Determination of the g-tensors and their orientations for cis,trans-(L-N2S2)MoVOX (X = Cl, SCH 2Ph) by single-crystal EPR spectroscopy and molecular orbital calculations

Inorganic Chemistry

Volumn 44, Issue 5, 2005, Pages 1290-1301

  Cosper, Michele Mader ^a   Neese, Frank ^b   Astashkin, Andrei V ^a   Carducci, Michael D ^a   Raitsimring, Arnold M ^a   Enemark, John H ^a  

^a University of Arizona   (United States)

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

Author keywords

[No Author keywords available]

Indexed keywords

MOLYBDENUM COMPLEX; SULFITE OXIDASE; SULFUR; XANTHINE OXIDASE;

ARTICLE; CHEMICAL BOND; CRYSTAL STRUCTURE; DENSITY FUNCTIONAL THEORY; ELECTRON SPIN RESONANCE; MATHEMATICAL ANALYSIS; MOLECULAR INTERACTION; PH;

ELECTRON SPIN RESONANCE SPECTROSCOPY; ENZYMES; MODELS, MOLECULAR; MOLECULAR CONFORMATION; MOLECULAR STRUCTURE; MOLYBDENUM; ORGANOMETALLIC COMPOUNDS; QUANTUM THEORY;

EID: 14744285443     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic0483850     Document Type: Article

References (127)

