The symmetry-broken formalism applied to the electronic structure of an iminosemiquinone copper(II) catalyst: A key to the qualitative understanding of its reactivity

Chemistry - A European Journal

Volumn 7, Issue 2, 2001, Pages 404-415

  Bachler, Vinzenz ^a   Chaudhuri, Phalguni ^a   Wieghardt, Karl ^a  

^a MAX PLANCK INSTITUTE FOR CHEMICAL ENERGY CONVERSION   (Germany)

Author keywords

Antiferromagnetic coupling; Copper; Density functional calculations; Magnetic properties; Radicals; Symmetry broken formalism

Indexed keywords

COPPER COMPLEX; FERROMAGNETIC MATERIAL; HYDROGEN; IMINOSEMIQUINONE COPPER; SEMIQUINONE; SODIUM ION; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; ELECTRON; MAGNETISM; TECHNIQUE;

EID: 0035910592     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20010119)7:2<404::AID-CHEM404>3.0.CO;2-1     Document Type: Article

References (75)

1. P. Chaudhuri, M. Hess, T. Weyermüller, K. Wieghardt, Angew. Chem. 1999, 111, 1165; Angew. Chem. Int. Ed. 1999 , 38, 1095.
2. P. Chaudhuri, M. Hess, T. Weyermüller, K. Wieghardt, Angew. Chem. 1999, 111, 1165; Angew. Chem. Int. Ed. 1999 , 38, 1095.
3. 2-S clusters, the form of the magnetic orbitals are given in: L. Noodleman, E. J. Baerends, J. Am. Chem. Soc. 1984, 106, 2316, in particular, Figure 2,; See also: ref. [5b] and A. Bencini, S. Midollini, Coord. Chem. Rev. 1992, 120, 87 (particularly p. 127).
4. 2-S clusters, the form of the magnetic orbitals are given in: L. Noodleman, E. J. Baerends, J. Am. Chem. Soc. 1984, 106, 2316, in particular, Figure 2,; See also: ref. [5b] and A. Bencini, S. Midollini, Coord. Chem. Rev. 1992, 120, 87 (particularly p. 127).
5. 2-S clusters, the form of the magnetic orbitals are given in: L. Noodleman, E. J. Baerends, J. Am. Chem. Soc. 1984, 106, 2316, in particular, Figure 2,; See also: ref. [5b] and A. Bencini, S. Midollini, Coord. Chem. Rev. 1992, 120, 87 (particularly p. 127).
6. C. Wang, K. Fink, V. Staemmler, Chem. Phys. 1994, 201, 87; K. Fink, R. Fink, V. Staemmler, Inorg. Chem. 1994, 33, 6219; C. Kolczewski, K. Fink, V. Staemmler, Int. J. Quant. Chem. 2000, 76, 137.
7. C. Wang, K. Fink, V. Staemmler, Chem. Phys. 1994, 201, 87; K. Fink, R. Fink, V. Staemmler, Inorg. Chem. 1994, 33, 6219; C. Kolczewski, K. Fink, V. Staemmler, Int. J. Quant. Chem. 2000, 76, 137.
8. C. Wang, K. Fink, V. Staemmler, Chem. Phys. 1994, 201, 87; K. Fink, R. Fink, V. Staemmler, Inorg. Chem. 1994, 33, 6219; C. Kolczewski, K. Fink, V. Staemmler, Int. J. Quant. Chem. 2000, 76, 137.
9. K. Fink, C. Wang, V. Staemmler, Inorg. Chem. 1999, 38, 3847.
10. a) L. Noodleman, J. Chem. Phys. 1981, 74, 5737;
11. b) L. Noodleman, E. R. Davidson, Chem. Phys. 1986, 109, 131.
12. a) K. Yamaguchi, T. Tsunekawa, Y. Toyota, T. Fueno, Chem. Phys. Lett. 1988, 143, 371;
13. b) J. R. Hart, A. K. Rappe, S. M. Gorun, T. H. Upton, Inorg. Chem. 1992, 31, 5254;
14. c) J. R. Hart, A. K. Rappe, S. M. Gorun, T. H. Upton, J. Phys. Chem. 1992, 96, 6264.
15. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
16. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
17. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
18. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
19. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
20. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
21. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
22. For recent work see, for example: a) T. C. Brunhold, E. I. Solomon, J. Am. Chem. Soc. 1999, 121, 8277; J. Cano, E. Ruiz, P. Alemany, F. Lloret, S. Alvarez, J. Chem. Soc. Dalton Trans. 1999, 1669; I. Demachy, Y. Jean, A. Lledo's, Chem. Phys. Lett. 1999, 303, 621; A. Caneschi, F. Fabrizi de Biani, L. Kloo, P. Zanello, Int. J. Quant. Chem. 1999, 72, 61; J. H. Rodrigues, D. E. Wheeler, J. K. McCusker, J. Am. Chem. 1998, 120, 12051; A. Lledo's, Y. Jean, Chem. Phys. Lett. 1998, 287, 243; J. Cano, P. Alemany, S. Alvarez, M Verdaguer, E. Ruiz, Chem. Eur. J. 1998, 4, 476; H. Kuramochi, L. Noodleman, D. A. Case, J. Am. Chem. Soc. 1997, 119, 11442;
23. b) A. Bencini, F. Totti, C. A. Daul, P. Doclo, P. Fantucci, V. Barone, Inorg. Chem. 1997, 36, 5022.
24. For a thorough discussion of the properties of the UHF wavefunction, see, for example: A. Szabo, N. S. Ostlund, Modern Quantum Chemistry, McGraw-Hill, New York, 1982, Section 3.8, in particular p. 207.
25. See for example: a) ref. [5a] in particular p. 5738;
26. b) L. Noodleman, C. Y. Peng, D. A. Case, J.-M. Mouesca, Coord. Chem. Rev. 1995, 144, 199 (particularly p. 212).
27. See for example: ref. [8], pp. 104-107.
28. See ref. [5a], Equation (34) which is the formula for the exchange coupling constant J.
29. The same is carried out in perturbation theory: the perturbed first-order wavefunction is expanded into the complete set of unperturbed eigenfunctions. See, for example: H. Eyring, J. Walter, G. E. Kimball, Quantum Chemistry, Wiley, New York, 1964, p. 93, Equations (7)-(10).
30. 2 share the same set of eigenfunctions. See, for example: W. Kutzelnigg, Einführung in die Theoretische Chemie, Band 1, Verlag Chemie, Weinheim, 1975, p. 33.
31. a) A. T. Amos, G. G. Hall, Proc. R. Soc. London Ser. A 1961, 263, 483 (in particular p. 490);
32. b) see also ref. [8], p. 106, Equation (2.270).
33. See, for example: F. L. Pilar, Elementary Quantum Chemistry, McGraw-Hill, New York, 1968, p. 288, Figure 11-1.
34. L. Noodleman, D. A. Case, Adv. Inorg. Chem. 1994, 38, 423, [in particular p. 431, Eq. (19)]; see also ref. [9b] p. 214, Equation (2).
35. A. A. Ovchinnikov, J. Labanowski, Phys. Rev. A, 1996, 53, 3946, in particular Figures 1 and 2.
36. J. M. Wittbrodt, H. B. Schlegel, J. Chem. Phys. 1996, 105, 6574.
37. See ref. [14a] p. 491, Table 2.
38. See ref. [17], Equation (6).
39. C. Adamo, V. Barone, A. Bencini, F. Totti, I. Ciofini, Inorg. Chem. 1999, 38, 1996, Equation (6).
40. R. Caballol, O. Castell, F. Illas, I. de P. R. Moreira, J.-P. Malrieu, J. Phys. Chem. A 1997, 101, 7860, in particular the simplified Equation (11) that leads to Equation (3).
41. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian 98, Revision A.5, Gaussian, Pittsburgh PA, 1998.
42. A. D. McLean, G. S. Chandler, J. Chem. Phys. 1980, 72, 5639; R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650.
43. A. D. McLean, G. S. Chandler, J. Chem. Phys. 1980, 72, 5639; R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650.
44. R. Seeger, J. A. Pople, J. Chem. Phys. 1977, 66, 3045.
45. J. A. Pople, M. Head-Gordon, K. Raghavachari, J. Chem. Phys. 1987, 87, 5968.
46. A. D. Becke, J. Chem. Phys. 1993, 98, 5648; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.
