Elucidation of a low spin cobalt(II) system in a distorted tetrahedral geometry

Journal of the American Chemical Society

Volumn 124, Issue 51, 2002, Pages 15336-15350

  Jenkins, David M ^a   Di Bilio, Angel J ^a   Allen, Matthew J ^a   Betley, Theodore A ^a   Peters, Jonas C ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

TETRAHEDRAL GEOMETRY;

ANTIFERROMAGNETIC MATERIALS; BROMINE COMPOUNDS; COBALT; COMPLEXATION; COPPER; DIMERS; MONOMERS; OXIDATION; PARAMAGNETIC RESONANCE; SPECTROSCOPIC ANALYSIS; SQUIDS; STOICHIOMETRY;

ANIONIC POLYMERIZATION;

BROMIDE; CHLORIDE; COBALT COMPLEX; COPPER COMPLEX; DIMER; LIGAND; PHOSPHINE DERIVATIVE; TRIS(PHOSPHINE); UNCLASSIFIED DRUG;

ACCELERATION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; ELECTRON SPIN RESONANCE; GEOMETRY; MOLECULAR DYNAMICS; OXIDATION; REACTION ANALYSIS; SOLID STATE; SPECTROSCOPY; STOICHIOMETRY; SYNTHESIS; TEMPERATURE DEPENDENCE;

EID: 0037176246     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja026433e     Document Type: Article

References (78)

