lett. 1998, 284, 6-11.
35. Solà, M.; Forés, M.; Duran, M. Adv. Mol. Similarity, in press.
36. Perdew, J. P.; Ernzerhof, M.; Burke, K. J. Chem. Phys. 1996, 105, 9982-9985.
37. 5 is reported to be 2.6. See: Dean, J. A., Ed. Lange's Handbook of Chemistry, 14th ed.; McGraw-Hill: New York, 1992.
38. Symons, M. Chemical and Biochemical Aspects of Electron-Spin Resonance Spectroscopy; Wiley: New York, 1978; pp 16-32.
39. Atkins, P. W.; Symons, M. C. R. The Structure of Inorganic Radicals; Elsevier: Amsterdam, 1967; pp 20-23, 255-256.
40. Weltner, W. Magnetic Atoms and Molecules; Van Nostrand Reinhold: New York, 1983; pp 57-61.
41. Gordy, W. Theory and Applications of Electron Spin Resonance; Wiley. New York, 1980; pp 199-202.
42. DeVore, T. C.; Weltner, W., Jr. J. Am. Chem. Soc. 1977, 99, 4700-4703.
43. Ammeter, J. H.; Oswald, N.; Bucher, R. Helv. Chim. Acta 1975, 58, 671-682.
44. Belanzoni, P.; Baerends, E. J.; van Asselt, S.; Langewen, P. B. J. Phys. Chem. 1995, 99, 13094-13102.
45. The figure was created with Spartan using the Gaussian 94 wave function. Spartan version 5.0.2, Wavefunction, Inc. 18401 Von Karman Ave., Suite 370, Irvine, CA 92612.