Photochemical heterolysis of the metal-metal bond in (Me3P)(OC)4OsW(CO)5

Organometallics

Volumn 16, Issue 15, 1997, Pages 3431-3438

  Male, Jonathan L ^a   Pomeroy, Roland K ^a   Tyler, David R ^b  

^a SIMON FRASER UNIVERSITY   (Canada)

^b UNIVERSITY OF OREGON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001116665     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om970275w     Document Type: Article

References (101)

1. Einstein, F. W. B.; Pomeroy, R. K.; Rushman, P.; Willis, A. C. J. Chem. Soc., Chem. Commun. 1983, 854.
2. Fleming, M. M.; Pomeroy, R. K.; Rushman, P. J. Organomet. Chem. 1984, 273, C33.
3. Einstein, F. W. B.; Pomeroy, R. K.; Rushman, P.; Willis, A. C. Organometallics 1985, 3, 250.
4. Del Paggio, A. A.; Muetterties, E. L.; Heinekey, D. M.; Day, V. W.; Day, C. S. Organometallics 1986, 5, 575.
5. Einstein, F. W. B.; Jennings, M. C.; Krentz, R.; Pomeroy, R. K.; Rushman, P.; Willis, A. C. Inorg. Chem. 1987, 26, 1341.
6. Usón, R.; Forniés, J.; Espinet, P.; Fortuño, C.; Tomas, M.; Welch, A. J. J. Chem. Soc., Dalton Trans. 1988, 3005.
7. (a) Einstein, F. W. B.; Jones, T.; Pomeroy, R. K.; Rushman, P. J. Am. Chem. Soc. 1984, 106, 2707.
8. (b) Davis, H. B.; Einstein, F. W. B.; Glavina, P. G.; Jones, T.; Pomeroy, R. K.; Rushman, P. Organometallics 1989, 8, 1030.
9. (c) Davis, H. B.; Einstein, F. W. B.; Johnston, V. J.; Pomeroy, R. K. J. Organomet. Chem. 1987, 319, C25.
10. Shipley, J. A.; Batchelor, R. J.; Einstein, F. W. B.; Pomeroy, R. K. Organometallics 1991, 10, 3620.
11. Irradiation of metal-metal-bonded organometallic dimers generally leads to either metal-metal bond homolysis or metal-ligand bond dissociation. See: (a) Geoffroy, G. L.; Wrighton, M. S. Organometallic Photochemistry; Academic Press: New York, 1979. (b) Meyer, T. J.; Casper, J. V. Chem. Rev. 1985, 85, 187.
12. Irradiation of metal-metal-bonded organometallic dimers generally leads to either metal-metal bond homolysis or metal-ligand bond dissociation. See: (a) Geoffroy, G. L.; Wrighton, M. S. Organometallic Photochemistry; Academic Press: New York, 1979. (b) Meyer, T. J.; Casper, J. V. Chem. Rev. 1985, 85, 187.
13. 16-17
14. Armentrout, P. B.; Sieions, J. J. Am. Chem. Soc. 1992, 114, 8627.
15. Allen, D. M.; Cox, A.; Kemp, T. J.; Sultana, Q. J.; Pitts, R. B. J. Chem. Soc., Dalton Trans. 1976, 1189.
16. Fletcher, S. C.; Poliakoff, M.; Turner, J. J. J. Organomet. Chem. 1984, 268, 259.
17. Haynes, A.; Poliakoff, M.; Turner, J. J.; Bender, B. R.; Norton, J. R. J. Organomet. Chem. 1990, 383, 497.
18. For example, the disproportionation reactions of many dinuclear complexes follow a pathway involving homolysis, followed by coordination of a ligand to form a 19-electron adduct, and then electron transfer. See: Stiegman, A. E.; Stieglitz, M.; Tyler, D. R. J. Am. Chem. Soc. 1983, 105, 6032-6037.
19. For a review of disproportionation, see: Stiegman, A. E.; Tyler, D. R. Coord. Chem. Rev. 1985, 63, 217-240.
20. Stufkens and Oskam reported several instances where heterolytic products are the result of photochemical homolysis followed by electron transfer between geminate cage radicals. See: (a) van Dijk, H. K.; van der Haar, J.; Stufkens, D. J.; Oskam, A. Inorg. Chem. 1989, 28, 75-81. (b) Knoll, H.; de Lange, W. J. G.; Hennig, H.; Stufkens, D. J.; Oskam, A. J. Organomet. Chem. 1992, 430, 123-132.
21. Stufkens and Oskam reported several instances where heterolytic products are the result of photochemical homolysis followed by electron transfer between geminate cage radicals. See: (a) van Dijk, H. K.; van der Haar, J.; Stufkens, D. J.; Oskam, A. Inorg. Chem. 1989, 28, 75-81. (b) Knoll, H.; de Lange, W. J. G.; Hennig, H.; Stufkens, D. J.; Oskam, A. J. Organomet. Chem. 1992, 430, 123-132.