1. Lippard, S. J.; Berg, J. M. Principles of Bioinorganic Chemistry; University Science Books: Mill Valley, CA, 1994; Chapter 12.
2. (a) Halpern, J. Science 1985, 227, 869-875.
3. (b) Geno, M. K.; Halpern, J. J. Am. Chem. Soc. 1987, 109, 1238-1240.
4. Perutz, M. F.; Fermi, G.; Luisi, B.; Shaanan, B.; Liddington, R. C. Acc. Chem. Res. 1987, 20, 309-321.
5. Raphael, A. L.; Gray, H. B. J. Am. Chem. Soc. 1991, 113, 1038-1040.
6. Garret, T. P. J.; Glingeleffer, D. J.; Guss, J. M.; Rogers, S. J.; Freeman, H. C. J. Biol. Chem. 1984, 259, 2822-2825.
7. Schultz, B. E.; Gheller, S. F.; Muetterties, M. C.; Scott, M. J.; Holm, R. H. Acc. Chem. Res. 1986, 19, 363-370.
8. Sellmann, D.; Sutter, J. Acc. Chem. Res. 1997, 30, 460-469.
9. (a) Everett, G. W.; Holm, R. H. J. Am. Chem. Soc. 1965, 87, 5266-5267.
10. (b) Cotton, F. A.; Soderberg, R. H. J. Am. Chem. Soc. 1962, 84, 872-873. Also see the general references 21, 22, and 38.
11. Stereochemical tuning of 4-coordinate structure types of cobalt(II), and the ground spin-state consequences of such tuning has been recently described: Jaynes, B. S.; Doerrer, L. H.; Liu, S.; Lippard, S. J. Inorg. Chem. 1995, 34, 5735-5744.
12. (a) Solomon, E. I.; Rawlings, J.; McMillin, J. R.; Stephens, P. J.; Gray, H. B. J. Am. Chem. Soc. 1976, 98, 8046-8048.
13. (b) Bertini, I.; Luchinat, C. Acc. Chem. Res. 1983, 16, 272-279.
14. (c) Bertini, I.; Lanini, G.; Luchinat, C. J. Am. Chem. Soc. 1983, 105, 5116-5118.
15. (d) Khalifah, R. G.; Rogers, J. I.; Harmon, P.; Morely, P. J.; Carroll, S. B. Biochemistry 1984, 23, 3129-3136.
16. (e) Briganti, F.; Pierattelli, R.; Scozzafava, A.; Supuran, C. T. Eur. J. Med. Chem. 1996, 31, 1001-1010.
17. Cobalt complexes supported by tris(pyrazolyl)borate ligands have been studied extensively. For recent examples, see: (a) Detrich, J.; Koneèny-Vetter, W. M.; Doren, D.; Rheingold, A. L.; Theopold, K. H. J. Am. Chem. Soc. 1996, 118, 1703-1712.
18. (b) Jewson, J. D.; Liable-Sands, L. M.; Yap, G. P. A.; Rheingold, A. L.; Theopold, K. H. Organometallics 1999, 18, 300-305.
19. (c) Thyagarajan, S.; Incarvito, C. D.; Rheingold, A. L.; Theopold, K. H. Chem. Commun. 2001, 2198-2199.
20. Cobalt complexes supported by tris(thioether)borate ligands have been studied recently. See: Schebler, P.; Mondimutsira, B.; Riordan, C. G.; Liable-Sands, L. M.; Incarvito, C. D.; Rheingold, A. L. J. Am. Chem. Soc. 2001, 123, 331-332.
21. (a) Peters, J. C.; Feldman, J. D.; Tilley, T. D. J. Am. Chem. Soc. 1999, 121, 9871-9872.
22. (b) Barney, A. A.; Heyduk, A. F.; Nocera, D. G. Chem. Commun. 1999, 2379-2380.
23. 2. In this manuscript, we restrict our use of the term triphos to represent the former ligand class.
24. (a) Benelli, C.; DiVaira, M.; Noccioli, G.; Sacconi, L. Inorg. Chem. 1977, 16, 182-187.
25. (b) Ghilardi, C.; Midollina, S.; Orlandini, A.; Sacconi, L. Inorg. Chem. 1980, 19, 301-306.
26. (c) Dapparto, P.; Midollini, S.; Orlandini, A.; Sacconi, L. Inorg. Chem. 1976, 15, 2768-2744.
27. 2+ chemistry, see: (a) Heinze, K.; Huttner, G.; Walter, O. Eur. J. Inorg. Chem. 1999, 593-600.
28. (b) Heinze, K.; Huttner, G.; Schober, P. Eur. J. Inorg. Chem. 1998, 183-189.
29. (c) Heinze, K.; Huttner, G.; Zsolnai, L. Z. Naturforsch (B) 1999, 54, 1147-1154.
30. (d) Winterhalter, U.; Zsolnai, L.; Kirscher, P.; Heinz, K.; Huttner, G. Eur. J. Inorg. Chem. 2001, 89-103.
31. (e) Rupp, R.; Huttner, G.; Kirscher, P.; Soltek, R.; Büchner, M. Eur. J. Inorg. Chem. 2000, 1745-1757.
32. Hewertson, W.; Watson, H. R. J. Chem. Soc. 1962, 1490-1494.
33. (a) Lu, C. C.; Peters, J. C. J. Am. Chem. Soc. 2002, 124, 5273-5273.
34. (b) Thomas, J. C.; Peters, J. C. J. Am. Chem. Soc. 2001, 123, 5100-5101.
35. (c) Shapiro, I. R.; Jenkins, D. M.; Thomas, J. C.; Day, M. W.; Peters, J. C. Chem. Commun. 2001, 2152-2153.
36. (d) Jenkins, D. M.; Betley, T. A.; Peters, J. C. J. Am. Chem. Soc. 2002, 124, 11238-11239.
37. -. Betley, T. A.; Peters, J. C. Inorg. Chem. 2002, in press.
38. This finding was briefly described in a previous communication. See ref 18c.
39. For a lucid discussion of cobalt(II) EPR spectroscopy, see: Bencini, A.; Gatteschi, D. Trans. Metal Chem. 1982, 8, 97-119.
