The Second Isolable B12-Thiolate Complex, (Pentafluorophenylthiolato)cobalamin: Synthesis and Characterization

Inorganic Chemistry

Volumn 37, Issue 20, 1998, Pages 5109-5116

  Hsu, Tsui Ling Carolyn ^a   Brasch, Nicola E ^a   Finke, Richard G ^a  

^a Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000002034     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic9704750     Document Type: Article

References (142)

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14. Protein-S-CoCbl products have been suggested following inuctivation of RTPR by 2′-deoxy-2′-methylenecytidine triphosphate and, apparently, a scrambling of CoCbl onto other HS-protein sites (Lawrence. C.; Stubbe, J., private communication). Hence a knowledge of bond energy and other properties of the RS-Co bonds should aid an understanding of these results as well.
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19. 11g In short, RS-Co complexes, such as those reported herein, and their ability to provide RS• and Co• at mild temperatures, are of both fundamental and practical interest.
20. 11e
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35. GluSCbl references: (a) EXAFS: Scheuring, E. M.; Sagi, I.; Chance, M. R. Biochemistry 1994, 33, 6310-6315. (b) NMR: Brown, K. L.; Zou, X.; Savon, S. R.; Jacobsen, D. W. Biochemistry 1993, 32, 8421-8428. (c) Law, P. V.; Wood, J. M. J. Am. Chem. Soc. 1973, 95, 914-919. (d) Adler, N.; Medwick, T.; Poznanski, T. J. J. Am. Chem. Soc. 1966, 88, 5018-5020. (e) Dolphin, D.; Johnson, A. W. J. Chem. Soc. 1965, 2174-2181. (f) Dubnoff, J. W. Biochem. Biophys. Res. Commun. 1964, 16, 484-488.
36. GluSCbl references: (a) EXAFS: Scheuring, E. M.; Sagi, I.; Chance, M. R. Biochemistry 1994, 33, 6310-6315. (b) NMR: Brown, K. L.; Zou, X.; Savon, S. R.; Jacobsen, D. W. Biochemistry 1993, 32, 8421-8428. (c) Law, P. V.; Wood, J. M. J. Am. Chem. Soc. 1973, 95, 914-919. (d) Adler, N.; Medwick, T.; Poznanski, T. J. J. Am. Chem. Soc. 1966, 88, 5018-5020. (e) Dolphin, D.; Johnson, A. W. J. Chem. Soc. 1965, 2174-2181. (f) Dubnoff, J. W. Biochem. Biophys. Res. Commun. 1964, 16, 484-488.
37. GluSCbl references: (a) EXAFS: Scheuring, E. M.; Sagi, I.; Chance, M. R. Biochemistry 1994, 33, 6310-6315. (b) NMR: Brown, K. L.; Zou, X.; Savon, S. R.; Jacobsen, D. W. Biochemistry 1993, 32, 8421-8428. (c) Law, P. V.; Wood, J. M. J. Am. Chem. Soc. 1973, 95, 914-919. (d) Adler, N.; Medwick, T.; Poznanski, T. J. J. Am. Chem. Soc. 1966, 88, 5018-5020. (e) Dolphin, D.; Johnson, A. W. J. Chem. Soc. 1965, 2174-2181. (f) Dubnoff, J. W. Biochem. Biophys. Res. Commun. 1964, 16, 484-488.
38. GluSCbl references: (a) EXAFS: Scheuring, E. M.; Sagi, I.; Chance, M. R. Biochemistry 1994, 33, 6310-6315. (b) NMR: Brown, K. L.; Zou, X.; Savon, S. R.; Jacobsen, D. W. Biochemistry 1993, 32, 8421-8428. (c) Law, P. V.; Wood, J. M. J. Am. Chem. Soc. 1973, 95, 914-919. (d) Adler, N.; Medwick, T.; Poznanski, T. J. J. Am. Chem. Soc. 1966, 88, 5018-5020. (e) Dolphin, D.; Johnson, A. W. J. Chem. Soc. 1965, 2174-2181. (f) Dubnoff, J. W. Biochem. Biophys. Res. Commun. 1964, 16, 484-488.
