The presumption of innocence? A DFT-directed verdict on oxidized amavadin and vanadium catecholate complexes

Inorganic Chemistry

Volumn 46, Issue 26, 2007, Pages 11297-11307

  Geethalakshmi, K R ^a   Waller, Mark P ^a   Bühl, Michael ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 38149126517     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic701650y     Document Type: Article

References (83)

1. See for instance: (a) Rehder, D. In Transition Metal Nuclear Magnetic Resonance; Pregosin, P. S., Ed.; Elsevier: Amsterdam, 1991; pp 1-58.
2. (b) Rehder, D.; Polenova, T.; Bühl, M. Ann. Rep. NMR Spectrosc. 2007, 62, 49-114.
3. Cornman, C. R.; Colopas, G. J.; Hoeschele, J. D.; Kampf, J.; Pecoraro, V. L. J. Am. Chem. Soc. 1992, 114, 9925-9933.
4. Maurya, M.; Khurana, S.; Zhang, W.; Rehder, D. J. Chem. Soc., Perkin Trans. 2 2002, 3015-3023.
5. Rath, S. P.; Rajak, K. K.; Chakravorty, A. Inorg. Chem. 1999, 38, 4376.
6. Baruah, B.; Das, S.; Chakravorty, A. Inorg. Chem. 2002, 41, 4502-4508.
7. Jørgensen, C. K. Coord. Chem. Rev. 1966, 1, 164.
8. See for instance: (a) Bühl, M.; Hamprecht, F. A. J. Comput. Chem. 1998, 119, 113.
9. (b) Bühl, M. J. Inorg. Biochem. 2000, 80, 137.
10. (c) Bühl, M.; Schurhammer, R.; Imhof, P. J. Am. Chem. Soc. 2004, 126, 3310.
11. Bayer, E.; Kneifel, H. Z. Naturforsch. 1972, 27B, 20.
12. Nawi, M. A.; Reichel, T. L. Inorg. Chim. Acta 1987, 136, 33.
13. Fraústo da Silva, J. J. R. Chem. Speciation Bioavailability 1989, 1, 139.
14. Kneifel, H.; Bayer, E. Angew. Chem. 1973, 85, 542-543.
15. Krauss, P.; Bayer, E.; Kneifel, H. Z. Naturforsch., B: Anorg. Chem. Org. Chem 1984, 39b, 829-832.
16. Bayer, E.; Koch, E.; Anderegg, G. Angew. Chem. 1987, 99, 570-572.
17. Bayer, E.; Koch, E.; Anderegg, G. Angew. Chem., Int. Ed. Engl. 1987, 26, 545-546.
18. Carrondo, M. A. A. F. de C. T.; Duarte, M. T. L. S.; Pessoa, J. C.; Silva, J. A. L.; Fraústo da Silva, J. J. R.; Vaz, M. C. T. A.; Vilas-Boas, L. F. J. Chem. Soc., Chem. Commun. 1988, 1158-1159.
19. Fraústo da Silva, J. J. R.; Guedas Da Silva, M. F. C.; Da Silva, J. A. L. Mol. Electrochem. Inorg. Bioinorg Organomet. Compds. 1993, 411-415.
20. Remenyi, C.; Munzarova, M. L.; Kaupp, M. J. Phys. Chem. B 2005, 109, 4227-4233.
21. Butler, A.; Clague, M. J.; Meister, G. Chem. Rev. 1994, 94, 625-638.
22. Nuber, B.; Wriss, J. Acta Crystallogr. 1981, B37, 947-948.
23. Quilitzsch, U.; Wieghardt, K. Z. Naturforsch. 1979, 34b, 640-641.
24. Meicheng, S.; Jing, L.; Zuohua, P.; Huadong, Z.; Youqi, T. HuaXue XueBao 1990, 11, 280-285.
25. Armstrong, E. M.; Beddoes, R. L.; Calviou, L. J.; Charnock, J. M.; Collison, D.; Ertok, S. N.; Naismith, J. H.; Garner, C. D. J. Am. Chem. Soc. 1993, 115, 807.
26. Smith, P. D.; Berry, R. E.; Harben, S. M.; Beddoes, R. L.; Helliwell, M.; Collison, D.; Garner. C. D. J. Chem. Soc., Dalton Trans. 1997, 4509. See ref 8 within.
27. Lenhardt, J.; Baruah, B.; Crans, D. C.; Johnson, M. D. Chem. Commun. 2006, 4641.
28. Paul, P. C.; Angus-Dunne, S. J.; Batchelor, R. J.; Einstein, F. W. B.; Tracey, A. S. Can. J. Chem. 1997, 75, 183.
29. (a) Keramidas, A. D.; Miller, S. M.; Anderson, O. P.; Crans, D. C. J. Am. Chem. Soc. 1997, 119, 8901.
30. (b) Tracey, A. S.; Jaswal, J. S. J. Am. Chem. Soc. 1992, 114, 3835.
31. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03; Gaussian, Inc.: Pittsburgh, PA, 2003.
32. Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 3098-3100.
33. Perdew, J. P. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 33, 8822-8824.
34. Perdew, J. P. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 34, 7406.
35. (a) Wachters, A. J. H. J. Chem. Phys. 1970, 52, 1033-1036.
36. (b) Hay, P. J. J. Chem. Phys. 1977, 66, 4377-4384.
37. (a) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257-2261.
38. (b) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213-222.
39. (c) Binning, R. C., Jr.; Curtiss, L. A. J. Comput. Chem. 1990, 11, 1206.
40. See for instance: Koch, W.; Holthausen, M. C. A Chemist's Guide to Density Functional Theory; Wiley-VCH: Weinheim, Germany, 2000 and the extensive bibliography therein.
41. Ahlrichs, R.; Bär, M.; Häser, M.; Korn, H.; Kölmel, M. Chem. Phys. Lett. 1989, 154, 165.
42. (a) Eichkorn, K.; Treutier, O.; Öhm, H.; Häser, M.; Ahlrichs, R. Chem. Phys. Lett. 1995, 240, 283.
43. (b) Eichkorn, K.; Weigend, F.; Treutier, O.; Ahlrichs, R. Theor. Chem. Acc. 1997, 97, 119.
44. Sherwood, P.; deVries, A. H. ChemShell - A Shell for Computational Chemistry; CCLRC Daresbury Laboratory. 1999; see http://www.dl.ac.uk.
45. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
46. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785-789.
47. Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294.
48. As implemented in Gaussian 03: (a) Barone, V.; Cossi, M.; Tomasi, J. J. Comput. Chem. 1998, 19, 404-417.
49. (b) Cossi, M.; Scalmani, G.; Rega, N.; Barone, V. J. Chem. Phys. 2002, 117, 43-54.
50. (c) Cossi, M.; Crescenzi, O. J. Chem. Phys. 2003, 19, 8863-8872.
51. LYP; for the original formulation of the "half-and-half" hybrid functional see: Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
52. Seeger, R.; Pople, J. A. J. Chem. Phys. 1977, 66, 3045.
53. Bühl, M.; Kabrede, H. J. Chem. Theory Comput. 2006, 2, 1282-1290.
54. The stationary point for 6 turned out be a transition state; we discuss it here because it has the same orientations of the OR groups as in 2a. The true minimum with an additional intramolecular H bridge is 0.65 kcal/mol lower in energy and it has a δ = -630.
55. (a) Koch, E.; Kneifel, H.; Bayer, E. Z. Naturforsch 1986, 41b, 359-362.
56. (b) For a recent X-ray crystallography and NMR study see: Hubregtse, T.; Kooijman, H.; Spek, A. L.; Maschmeyer, T.; Sheldon, R. A.; Arends, I. W.; Hanafield, U. J. Inorg. Biochem. 2007, 101, 900-908.
57. (a) Grigoleit, S.; Bühl, M. Chem. - Eur. J. 2004, 10, 5541-5552.
58. (b) Bühl, M.; Grigoleit, S. Organometallics 2005, 24, 1516-1527.
59. In each case, the mean values over the entire trajectories correspond closely to the mean values over the snapshots selected for the NMR computations.
60. Cooper, S. R.; Koh, Y. B.; Raymond, K. N. J. Am. Chem. Soc. 1982, 104, 5092.
61. Kraft, B. J.; Coalter, N. L.; Nath, M.; Clark, A. E.; Siedle, A. R.; Huffman, H. C.; Zaleski, J. M. Inorg. Chem. 2003, 42, 1663.
62. Kabanos, T. A.; White, A. J. P.; Williams, D. J.; Woollins, J. D. Chem. Commun. 1992, 17.
63. Simpson, C. L.; Pierpont, C. G. Inorg. Chem. 1992, 31, 4308.
64. Hou, Z.; Stack, T. D. P.; Sunderland, C. J.; Raymond, K. N. Inorg. Chim. Acta 1997, 263, 341.
65. Manos, M. J.; Tasiopoulos, A. J.; Raptopoulou, C.; Terzis, A.; Woollins, J. D.; Slawin, A. M. Z.; Keramidas, A. D.; Kabanos, T. A. J. Chem. Soc., Dalton Trans. 2001, 1556.