40. A thorough discussion of the electronic structure of cobalt(II) systems in 4-, 5-, and 6-coordinate geometries has been provided by Lever: Lever, A. B. P. Inorganic Electronic Spectroscopy, 2nd Ed.; Elsevier: New York, 1984; pp 480-505.
41. (a) Sacconi, L.; Midollini, S. J. Chem. Soc., Dalton. Trans. 1972, 1213-1216.
42. (b) Dapporto, P.; Midollini, S.; Sacconi, L. Inorg. Chem. 1975, 14, 1643-1650.
43. (c) Mealli, C.; Midollini, S.; Sacconi, L. Inorg. Chem. 1975, 14, 2513-2521.
44. (d) Ghilardi, C. A.; Midollini, S.; Sacconi, L. J. Organomet. Chem. 1980, 186, 279-287.
45. See Heinze, K.; Huttner, G.; Zsolnai, L.; Schober, P. Inorg. Chem. 1997, 36, 5457-5469.
46. Complex 1 contained two crystallographically independent molecules in the asymmetric unit. For brevity, only one of the molecules is explicitly discussed in the main text. The Supporting Information contains crystal coordinates, bond lengths, and bond angles for both molecules of the asymmetric unit.
47. Reinaud, O.; Rheingold, A.; Theopold, K. Inorg. Chem. 1994, 33, 2306-2308.
48. tert-butyl]CoI has also been fully characterized but is not yet published (Riordan, C., personal communication).
49. Casey, A. T.; Mitra, S. Theory and Application of Molecular Paramagnetism; Bourduaux, E. A., Mulay, N. L., Eds.; Wiley: New York, 1976.
50. (a) Sur, S. K. J. Magn. Reson. 1989, 82, 169-173.
51. (b) Evans, D. F. J. Chem. Soc. 1959. 2003-2005.
52. (a) Sinn, E. Coord. Chem. Rev. 1970, 5, 313-347, and references therein.
53. (b) Ball, P. W. Coord. Chem. Rev. 1969, 4, 361-383.
54. (c) Kato, M.; Jonassen, H. B.; Fanning, J. C. Chem. Rev. 1964, 64, 99-128.
55. Ghilardi, C. A.; Mealli, C.; Midollini, S.; Nefedov, V. I.; Orlandini, A.; Sacconi, L. Inorg. Chem. 1980, 19, 2454-2462.
56. Note that the solution susceptibilities for 2 and 3 are calculated by the Evans method assuming a monomeric formulation for each complex.
57. Sealy, R.; Hyde, J. S.; Antholine, W. E. Modern Physical Methods in Biochemistry: Neuberger, A., Van Deenen, L. L. M., Eds.; Elsevier: New York, 1985: p 69.
58. Superhyperfine coupling to phosphorous in a 5-coordinate cobalt(II) phosphine complex has been treated previously. See: Stelzer, O.; Sheldrick, W. S.; Subramanian, J. J. Chem. Soc., Dalton Trans. 1976, 966-970.
59. Gatteschi, D. J. Mol. Catal. 1985, 23, 145-150.
60. 2+ complexes did not produce a similarly isolable species. See: Heinze, K.; Huttner, G.; Zsolnai, L. Chem. Ber. 1997, 130, 1393-1403.
61. Banci, L.; Bencini, A.; Benelli, C.; Gatteschi, D.; Zanchini, C. Struct. Bonding 1982, 52, 37-86.
62. Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry, 5th Ed.; Wiley: New York, 1988; p 729. See ref 22 for a more thorough discussion and representative references.
63. Osmometric measurements to determine the solution molecular weights of 2 and 3 by the method of Signer were vitiated due to the tendency of these species to precipitate from toluene and benzene solution at moderate concentrations.
64. Sacconi, L.; Ciampolini, M.; Speroni, C. P. Inorg. Chem. 1965, 4, 1116-1119.
65. Nicolini, M.; Pecile, C.; Turco, A. J. Am. Chem. Soc. 1965, 87, 2379-2384.
66. 3v symmetry, see the following: Garrett, B. B.; Goedken, V. L.; Quagliano, J. V. J. Am. Chem. Soc. 1970, 92, 489-493.
67. Bertini, I.; Gatteschi, D.; Mani, F. Inorg. Chim. Acta 1973, 7, 717-720.
68. Gerloch, M.; Hanton, L. R. Inorg. Chem. 1980, 19, 1692-1698.
69. Gerloch, M.; Manning, M. R. Inorg. Chem. 1981, 20, 1051-1056.
70. Banci, L.; Benelli, C.; Gatteschi, D.; Mani, F. Inorg. Chem. 1982, 21, 1133-1136.
71. A series of related 5-coordinate [PhBP3]Co(I1) complexes has been prepared that will be reported in due course.
72. Jazdzewski, B. A.; Holland, P. L.; Pink, M.; Young, V. G.; Spencer, D. J. E.; Tolman, W. B. Inorg. Chem. 2001, 40, 6097-6107.
73. Kahn, O. Molecular Magnetism; VCH Publishers: New York, 1993; pp 1-10.
74. Swalen, J. D.; Gladney, H. M. IBM J. Res. Dev. 1964, 8, 515-526.
75. van Veen, G. J. Magn. Resonance 1978, 30, 91-109.
76. (a) Pilbrow, J. R. Transition Ion Electron Paramagnetic Resonance; Clarendon Press: Oxford, 1990.
77. (b) Aasa, R.; Vänngård, T. J. Magn. Resonance 1975, 19, 308-315.
78. Orgel, L. E. An Introduction to Transition-Metal Chemistry; Wiley: New York, 1960: p 174.