39. GluSCbl references: (a) EXAFS: Scheuring, E. M.; Sagi, I.; Chance, M. R. Biochemistry 1994, 33, 6310-6315. (b) NMR: Brown, K. L.; Zou, X.; Savon, S. R.; Jacobsen, D. W. Biochemistry 1993, 32, 8421-8428. (c) Law, P. V.; Wood, J. M. J. Am. Chem. Soc. 1973, 95, 914-919. (d) Adler, N.; Medwick, T.; Poznanski, T. J. J. Am. Chem. Soc. 1966, 88, 5018-5020. (e) Dolphin, D.; Johnson, A. W. J. Chem. Soc. 1965, 2174-2181. (f) Dubnoff, J. W. Biochem. Biophys. Res. Commun. 1964, 16, 484-488.
40. GluSCbl references: (a) EXAFS: Scheuring, E. M.; Sagi, I.; Chance, M. R. Biochemistry 1994, 33, 6310-6315. (b) NMR: Brown, K. L.; Zou, X.; Savon, S. R.; Jacobsen, D. W. Biochemistry 1993, 32, 8421-8428. (c) Law, P. V.; Wood, J. M. J. Am. Chem. Soc. 1973, 95, 914-919. (d) Adler, N.; Medwick, T.; Poznanski, T. J. J. Am. Chem. Soc. 1966, 88, 5018-5020. (e) Dolphin, D.; Johnson, A. W. J. Chem. Soc. 1965, 2174-2181. (f) Dubnoff, J. W. Biochem. Biophys. Res. Commun. 1964, 16, 484-488.
41. 12 and Intrinsic Factor: Zagalak, B., Fredrieh, W., Eds.; Walter de Gruyter: New York, 1979; pp 605-608.
42. A related complex, but with a thiol bound to the c side chain, is being investigated by Professor Ken Brown and his research group: Brown, K. L.; Zou, X. Abstracts of Papers, 211th National Meeting of the American Chemical Society. New Orleans. LA: American Chemical Society: Washington, DC. 1996; INOR 0489.
43. 12; Walter de Gruyter & Co: Berlin. 3987; pp 44-92.
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46. (d) Hill, H. A. O.; Pratt, J.M.; Williams, R. J. P. Chem. Br. 1969, 156-161. Hill, H. A. O.; Pratt, J. M.; Thorp, R. G.; Ward, B.; Williams, R. J. P. Biochem. J. 1970, 120, 263-269 (see p 264 and also Table 2 therein for an early summary of "atypical" RSCbl spectral data).
47. (d) Hill, H. A. O.; Pratt, J.M.; Williams, R. J. P. Chem. Br. 1969, 156-161. Hill, H. A. O.; Pratt, J. M.; Thorp, R. G.; Ward, B.; Williams, R. J. P. Biochem. J. 1970, 120, 263-269 (see p 264 and also Table 2 therein for an early summary of "atypical" RSCbl spectral data).
48. 1 with lattice constants a = 16.1403(4) Å, b = 21.3865(2) Å, c = 25.4074(7) Å, with 2 = 4. Although a clear Co-S bond is apparent, only 8 of the 19 remaining non-hydrogen atoms of the glutathionyl moiety could located due, apparently, to significant apparent disorder and a lack of clear electron density in the remaining regions of the glutathione moiety (Suto, R.; Finke, R. G. Unpublished results). We are investigating this complex further, in collaboration with Professor L. Randaccio and his research group, and using synchrotron radiation.
49. Zhao, R.; Lind, J.; Merényi, G.; Eriksen, T. J. Am. Chem. Soc. 1994, 116, 12010-12015.
50. Alkylthiolato(pyridinato)cobaloximes: (a) Polson, S. M.; Hansen, L.; Marzilli, L. G. Inorg. Chem. 1997, 36, 307-333. (b) Schrauzer, G. N. Acc. Chem. Res. 1968, 1, 97-105. (c) Schrauzer, G. N.; Windgassen, R. J. J. Am. Chem. Soc. 1967, 89, 3607-3612. Alkyl(thiolato)cobaloximes: (d) Brown, K. L.; Kallen, R. G. J. Am. Chem. Soc. 1972, 94, 1894-1901.
51. Alkylthiolato(pyridinato)cobaloximes: (a) Polson, S. M.; Hansen, L.; Marzilli, L. G. Inorg. Chem. 1997, 36, 307-333. (b) Schrauzer, G. N. Acc. Chem. Res. 1968, 1, 97-105. (c) Schrauzer, G. N.; Windgassen, R. J. J. Am. Chem. Soc. 1967, 89, 3607-3612. Alkyl(thiolato)cobaloximes: (d) Brown, K. L.; Kallen, R. G. J. Am. Chem. Soc. 1972, 94, 1894-1901.