1. Hille, R. Chem. Rev. 1996, 96, 2757-2816.
2. Sigel, A.; Sigel, H. Molybdenum and Tungsten: Their Roles in Biological Processes; Metals Ions in Biological Systems Vol. 39; Dekker: New York, 2002.
3. Hille, R. In Metals Ions in Biological Systems; Sigel, A., Sigel, H., Eds.; Dekker: New York, 2002; pp 187-226.
4. Hille, R.; George, G. N.; Eidsness, M. K.; Cramer, S. Inorg. Chem. 1989, 28, 4018-4022.
5. George, G. N.; Prince, R. C.; Mukund, S.; Adams, M. W. W. J. Am. Chem. Soc. 1992, 114, 3521-3523.
6. George, G. N.; Garrett, R. M.; Prince, R. C.; Rajagopalan, K. V. J. Am. Chem. Soc. 1996, 118, 8588-8592.
7. Baugh, P. E.; Garner, C. D.; Charnock, J. M.; Collison, D.; Davies, E. S.; McAlpine A. S.; Bailey, S.; Lanes, I.; Hanson, G. R.; McEwan, A. G. J. Biol. Inorg. Chem. 1997, 2, 634-643.
8. George, G. N.; Hilton, J.; Temple, C.; Prince, R. C.; Rajagopalan, K. V. J. Am. Chem. Soc. 1999, 121, 1256-1266.
9. Dobbeck, H.; Huber, R. In Metals Ions in Biological Systems; Sigel, A., Sigel, H., Eds.; Dekker: New York, 2002, pp 228-263.
10. Kisker, C. Handbook of Metalloproteins; Messerschmidt, A., Huber, R., Poulos, T., Wieghardt, K., Eds.; John Wiley & Sons Ltd.: Ne™ York, 2001; Vol. 2, pp 1121-1135.
11. Kisker, C.; Schindelin, H.; Rees, D. C. Annu. Rev. Biochem. 1997, 66, 233-267.
12. George, G. N.; Pickering, I. J.; Kisker, C. Inorg. Chem. 1999, 38 (10), 2539-2540.
13. Kisker, C.; Schindelin, H.; Pacheco, A.; Wehbi, W. A.; Garrett, R. M.; Rajagopalan, K. V.; Enemark, J. H.; Rees, D. C. Cell 1997, 91, 973-983.
14. Hille, R. JBIC, J. Biol. Inorg. Chem. 1997, 2, 804-809.
15. Fischer, B.; Enemark, J. H.; Basu, P. J. Inorg. Biochem. 1998, 72, 13-21.
16. Rajagopalan, K. Enzymol. Relat. Areas Mol. Biol. 1991, 64, 215-289.
17. Rajagopalan, K. V.; Johnson, J. L. J. Biol. Chem. 1992, 267, 10199-10202.
18. Cramer, S. P.; Hille, R. J. Am. Chem. Soc. 1985, 107, 8164-8169.
19. George, G. N.; Bray, R. C. Biochemistry 1988, 27, 3603-3609.
20. Wilson, G. L.; Greenwood, R. J.; Pilbrow, J. R.; Spence, J. T.; Wedd, A. G. J. Am. Chem. Soc. 1991, 113, 6803-6812.
21. Greenwood, R. J.; Wilson, G. L.; Pilbrow, J. R.; Wedd, A. G. J. Am. Chem. Soc. 1993, 115, 5385-5392.
22. Romão, M. J.; Archer, M.; Moura, J. J. G.; LeGall, J.; Engh, R.; Schneider, M.; Hof, P.; Huber, R. Science 1995, 270, 1170-11776.
23. Huber, R.; Hof, P.; Duarter, R. O.; Moura, J. J. G.; Moura, I.; Liu, M.; LeGall, J.; Hille, R.; Archer, M.; Romão, M. Proc. Natl. Acad. Sci. U.S.A. 1996, 93, 8846-8851.
24. Enroth, C.; Eger, B. T.; Okamoto, K.; Nishino, T.; Nishino, T.; Pai, E. F. Proc. Natl. Acad. Sci U.S.A. 2000, 97, 10723-10728.
25. Truglio, J. J.; Theis, K.; Leimkuhler, S.; Rappa, R.; Rajagopalan, K.; Kisker, C. Structure 2002, 10, 115-125.
26. Rajagopalan, K. Molybdenum and Molybdenum Containing Enzymes; Coughlan, M., Ed.; Pergamon: Oxford, U.K., 1980; pp 241-272.
27. Brody, M. S.; Hille, R. Biochemistry 1999, 38, 6668-6677.
28. Pacheco, A.; Hazzard, J. T.; Tollin, G.; Enemark, J. H. JBIC, J. Biol. Inorg. Chem. 1999, 4, 390-401.
29. Astashkin, A. V.; Mader, M. L.; Pacheco, A.; Enemark, J. H.; Raitsimring, A. M. J. Am. Chem. Soc. 2000, 122, 5294-5302.
30. Dhawan, I. K.; Pacheco, A.; Enemark, J. H. J. Am. Chem. Soc. 1994, 116, 7911-7912.
31. Dhawan, I. K.; Enemark, J. H. Inorg. Chem. 1996, 35, 4873-4882.