22. For a review, see: Zinato, E. In Concepts of Inorganic Photochemistry; Adamson, A. W., Fleischauer, P. D., Eds.; Wiley-Interscience: New York, 1975.
23. 2-4,6,7
24. Dey, K.; Werner, H. Chem. Ber. 1979, 112, 823.
25. Roberts, D. A.; Mercer, W. C.; Geoffroy, G. L.; Pierpont, C. G. Inorg. Chem. 1986, 25, 1439 and ref 3 therein.
26. Deubzer, B.; Kaesz, H. D. J. Am. Chem. Soc. 1968, 90, 3276.
27. Male, J. L.; Davis, H. B.; Pomeroy, R. K.; Tyler, D. R. J. Am. Chem. Soc. 1994, 116, 9353.
28. Abrahamson, H. B.; Wrighton, M. S. Inorg. Chem. 1978, 17, 1003.
29. Davis, H. B. Ph. D. Thesis, Simon Fraser University, Jan 1991.
30. (a) Arndt, L. W.; Darensbourg, M. Y.; Delord, T.; Bancroft, B. T. J. Am. Chem. Soc. 1986, 108, 2617 and references therein.
31. (b) Arndt, L. W.; Bancroft, B. T.; Darensbourg, M. Y.; Janzen, C. P.; Kim, C. M.; Reibenspies, J.; Varner, K. E.; Youngdahl, K. A. Organometallics 1988, 7, 1302.
32. (c) Arndt, L. W. Ph. D. Thesis, Texas A&M University, May 1986.
33. No electronic spectroscopic studies have been published on complexes with metal-metal dative bonds. However, theoretical studies suggest that the lowest energy transitions in these complexes are σ → σ* or possibly dπ → σ* transitions. See: Nakatsuji, H.; Hada, M.; Kawashima, A. Inorg. Chem. 1992, 31, 1740. Rosa, A.; Ricciardi, G.; Baerends, E. J.; Stufkens, D. J. Inorg. Chem. 1996, 35, 2886-2897.
34. No electronic spectroscopic studies have been published on complexes with metal-metal dative bonds. However, theoretical studies suggest that the lowest energy transitions in these complexes are σ → σ* or possibly dπ → σ* transitions. See: Nakatsuji, H.; Hada, M.; Kawashima, A. Inorg. Chem. 1992, 31, 1740. Rosa, A.; Ricciardi, G.; Baerends, E. J.; Stufkens, D. J. Inorg. Chem. 1996, 35, 2886-2897.
35. (a) Dennenberg, R. J.; Darensbourg, D. J. Inorg. Chem. 1972, 11, 72 and references therein.
36. (b) Hyde, C. L.; Darensbourg, D. J. Inorg. Chem. 1973, 12, 1286.
37. -1.
38. -1.
39. 2 + CO
40. See ref 9a, p 68, and ref 28.
41. Tyler, D. R.; Petrylak, D. P. J. Organomet. Chem. 1981, 212, 389.
42. (a) Reference 9a, p 69.
43. (b) Leventis, N.; Wagner, P. J. J. Am. Chem. Soc. 1985, 107, 5807.
44. (c) Albano, V. G.; Busetto, L.; Castellari, C.; Monari, M.; Palazzi, A.; Zanotti, V. J. Chem. Soc., Dalton Trans. 1993, 3661.
45. (a) Wrighton, M. S.; Ginley, D. S. J. Am. Chem. Soc. 1975, 97, 4246.
46. (b) Laine, R. M.; Ford, P. C. Inorg. Chem. 1977, 16, 388.
47. (c) Scott, S. L.; Espenson, J. H.; Zhu, Z. J. Am. Chem. Soc. 1993, 115, 1789.
48. Male, J. L.; Einstein, F. W. B.; Leong, W. K.; Pomeroy, R. K.; Tyler, D. R., submitted to J. Organomet. Chem.
49. -1).
50. Bellachioma, G.; Cardaci, G.; Macchioni, A.; Zanazzi, P. Inorg. Chem. 1993, 32, 547-553.
51. 6 still remained after this time.
52. (a) Abel, E. W.; Butler, I. S.; Reid, J. G. J. Chem. Soc. 1963, 2068.
53. (b) King, R. B. Adv. Organomet. Chem. 1964, 2, 157.
54. Borowczak, D.; Szymanska-Buzar, T.; Ziólkowski, J. J. J. Mol. Catal. 1984, 27, 355.
55. (a) Krausz, P.; Garnier, F.; Dubois, J. E. J. Am. Chem. Soc. 1975, 97, 437.
56. (b) Krausz, P.; Garnier, F.; Dubois, J. -E. J. Organomet. Chem. 1976, 108, 197.
57. 3), which was complete after 58 h. During this period all of fac-3 had converted to fac-2.
58. 2Cl reaction is less efficient because two molecules are required to form the product.
59. (a) Roper, W. R. J. Organomet. Chem. 1986, 300, 167.
60. (b) Clark, G. R.; Marsden, K.; Roper, W. R.; Wright, L. J. J. Am. Chem. Soc. 1980, 102, 1206.