47. A. D. Becke, J. Chem. Phys. 1993, 98, 5648; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.
48. R. Bauernschmitt, R. Ahlrichs, J. Chem. Phys. 1996, 104, 9047.
49. J. Gräfenstein, A. M. Hjerpe, E. Kraka, D. Cremer, J. Phys. Chem. A 2000, 104, 1748.
50. Tables of Interatomic Distances and Configurations in Molecules and Ions, The Chemical Society, London, 1958, S7.
51. E. Ruiz, J. Cano, S. Alvarez, P. Alemany, J. Comp. Chem. 1999, 20, 1391.
52. See for example: ref. [22] in particular Tables 2 and 3.
53. E. Ruiz, P. Alemany, S. Alvarez, J. Cano, J. Am. Chem. Soc. 1997, 119, 1297.
54. See ref. [22] in particular p. 7864.
55. We thank R. Trinoga for implementing Gaussian 98 on the Origin 2000 computer.
56. A. D. Becke, Phys. Rev. A 1988, 38, 3098.
57. J. P. Perdew, Phys. Rev. B 1986 33, 8822.
58. T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry, Vol. 3 (Ed.: H. F. Schaeffer, III), Plenum, New York, 1977; M. Dolg, U. Wedig, H. Stoll, H. Preuss, J. Chem. Phys. 1987, 86, 866.
59. T. H. Dunning, P. J. Hay in Modern Theoretical Chemistry, Vol. 3 (Ed.: H. F. Schaeffer, III), Plenum, New York, 1977; M. Dolg, U. Wedig, H. Stoll, H. Preuss, J. Chem. Phys. 1987, 86, 866.
60. V. Jonas, W. Thiel, J. Chem. Phys. 1995, 102, 8474.
61. We thank Dr. T. Weyhermüller for providing this information.
62. [22, 30] Linear combination of the two determinants leads to a solution where the spin densities vanish.
63. We thank one referee for making this suggestion.
64. E. I. Solomon, F. Tuczek, D. E. Root, C. A. Brown, Chem. Rev. 1994, 94, 827.
65. The MOs were plotted by means of the public-domain program MOLDEN.
66. See, for example: O. Kahn, Molecular Magnetism, VCH Publishers, 1993, Chapter 8
67. See, for example for the two-electron case: W. Kutzelnigg, Einführung in die Theoretische Chemie, Band 1, Verlag Chemie, Weinheim, 1975, in particular p. 204. The n-electron case is mentioned for example in: R. McWeeny, Methods of Molecular Quantum Mechanics, Academic Press, London, 1996, in particular p. 126, Equation (5.3.9).
68. See, for example for the two-electron case: W. Kutzelnigg, Einführung in die Theoretische Chemie, Band 1, Verlag Chemie, Weinheim, 1975, in particular p. 204. The n-electron case is mentioned for example in: R. McWeeny, Methods of Molecular Quantum Mechanics, Academic Press, London, 1996, in particular p. 126, Equation (5.3.9).
69. See, for example: A. Gilbert, J. Baggot, Essentials of Molecular Photochemistry, Blackwell, Oxford, 1991, Sect. 2.5.1., pp. 42-43, p. 40, and Figure 9.10.
70. See for example: a) N. J. Turro, Modern Molecular Photochemistry, Benjamin, Menlo Park, 1978, pp. 367-372;
71. b) ref. [47], pp. 302-328, for intramolecular hydrogen abstraction, see pp. 310-328.
72. See, for example: J. A. Barltrop, J. D. Coyle, Excited States in Organic Chemistry, Wiley, London, 1975, pp. 190-200 (in particular p. 191).
73. This holds for the intramolecular hydrogen-atom abstractions: See for example: J. A. Barltrop, J. D. Coyle, Excited States in Organic Chemistry, Wiley, London, 1975, pp. 193-200, in particular p. 194, Table 7.3.
74. See A. Gilbert, J. Baggot, Essentials of Molecular Photochemistry, Blackwell, Oxford, 1991, pp. 412-415.
75. See A. Gilbert, J. Baggot, Essentials of Molecular Photochemistry, Blackwell, Oxford, 1991, p. 413.