Mechanistic studies of the thermolysis of tetraneopentyltitanium(IV). 1. Solution evidence that titanium alkylidenes activate saturated hydrocarbons

Journal of the American Chemical Society

Volumn 119, Issue 29, 1997, Pages 6804-6813

  Cheon, Jinwoo ^a   Rogers, Deborah M ^a   Girolami, Gregory S ^a  

^a University of Illinois at Urbana Champaign   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE; CYCLOHEXANE; DEUTERIUM; HEXAFLUOROBENZENE; HYDROCARBON; ORGANOMETALLIC COMPOUND; PENTANE; TITANIUM DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL BOND; CHEMICAL REACTION KINETICS; DECOMPOSITION; HYDROLYSIS; PROTON NUCLEAR MAGNETIC RESONANCE; STOICHIOMETRY; TEMPERATURE;

EID: 0030812081     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970811b     Document Type: Article

References (96)

1. Girolami, G. S.; Jensen, J. A.; Pollina, D. M.; Williams, W. S.; Kaloyeros, A. E.; Allocca, C. M. J. Am. Chem. Soc. 1987, 109, 1579-1580.
2. Kaloyeros, A. E.; Allocca, C. M.; Williams, W. S.; Pollina, D. M.; Girolami, G. S. Adv. Ceram. Mater. 1987, 23, 257-263.
3. For analogous studies of the deposition of tungsten carbide from tungsten alkyl/alkylidyne precursors, see: Caulton, K. G.; Chisholm, M. H.; Xue, Z. Chem. Mater. 1991, 3, 384-386.
4. Davidson, P. J.; Lappert, M. F.; Pearce, R. Chem. Rev. 1976, 76, 219-242.
5. Schrock, R. R.; Parshall, G. W. Chem. Rev. 1976, 76, 243-268.
6. Braterman, P. S.; Cross, R. J. Chem. Soc., Dalton Trans. 1972, 657-661.
7. D'yachkovskii, F. S.; Krunshch, N. E. J. Gen. Chem. USSR (Engl. Transl.) 1971, 41, 1787-1791.
8. Razuvaev, G. A.; Latyaeva, V. N.; Malysheva, A. V. J. Gen. Chem. USSR (Engl. Transl.) 1967, 37, 2224-2229.
9. Latyaeva, V. N.; Batalov, A. P.; Malysheva, A. V.; Kulemin, V. I. J. Gen. Chem. USSR (Engl. Transl.) 1968, 38, 282-284.
10. Schrock, R. R. J. Organomet. Chem. 1976, 122, 209-225.
11. Erskine, G. J.; Wilson, R. A.; McCowan, J. D. J. Organomet. Chem. 1976, 114, 119-125.
12. Erskine, G. J.; Hartgerink, J.; Weinbergh, E. L.; McCowan, J. D. J. Organomet. Chem. 1979, 170, 51-61.
13. Alt, H. G.; DiSanzo, F. P.; Rausch, M. D.; Uden, P. C. J. Organomet. Chem. 1976, 107, 257-263.
14. Chang, B. H.; Tung, H.-S.; Brubaker, C. H. Inorg. Chim. Acta 1981, 51, 143-148.
15. Boekel, C. P.; Teuben, J. H.; de Liefde Meijer, H. J. J. Organomet. Chem. 1975, 102, 317-320.
16. Waters, J. A.; Vickroy, V. V.; Mortimer, G. A. J. Organomet. Chem. 1971, 33, 41-52.
17. McDade, C.; Green, J. C.; Bercaw, J. E. Organometallics 1981, 1, 1629-1634.
18. Bulls, A. R.; Schaefer, W. P.; Serfas, M.; Bercaw, J. E. Organometallics 1987, 6, 1219-1226.
19. Malatesta, V.; Ingold, K. U.; Schrock, R. R. J. Organomet. Chem. 1978, 152, C53-C56.
20. Schrock, R. R.; Fellmann, J. D. J. Am. Chem. Soc. 1978, 100, 3359-3370.
21. Li, L.; Hung, M.; Xue, Z. J. Am. Chem. Soc. 1995, 117, 12746-12750.
22. Wood, C. D.; McLain, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1979, 101, 3210-3222.
23. Schwartz, J.; Gell, K. I. J. Organomet. Chem. 1980, 184, C1 and C2.
24. Hartner, F. W.; Schwartz, J.; Clift, S. M. J. Am. Chem. Soc. 1983, 105, 640-641.
25. Fryzuk, M. D.; Moo, S. S. H.; Zaworotko, M. J.; MacGillivray, L. R. J. Am. Chem. Soc. 1993, 115, 5336-5337.
26. Schrock, R. R. Acc. Chem. Res. 1979, 12, 98-104.
27. Ivin, K. J.; Rooney, J. J.; Stewart, C. D.; Green, M. L. H.; Mahtab, R. J. Chem. Soc., Chem. Commun. 1978, 604-606
28. Barger, P. T.; Santarsiero, B. D.; Armantrout, J.; Bercaw, J. E. J. Am. Chem. Soc. 1984, 106, 5178-5186.
29. Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J. Am. Chem. Soc. 1978, 100, 3611-3613.
30. Rice, G. W.; Ansell, G. B.; Modrick, M. A.; Zentz, S. Organometallics 1983, 2, 154-157.
31. For unsuccessful attempts to prepare group 4 alkylidene complexes, see: Wengrovius, J. H.; Schrock, R. R. J. Organomet. Chem. 1981, 205, 319-327.