66. Barauh, B.; Chakravorty, A. Indian J. Chem., Sect. A: Inorg., Bioinorg., Phys., Theor. Anal. Chem. 2003, 42, 2677.
67. Maurya, M. R.; Agarwal, S.; Abid, M.; Azam, A.; Bader, C.; Ebel, M.; Rehder, D. Dalton Trans. 2006, 937-947.
68. According to TDDFT computations at the B3LYP/AE1+ level, the lowest excited state in 9 (at λ = 720 nm) can to a large extent be described as a HOMO-LUMO transition. Despite the known deficiencies of TDDFT for charge-transfer states (see, e.g., Dreuw, A.; Head-Gordon, M. J. Am. Chem. Soc. 2004, 126, 4007), this number compares reasonably well to experiment, λ = 870 nm (ref 2). A much higher excitation energy, corresponding to λ = 552 nm, is predicted for the innocent complex 11.
69. We have also looked at other systems related to 9 and 11 that contained different tridendate ligands and/or alkyl-substituted catechols and which afforded results very similar to the ones reported here.
70. For pictorial rationalizations of such paramagnetic contributions in transition-metal complexes see, e.g.: (a) Berger, S.; Bock, W.; Frenking, G.; Jonas, V.; Müller, V. J. Am. Chem. Soc. 1995, 117, 3820.
71. (b) Ruiz-Morales, Y.; Ziegler, T. J. Phys. Chem. A 1998, 102, 3970. Unfortunately, the Gaussian program employed in the present study does not allow for a detailed analysis of such individual MO contributions.
72. See for example: Ghosh, A. J. Biol. Inorg. Chem. 2006, 11, 712 and references therein.
73. (a) Reiher, M.; Salomon, O.; Hess, B. A. Theor. Chem. Acc. 2001, 107, 48.
74. (b) Reiher, M. Inorg. Chem. 2002, 41, 6928.
75. 51V) value of, e.g., 9, closer to experiment, the overall performance for a larger set of normal vanadium complexes deteriorates significantly (Geethalakshmi, K. R.; Bühl, M. unpublished results).
76. 51V NMR spectrum can be recorded), then the amount of HF exchange would certainly have to be reduced below the 20% contained in the standard version of this functional, down to a value at which a singlet ground state would be obtained.
77. Even though such single-reference BS solutions do not provide an appropriate description of the true open-shell wavefunction, they can be used to estimate magnetic exchange couplings in transition-metal complexes, cf: (a) Noodleman, L. J. Chem. Phys. 1981, 74, 5737.
78. For a recent review see: (b) Ciofini, I.; Daul, C. Coord. Chem. Rev. 2003, 238-239, 187.
79. In that case, the observed resonances should shift strongly with temperature. To our knowledge, no such temperature-dependent NMR studies have been performed yet for the complexes in question. Admixture of paramagnetic states should also lead to substantial line broadening, and indeed, very broad lines (half-width 2-4 kHz) have been reported for some of the catchol complexes in ref 2.
80. Moon, S.; Patchkovskii, S. In Calculation of NMR and EPR Parameters. Theory and Applications; Kaupp, M.; Bühl, M.; Malkin, V. G., Eds.; Wiley-VCH: Weinheim, Germany, 2004; p 325.
81. Hrobarik, P.; Reviakine, R.; Arbuznikov, A. V.; Malkina, O. L.; Malkin, V. G.; Köhler, F. H.; Kaupp, M. J. Chem. Phys. 2007, 126, 024107.
82. It cannot be excluded, however, that the good performance of the restricted B3LYP method in systems with an unstable closed-shell wavefunction is to some extent fortuitous.
83. See for instance: Grimme, S.; Waletzke, M. J. Chem. Phys. 1999, 111, 5645.