32. Bray, R. C. In Biological Magnetic Resonance; Reuben, J., Berliner, L. J., Eds.; Plenum Press: New York, 1980; pp 45-84.
33. Collison, D.; Mabbs, F. E.; Enemark, J. H.; Cleland, W. E., Jr. Polyhedron 1986, 5, 423-425.
34. Guiles, R. D. M.S. Thesis, San Francisco State University, San Francisco, CA, 1983.
35. Dowerah, D.; Spence, J. T.; Singh, R.; Wedd, A. G.; Wilson, G. L.; Farchione, F.; Enemark, J. H.; Kristofski, J.; Bruck, M. J. Am. Chem. Soc. 1987, 109, 5655-5665.
36. Enemark, J. H.; Young, C. G. Adv. Inorg. Chem. 1993, 40, 1-88.
37. Peariso, K.; Chohan, B. S.; Carrano, C. J.; Kirk, M. L. Inorg. Chem. 2003, 42, 6194-6203.
38. Chang, C. S. J.; Enemark, J. H. Inorg. Chem. 1991, 30, 683-688.
39. Chang, C. S. J.; Collison, D.; Mabbs, F. E.; Enemark, J. H. Inorg. Chem. 1990, 29, 2261-2267.
40. Chang, C. S. J.; Pecci, T. J.; Carducci, M. D.; Enemark, J. H. Inorg. Chem. 1993, 32, 4106-4110.
41. Cleland, W. E., Jr.; Barnhart, K. M.; Yamanouchi, K.; Collison, D.; Mabbs, F. E.; Ortega, R. B.; Enemark, J. H. Inorg. Chem. 1987, 26, 1017-1025.
42. Lim, B. S.; Willer, M. W.; Maio, M.; Holm, R. H. J. Am. Chem. Soc. 2001, 123, 8343-8349.
43. Mader, M. L.; Carducci, M. D.; Enemark, J. H. Inorg. Chem. 2000, 39, 525-531.
44. Garner, C. D.; Hill, L. H.; Mabbs, F. E.; McFadden, D. L.; McPhail, A. T. J. Chem. Soc., Dalton Trans. 1977, 853-858.
45. Collison, D.; Eardley, D. R.; Mabbs, F. E.; Rigby, K.; Enemark, J. H. Polyhedron 1989, 8, 1833-1834.
46. Garner, C. D.; Lambert, P.; Mabbs, F. E.; King, T. J. J. Chem. Soc., Dalton Trans. 1977, 1191-1198.
47. Garner, C. D.; Howlander, N. C.; Mabbs, F. E.; Boorman, P. M.; King, T. J. J. Chem. Soc., Dalton Trans. 1978, 1350-1354.
48. Gahan, B.; Howlander, N. C.; Mabbs, F. E. J. Chem. Soc., Dalton Trans. 1981, 142-149.
49. Collison, D.; Eardley, D. R.; Mabbs, F. E.; Rigby, K.; Bruck, M. A.; Enemark, J. H.; Wexler, P. A. J. Chem. Soc., Dalton Trans. 1994, 1003-1011.
50. Balagopalakrishna, C.; Kimbrough, J. T.; Westmoreland, T. D. Inorg. Chem. 1996, 35, 7758-7768.
51. Nipales, N. S.; Westmoreland, T. D. Inorg. Chem. 1997, 36, 756-757.
52. Mader, M. L. Ph.D. Dissertation, University of Arizona, Tucson, AZ, 2000.
53. Mabbs, F. E.; Collison, D. Electron Paramagnetic Resonance of d Transition Metal Compounds; Elsevier Science: Amsterdam, 1992.
54. Barnard, K. R.; Bruck, M.; Huber, S.; Grittini, C.; Enemark, J. H., Gable; Wedd, A. G. Inorg. Chem. 1997, 36, 637-649.
55. Jalilehvand, F.; Lim, B. S.; Holm, R. H.; Hedman, B.; Hodgson, K. O. Inorg. Chem. 2003, 42, 5531-5536.
56. Neese, F. Curr. Opin. Chem. Biol. 2003, 7, 125.
57. Neese, F.; Solomon, E. In Magnetoscience-From Molecules to Materials; Miller, J. S., Drillon, M., Eds.; Wiley: New York, 2003; pp 345-466.
58. Peng, G.; Nichols, J.; McCullough, E. A.; Spence, J. Inorg. Chem. 1994, 33, 2857-2864.
59. Swann, J.; Westmoreland, T. D. Inorg. Chem. 1997, 36, 5348-5357.
60. Schreckenbach, G.; Ziegler, T. J. Phys. Chem. A 1997, 101, 3388-3399.
61. Malkina, O. L.; Vaara, J.; Schimmelpfennig, B.; Munzarová, M.; Malkin, V. G.; Kaupp, M. J. Am. Chem. Soc. 2000, 122, 9206-9218.
62. Kaupp, M.; Reviakine, R.; Malkina, O. L.; Arbuznikov, A.; Schimmelpfennig, B.; Malkin, V. G. J. Comput. Chem. 2002, 23, 794-803.
63. Van Lenthe, E.; Wormer, P. E. S.; Van Der Avoird, A. J. Chem. Phys. 1997, 107, 2488-2498.
64. Neyman, K. M.; Ganyushin, D. I.; Matveev, A. V. J. Chem. Phys. A 2002, 106, 5022-5030.