61. (c) Gallop, M. A.; Roper, W. R. Adv. Organomet. Chem. 1986, 25, 121.
62. 4 has been proposed to produce a variety of chlorinating agents, including phosgene. See, for example, refs 41 and 42.
63. 2Cl.
64. 49,50
65. (a) Silavwe, N. D.; Pan, X.; Tyler, D. R. Inorg. Chim. Acta 1988, 144, 123.
66. (b) Silavwe, N. D.; Goldman, A. S.; Ritter, R.; Tyler, D. R. Inorg. Chem. 1989, 28, 1231.
67. Phillips, J. R.; Trogler, W. C. Inorg. Chim. Acta 1992, 198, 633.
68. 54
69. McLean, R. A. N. J. Chem. Soc., Dalton Trans. 1974, 1568.
70. (a) Dahlgren, R. M.; Zink, J. I. J. Chem. Soc., Chem. Commun. 1978, 863.
71. (b) Dahlgren, R. M.; Zink, J. I. Inorg. Chem. 1977, 16, 3154-3161.
72. (a) Dobson, G. R.; Amr El Sayed, M. F.; Stolz, I. W.; Sheline, R. K. Inorg. Chem. 1962, 1, 526.
73. (b) Strohmeier, W. Angew. Chem., Int. Ed. Engl. 1964, 3, 730.
74. 49
75. + 57 are known and are stable in solution.
76. Rushman, P.; Van Buuren, G. N.; Shiralian, M.; Pomeroy, R. K. Organometallics 1983, 2, 693-694.
77. 4.
78. Wawzonek, S.; Duty, R. C. J. Electrochem. Soc. 1961, 108, 1135.
79. Briegleb, G. Angew. Chem., Int. Ed. Engl. 1964, 3, 617.
80. Fogg, P. G. T.; Gerrard, W. Solubility of Gases in Liquids - A Critical Evaluation of Gas/Liquid Systems in Theory and Practice; John Wiley & Sons: Chichester, 1991; pp 2, 277.
81. 6 at room temperature). Less than 15% of the bimetallic complex 1 was allowed to react in these measurements. Note that the quantum yields reported in this paper differ from those reported in ref 23 by a factor of 2.23. We used an incorrect quantum yield for the Aberchrome 540 actinometer in our prior calculations.
82. -2 M).
83. Covert, K. J.; Askew, E. F.; Grunkemeier, J.; Koenig, T.; Tyler, D. R. J. Am. Chem. Soc. 1992, 114, 10446.
84. Atkins, P. W. Physical Chemistry, 5th ed.; Oxford University Press: Oxford, 1994; p 833, C27.
85. Lide, D. R. Handbook of Chemistry and Physics, 71st ed.; CRC Press: Boston, 1990; pp 6-142.
86. 6 solvent system because of the similar natures of the solvent and the viscosity enhancer.
87. (a) Hillhouse, G. L.; Haymore, B. L. Inorg. Chem. 1987, 26, 1876.
88. (b) Darensbourg, D. J.; Bischoff, C. J. Inorg. Chem. 1993, 32, 47.
89. P-H = 10.3 Hz). The major:minor isomer ratio was 2.6:1.0. At 6°C, the major:minor isomer ratio was 2.7:1.0. There seems, therefore, to be little variation in the ratio of the isomers in the temperature range 6-26°C, the temperature range expected during the photolysis of 1. For this reason, the determination of the potentially different molar absorption coefficients of the two isomers of 1 in this solvent was not possible. Carrying out the studies at a higher temperature would increase the probability of thermal reactions occurring in conjunction with photochemical reactions.
90. Leonhard, K, Werner, H. Angew. Chem., Int. Ed. Engl. 1977, 16, 649.
91. Zhang, S.; Brown, T. L. J. Am. Chem. Soc. 1993, 115, 1779.
92. (a) Griffiths, P. G.; Moad, G.; Rizzardo, E.; Solomon, D. H. Aust. J. Chem. 1983, 36, 397.
93. (b) See also ref 47.
94. (a) Matthews, C. N.; Magee, T. A.; Wotiz, J. H. J. Am. Chem. Soc. 1959, 81, 2273.
95. (b) Magee, T. A.; Matthews, C. N.; Wang, T. S.; Wotiz, J. H. J. Am. Chem. Soc. 1961, 83, 3200.
96. Martin, L. R.; Einstein, F. W. B.; Pomeroy, R. K. Inorg. Chem. 1985, 24, 2777.
97. Ungurenasu, C.; Palie, M. J. Chem. Soc., Chem. Commun. 1975, 388.
98. Schwindt, M. A.; Lejon, T.; Hegedus, L. S. Organometallics 1990, 9, 2814.
99. Van Geet, A. L. Anal. Chem. 1970, 42, 679.
100. Lindfors, B. E.; Nieckarz, G. F.; Tyler, D. R.; Glenn, A. G. J. Photochem. Photobiol. 1996, 94, 101.
101. Heller, H. G.; Langan, J. R. J. Chem. Soc., Perkin Trans. 2 1981, 341.