52. Alkylthiolato(pyridinato)cobaloximes: (a) Polson, S. M.; Hansen, L.; Marzilli, L. G. Inorg. Chem. 1997, 36, 307-333. (b) Schrauzer, G. N. Acc. Chem. Res. 1968, 1, 97-105. (c) Schrauzer, G. N.; Windgassen, R. J. J. Am. Chem. Soc. 1967, 89, 3607-3612. Alkyl(thiolato)cobaloximes: (d) Brown, K. L.; Kallen, R. G. J. Am. Chem. Soc. 1972, 94, 1894-1901.
53. Alkylthiolato(pyridinato)cobaloximes: (a) Polson, S. M.; Hansen, L.; Marzilli, L. G. Inorg. Chem. 1997, 36, 307-333. (b) Schrauzer, G. N. Acc. Chem. Res. 1968, 1, 97-105. (c) Schrauzer, G. N.; Windgassen, R. J. J. Am. Chem. Soc. 1967, 89, 3607-3612. Alkyl(thiolato)cobaloximes: (d) Brown, K. L.; Kallen, R. G. J. Am. Chem. Soc. 1972, 94, 1894-1901.
54. 2. Hennig, H.; Ritter, K. J. Prakt, Chem. 1995, 337, 125-132.
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56. Costa-type RS - Co complexes: (a) Alexander, V. Inorg. Chim. Acta 1989, 163, 143-151. (b) Pellizer, G.; Tauszik, G. R.; Costa, G. J. Chem. Soc., Dalton Trans. 1973, 317-322.
57. II redox potential as compared to cobalamins. However, they should have somewhat stronger Co-SR bonds which, depending upon the application or goal, could be a distinct advantage.
58. 5S• (X = Cl) and its ability to abstract H• from unactivated alkanes are described in: Tanner, D. D.; Wada, N.; Brownlee, B. G. Can. J. Chem. 1973, 51, 1870-1879.
59. 5 - group in comparison to less electronegative aromatic and alkyl groups; see: Labinger, J. A.; Bercaw, J. E. Organometallics 1988, 7, 926-928 and references therein.
60. Jencks, W. P.; Salvesen, K. J. Am. Chem. Soc. 1971, 93, 4433-4436.
61. (a) See the Supporting Information. Table A.
62. a 8.5); see: Kallen, R. G. J. Am. Chem. Soc. 1971, 93, 6227-6235.
63. 27b,c while those of nonelectron-withdrawing RS- are uncommon.
64. (b) Thompson, J. S.; Sorrell, T.; Marks, T. J.; Ibers, J. A. J. Am. Chem. Soc. 1979, 101, 4193.
65. (c) Doppelt, P.; Fischer, J.; Weiss, R. J. Am. Chem. Soc. 1984, 106, 5188. Doppelt, P.; Fischer, J.; Ricard, L.; Weiss, R. New J. Chem. 1987, 11, 357.
66. (c) Doppelt, P.; Fischer, J.; Weiss, R. J. Am. Chem. Soc. 1984, 106, 5188. Doppelt, P.; Fischer, J.; Ricard, L.; Weiss, R. New J. Chem. 1987, 11, 357.
67. (d) Peach, M. E. Can. J. Chem. 1968, 46, 2699-2706.
68. 12 model system: Jaynes, B. S.; Doerrer, L. H.; Liu, S.; Lippard, S. J. Inorg. Chem. 1995, 34, 5735-5744; Jaynes, B. S.; Masschelein, A.; Ren, T.; Lippard, S. J. J. Am. Chem. Soc. 1993, 115, 5589-5599.
69. 12 model system: Jaynes, B. S.; Doerrer, L. H.; Liu, S.; Lippard, S. J. Inorg. Chem. 1995, 34, 5735-5744; Jaynes, B. S.; Masschelein, A.; Ren, T.; Lippard, S. J. J. Am. Chem. Soc. 1993, 115, 5589-5599.
70. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
71. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
72. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
73. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
74. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
75. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
76. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
77. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
78. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
79. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
80. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
81. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
82. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
83. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
84. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
85. 1H
86. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
87. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
88. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
89. 1H NMR aromatic region of cobalamins (although it is not explicitly stated how useful it is) include: (a) Brown. K. L.; Zou, X.; Evans, D. R. Inorg. Chem. 1994, 33, 5713-5720. (b) Rossi, M.; Glusker, J. P.; Randaccio, L.; Summers, M. F.; Toscane, P. J.; Marzilli, L. G. J. Am. Chem. Soc. 1985, 107, 1729-1738. (c) Waddington, M. D.; Finke, R. G. J. Am. Chem. Soc. 1993, 115, 4629-4640. (d) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1987, 109, 8012-8018. (e) Martin, B. D.; Finke, R. G. J. Am. Chem. Soc. 1992, 114, 585-592. (f) Brasch, N. E.; Hamza, M. S. A.; van Eldik, R. Inorg. Chem. 1997, 36, 3216-3222. (g) Brasch, N. E.; Müller, F.; Zahl, A.; van Eldik, R. Inorg. Chem. 1997, 36, 4891-4894.
90. Brasch, N. E.; Finke, R. G. Manuscript in preparation.
91. (31 ) Hay, B. P.; Finke, R. G. J. Am. Chem. Soc. 1986, 108, 4820-4829.
92. 32d
93. 32c
94. (c) McMaster, M. C. In HPLC: A practical user's guide; VCH Publishers: New York, 1994.
95. (d) Alelyunas, Y. W.; Fleming, P. E.; Finke, R. G.; Pagano, T. G.; Marzilli, L. G. J. Am. Chem. Soc. 1991, 113, 3781-3794 (see p 3792, second column, and footnote 53 therein).
96. A referee commented on an earlier draft of this paper, which was less detailed and failed to document fully the complexities of these syntheses, that "the synthesis and isolation (of RSCbls complexes) are very straightforward...". We hope the present paper makes clearer the subtleties and complexities - which also surprised us somewhat - in the synthesis and isolation of pure examples of this little-studied subclass of cobalamins.
97. Blaser, H.-U.; Halpern, J. J. Am. Chem. Soc. 1980, 102, 1684-1689.
98. 19F NMR, indicating that 24% of Co - SR homolysis has occurred. (A control showed that the disulfide is not present in the starting complex.) We believe that this indicates that an insoluble (and thus invisible to NMR) cobaiamin complex has been formed, the nature of which is under investigation.
99. 12g
100. Hogenkamp, H. P. C.; Bratt, G. T.; Kotchevar, A. T. Biochemistry 1987, 26, 4723-4727.
101. 1H NMR method developed herein, and its use to detect impurities in commercial cobalamin starting materials: Brasch, N. E.; Hsu, T.-L. C.; Doll, K. M.; Finke, R. G. J. Inorg. Biochem., in press.
102. 12b
103. 38h).
104. 381).
105. 38n
106. (e) Kallen, R. G. J. Am. Chem. Soc. 1971, 93, 6227-6235.
107. (f) Reenstra, W. W.; Jeneks, W. P. J. Am. Chem. Soc. 1979, 101, 5780-5791.
108. (g) Baldwin, D. A.; Betterton, E. A.; Pratt, J. M. J. Chem. Soc., Dalton Trans. 1983, 217-223.
109. (h) Manques, H. M.; Bradley, J. C.; Brown, K. L.; Brooks, H. Inorg. Chim. Acta 1993, 209, 161-169.
110. (i) Hamza, M. S. A.; Pratt, J. M.; J. Chem. Soc., Dalton Trans. 1994, 1367-1369.
111. (j) Marques, H. M.; Marsh, J. H.; Mellor, J. R.; Munro, O. Q. Inorg. Chem. Acta 1990, 170, 259-269.
112. (k) Eilbeck, W. J.; West, M. S. J. Chem. Soc., Dalton Trans. 1976, 274-278.
113. (l) Hanania, G. I. H.; Irvine, D. H. J. Chem. Soc. 1964, 5694-5697.
114. (m) Marques, H. M.; Egan, T. J.; Marsh, J. H.; Mellor, J. R.; Munro, O. Q. Inorg. Chim. Acta 1989, 166, 249-255.
115. (n) Marques, H. M. Inorg. Chim. Acta 1990, 174, 271-273.