65. Neese, F. J. Chem. Phys. 2001, 115, 11080-11096.
66. Neese, F. Int. J. Quantum Chem. 2001, 83, 104-114.
67. Neese, F.; Solomon, E. I. Inorg. Chem. 1998, 37, 6568-6582.
68. Kaupp, M., Malkin, V., Bühl, M., Eds. Calculation of NMR and EPR Parameters, Wiley-VCH, 2004.
69. SAINT V. 5.01: Software for the CCD Detector System; Brucker Analytical X-ray System: Madison, WI, 1998.
70. Blessing, R. H. SADABS: Program for absorption corrections using Seimens CCD based in the method of Robert Blessing. Acta Crystallogr. 1995, A51, 33-38.
71. Altomare, A.; Cascarano, M.; Giacovazzo, C.; Guagliardi, A. J. Appl. Crystallogr. 1993, 26, 343.
72. teXsan: Single-Crystal Structure Analysis Software, V. 1.8; Molecular Structure Corp.: 3200 Research Forest Drive, The Woodlands, TX 77381, 1992, 1997.
73. SMART, Software for the Bruker AXS Single-Crystal Diffractometer; Brucker Analytical X-ray System: Madison, WI, 1998.
74. Morton, J. R.; Preston, K. F. J. Magn. Reson. 1983, 52, 457.
75. Neese, F. Unpublished program, 2000.
76. Ridley, J.; Zerner, M. Theor. Chim. Acta 1973, 32, 111-134.
77. Zerner, M. C.; Loew, G. H.; Kirchner, R. F.; Mueller-Westerhoff, U. T. J. Am. Chem. Soc. 1980, 102, 589-599.
78. Edwards, W. D.; Zerner, M. C. Theor. Chim. Acta 1987, 72, 347-361.
79. Reeves, C. M. Commun. ACM 1966, 9, 276.
80. Cooper, I. L.; McWeeny, R. J. Chem. Phys. 1966, 45, 226-234.
81. Sutcliffe, B. T. J. Chem. Phys. 1966, 45, 235-239.
82. van Lenthe, E.; Snijders, J. G.; Baerends, E. J. Chem. Phys. 1996, 105, 6505.
83. Neese, F. ORCA-an ab initio, Density Functional and Semiempirical Program Package, version 2.4, revision 12; Max Planck Institut für Bioanorganische Chemie: Mülheim an der Ruhr, Germany, July 2004.
84. van Wüllen, C. J. Chem Phys. 1998, 109, 392.
85. Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571.
86. Schäfer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829.
87. Ahlrichs, R.; May, K. Chem. Phys. 2000, 2, 943.
88. Huzinaga, S.; Miguel, B. Chem. Phys. Lett. 1990, 175, 289.
89. Huzinaga, S.; Klobukowski, M. Chem. Phys. Lett. 1993, 212, 260.
90. Neese, F. Inorg. Chim. Acta 2002, 337C, 181.
91. von Armim, M.; Ahlrichs, R. J. Chem. Phys. 1999, 111, 9183.
92. Ahlrichs, R.; Bär, M.; Baron, H.; Bauernschmitt, R.; Böcker, S.; Ehrig, M.; Eichkorn, K.; Elliott, S.; Furche, F.; Haase, F.; Häser, M.; Horn, H.; Huber, C.; Öhm, H.; Schäfer, A.; Schneider, U.; Treutler, O.; von Arnim, M.; Weigend, F.; Weis, P.; Weiss, H. TURBOMOLE Program System for ab initio Electronic Structure Calculations, Version 5.2; University of Karlsruhe: Karlsruhe, Germany, 2000.
93. van Lenthe, J.; Fass, S.; Snijders, J. G. Chem. Phys. Lett. 2000, 328, 107.
94. van Lenthe, E.; van der Avoird, A.; Wormer, E. J. Chm. Phys. 1998, 108, 4783.
95. Neese, F. J. Chem. Phys. 2003, 118, 3939.
96. Neese, F. J. Chem. Phys. 2005, 122, 34107.
97. Hess, B.; Marian, C.; Wahlgren, U.; Gropen, O. Chem. Phys. Lett. 1996, 251, 365.
98. Schimmelpfennig, B. The Atomic Mean Field Spin-Orbit Coupling (AMFI) Program; Stockholm University: Stockholm, Sweden, 1996.
99. Neese, F. J. Chem. Phys. 2001, 115, 11080.
100. Becke, A. Phys. Rev. A. 1988, 38, 3098.
101. Perdew, J. Phys. Rev. B. 1986, 33, 8822.
102. Klamt, A.; Schuurmann, G. J. Chem. Soc., Perkin Trans. 1993, 2, 799.
103. Wennmohs, F.; Diedhenhofen, M.; Klamt, A.; Neese, F. Manuscript in preparation.
104. Waller, W.; Rogers, M. J. Magn. Reson. 1973, 9, 92-107.
105. Weil, J. A.; Bolton, J. R.; Wertz, J. E. Electron Paramagnetic Resonance: Elementary Theory and Practical Applications; John Wiley and Sons: New York, 1994.
106. Hare, C. R.; Bernal, I.; Gray, H. B. Inorg. Chem. 1962, 1, 831-835.
107. Carducci, M. D.; Brown, C.; Solomon, E. I.; Enemark, J. H. J. Am. Chem. Soc. 1994, 116, 11856-11868.
108. Inscore, F. E.; McNaughton, R.; Westcott, B.; Helton, M. E.; Jones, R.; Dhawan, I. K.; Enemark, J. H.; Kirk, M. L. Inorg. Chem. 1999, 38, 1401-1410.
109. Note that the energies in Figure 7 are drawn to scale and reflect the zeroth order approximation to the transition energy with the SOMO as the reference MO. Thus, virtual orbital energies reflect the energy of promoting the unpaired electron from the SOMO to the virtual orbital while the energies of the doubly occupied MOs reflect the transition energy from this orbital to the SOMO. This way of plotting orbital energies yields a more intuitively appealing picture than the canonical orbital energies which, in Hartree-Fock and related theories, often leads to SOMO energies that are below some doubly occupied MOs because the canonical MO energies do not properly reflect the electronic relaxation accompanying excitation or ionisation processes and which is very different for metal- and ligand-based MOs.
110. Zerner, M. C. Metal-Ligand Interactions: From Atoms, to Clusters, to Surfaces; Russo, N., Salahub, D. R., Eds.; Kluwer: Dordrecht, The Netherlands, 1992; pp 101-123.
111. Zerner, M. C. Metal-Ligand Interactions: Structure and Reactivity; Russo, N., Salahub, D. R., Eds.; Kluwer: Dordrecht, The Netherlands, 1996; pp 493-531.
112. Kirk, M. L.; Peariso, K. Curr. Opin. Chem. Biol. 2003, 7, 220-227.
113. McNaughton, R. L.; Tipton, A. A.; Ruble, N. D.; Conry, R. R.; Kirk, M. L. Inorg. Chem. 2000, 39, 5697-5706.
114. McNaughton, R. L.; Helton, M. E.; Rubie, N. D.; Kirk, M. L. Inorg. Chem. 2000, 39, 4386-4387.
115. Helton, M. E.; Kirk, M. L. Inorg. Chem. 1999, 38, 4384-4385.
116. McMaster, J.; Carducci, M. D.; Yang, Y.-S.; Solomon, E. I.; Enemark, J. H. Inorg. Chem. 2001, 40, 687-702.
117. McNaughton, R. L.; Helton, M. E.; Cosper, M. M.; Enemark, J. H.; Kirk, M. L. Inorg. Chem. 2004, 43, 1625-1637.
118. Munzarova, M.; Kaupp, M. J. Phys. Chem. A 1999, 103, 9966.
119. Astashkin, A. V.; Cosper, M. M.; Raitsimring, A. M.; Enemark, J. H. Inorg. Chem. 2000, 39, 4989-4992.
120. Bray, R. C.; Malström, B. G.; Vänngård, T. Biochem. J. 1959, 73, 193.
121. (a) Patchkovskii, S.; Ziegler, T. J. Chem. Phys. 1999, 111, 5730.
122. (b) Patchkovskii, S.; Ziegler, T. J. Phys. Chem. 2001, 105, 54490.
123. (c) Patchkovskii, S.; Ziegler, T. J. Am. Chem. Soc. 2000, 122, 3506.
124. (d) Arbuznikov, A.; Kaupp, M.; Malkin, V.; Reviakine, R.; Malkina, O. Phys. Chem. Chem. Phys. 2002, 4, 5467.
125. (e) Frantz, S.; Hartmann, H.; Doslik, N.; Wanner, M.; Kaim, W.; Kümmerer, H.-J.; Denninger, G.; Barra, A.-L.; Duboc-Toia, C.; Fiedler, J.; Ciofini, I.; Urban, C.; Kaupp, M. J. Am. Chem. Soc. 2002, 124, 10563.
126. (f) Kaupp, M.; Reviakine, R.; Malkina, O.; Arbuznikov, A.; Schimmelpfennig, B.; Malkin, V. J. Comp. Chem. 2002, 23, 794.
127. (g) Arratia-Perez, R.; Hernandez-Acevedo, L. J. Chem. Phys. 2003, 118, 7425.