116. 39b characteristic of base-off cobalamins.
117. 12; Dolphin, D., Ed.; Wiley-Imerseience: New York, 1982; Vol. 1, p 357.
118. 5SH (Figures E and F, Supporting Information).
119. The Universal Force Field (UFF): (a) Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024-10035. (b) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc, 1992, 114, 10035-10046. (c) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10046-10053. (d) Rappé, A. K.; Colwell, K. S.; Casewit, C. J. Inorg. Chem. 1993, 32, 3438-3450.
120. The Universal Force Field (UFF): (a) Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024-10035. (b) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc, 1992, 114, 10035-10046. (c) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10046-10053. (d) Rappé, A. K.; Colwell, K. S.; Casewit, C. J. Inorg. Chem. 1993, 32, 3438-3450.
121. The Universal Force Field (UFF): (a) Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024-10035. (b) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc, 1992, 114, 10035-10046. (c) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10046-10053. (d) Rappé, A. K.; Colwell, K. S.; Casewit, C. J. Inorg. Chem. 1993, 32, 3438-3450.
122. The Universal Force Field (UFF): (a) Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024-10035. (b) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc, 1992, 114, 10035-10046. (c) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10046-10053. (d) Rappé, A. K.; Colwell, K. S.; Casewit, C. J. Inorg. Chem. 1993, 32, 3438-3450.
123. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
124. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
125. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
126. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
127. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
128. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
129. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
130. 1H NMR of monocarboxylic acids of HOCbl have not been reported in the literature. Sigma informed us that they too are also concerned with the purity of their HOCbl·HOAc, and have recently investigated it for possible cyanocobalamin (1-3%) and dicyanocobinamide (undetectable amount) contaminants, (a) Katada, M.; Tyagi, S.; Rajoria, D. S.; Nath, A, In Porphyrin Chemistry Advances; Longo, F. R., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 157-164. (b) Kohli, R. K.; Nath, A. Inorg. Chim. Acta 1987, 136, 75-79. (c) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Biochim. Biophys. Acta 1981, 668, 406-412. (d) Katada, M.; Tyagi, S.; Nath, A.; Petersen, R. L.; Gupta, R. K. Biochim. Biophys. Acta 1979, 584, 149-163. (e) Mishra, P. K.; Gupta, R. K.; Goswami, P. C.; Venkatasubramanian, P. N.; Nath, A. Polyhedron 1982, 1, 321-325. (f) Kohli, R. K.; Nath, A. Biochim. Biophys. Res. Commun. 1984, 125, 698-703. (g) Marzilli, L. G.; Parker, W, O., Jr.; Kohli, R. K.; Carell, H. L.; Glusker, J, P. Inorg. Chem. 1986, 25, 127-129. (h) Pagano, T. G.; Marzilli, L. G. Biochem. 1989, 28, 7213-7223.
131. Hsu, T.-L. C.; Finke, R. G.; Doll, K. Experiments currently in progress.
132. Hay, B. P.; Finke, R. G, Polyhedron 1988, 7, 1469-1481.
133. Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air-Sensitive Compounds: John Wiley and Sons: New York, 1986.
134. Robson, P.; Stacey, M.; Stephens, R.; Tatlow, J. C. J. Chem. Soc. 1960, 4754-4760.
135. 47c
136. (b) From the parameter defined as a "good" fit for modeling vs X-ray crystal structures, one can state thai the maximum error expected when comparing different model stuctures is 0.02 Å.
137. (c) Rappé. A. K.; Colwell, K. S.; Casewit, C. J. Inorg. Chem. 1993, 32, 3438-3450.
138. Marques, H. M.; Brown, K. L. J. Mol. Struct. (THEOCHEM) 1995, 340, 97-124.
139. (a) Lenhert, P. G. Proc. R. Soc. London, Ser. A 1968, 303, 45-84.
140. (b) Rappé, A. K.; Casewit, C. J. Molecular Mechanics across Chemistry; University Science Books: Sausalito, CA, 1997.
141. Dubnoff, J. W. Biochem. Biophys. Res. Commun. 1964, 16, 484-488.
142. See for example the RS-Co distance listed in Marzilli's Table 3 in ret 19a or on p 5191 in the following: Doppelt, P.; Fischer, J.; Weiss, R. J. Am. Chem. Soc. 1984, 106, 5188-5193.