32. Lockwood, M. A.; Clark, J. R.; Bernardeta, C. P.; Rothwell, I. P. Chem. Commun. 1996, 1973-1974.
33. van Doorn, J. A.; van der Heijden, H.; Orpen, A. J. Organometallics 1994, 13, 4271-4277.
34. van der Heijden, H.; Hessen, B. J. Chem. Soc., Chem. Commun. 1995, 145-146.
35. Schaller, C. P.; Cummins, C. C.; Wolczanski, P. T. J. Am. Chem. Soc. 1996, 118, 591-611.
36. Walsh, P. J.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1988, 110, 8729-8731.
37. Bennett, J. L.; Wolczanski, P. T. J. Am. Chem. Soc. 1994, 116, 2179-2180.
38. de With, J.; Horton, A. D. Angew. Chem., Int. Ed. Engl. 1993, 32, 903-905.
39. Schaller, C. P.; Cummins, C. C.; Wolczanski, P. T. Inorg. Chem. 1993, 32, 131-144.
40. Davidson, P. J.; Lappert, M. F.; Pearce, R. J. Organomet. Chem. 1973, 57, 269-277.
41. Collier, M. J.; Lappen, M. F.; Pearce, R. J. Chem. Soc., Dalton Trans. 1973, 445-451.
42. Cheon, J.; Dubois, L. H.; Girolami, G. S. J. Am. Chem. Soc. 1997, 119, 6814.
43. Whitmore, B. C.; Porkin, A. H.; Bernstein, H. I.; Wilkins, J. P. J. Am. Chem. Soc. 1941, 63, 124-127.
44. Anderson, K. H.; Benson, S. W. J. Chem. Phys. 1964, 40, 3747-3748.
45. Caulton, K. G.; Chisholm, M. H.; Streib, W. E.; Xue, Z. J. Am. Chem. Soc. 1991, 113, 6082-6090.
46. Westheimer, F. H. Chem. Rev. 1961, 61, 265-273.
47. Bigeleisen, J. Pure Appl. Chem. 1964, 8, 217-223.
48. Melander, R. C.; Saunders, R. H., Jr. Reaction Rates of Isotopic Molecules; Wiley: New York, 1980; pp 140-152.
49. Moore, J. W.; Pearson, R. G. Kinetics and Mechanism; Wiley: New York, 1981; pp 367-370.
50. Kwart, H. Acc. Chem. Res. 1982, 15, 401-408.
51. Strong, H. L.; Brownawell, M. L.; San Fillipo, J., Jr. J. Am. Chem. Soc. 1983, 105, 6526-6528.
52. 53,54
53. Lappert, M. F.; Patil, D. S.; Pedley, J. B. J. Chem. Soc., Chem. Commun. 1975, 830-831.
54. Connor, J. A. Top. Curr. Chem. 1977, 71, 71-110.
55. 15
56. Bruno, J. W.; Smith, G. M.; Marks, T. J.; Fair, C. K.; Schultz, A. J.; Williams, J. M. J. Am. Chem. Soc. 1986, 108, 40-56.
57. Smith, G. M.; Carpenter, J. D.; Marks, T. J. J. Am. Chem. Soc. 1986, 108, 6805-6807.
58. Bruno, J. W.; Marks, T. J.; Day, V. W. J. Organomet. Chem. 1983, 250, 237-246.
59. Schock, L. E.; Brock, C. P.; Marks, T. J. Organometallics 1987, 6, 232-241.
60. Chamberlain, L. R.; Rothwell, J. P.; Huffman, J. C. J. Am. Chem. Soc. 1986, 108, 1502-1509.
61. Tebbe, F. N.; Harlow, R. L. J. Am. Chem. Soc. 1980, 102, 6149-6151.
62. Shortland, A. J.; Wilkinson, G. J. Chem. Soc., Dalton Trans. 1973, 872-876.
63. These values have been corrected for the deuterium content of the neopentane.
64. 3 liberated and subtracting the amounts of neopentane isotopologs calculated to result from the α-hydrogen abstraction process. As we will see, different mechanisms predict different distributions of deuterium in the neopentane evolved in the second step of the thermolysis sequence.
65. The determination of the isotopic composition of mixtures of deuterated neopentanes can be accomplished by mass spectroscopy provided that some care is taken (see the Experimental Section). We made only one assumption: that in the mixtures of deuterated neopentanes, the deuterium labels present in any one molecule were all attached to the same carbon atom. As long as scrambling of deuterium labels into the γ-hydrogen positions (i.e., the methyl groups) of the neopentyl ligands is slow, this will be a reasonable assumption. The satisfactory analyses of the neopentane isotopolog distributions from the observed spectrometric cracking patterns suggest that the assumption does in fact hold true.
66. 3.
67. Note Added in Proof: A similar reaction of a tungsten alkylidene has recently been reported: Tran, E.; Legzdins, P. J. Am. Chem. Soc. 1997, 119, 5071-5072.
68. 2.
69. 2 is eliminated.
70. McLain, S. J.; Schrock, R. R.; Sharp, P. R.; Churchill, M. R.; Young, W. J. J. Am. Chem. Soc. 1979, 101, 263-265.
71. Latyaeva, V. N.; Vyshinskaya, L. I.; Shur, V. B.; Fedorov, L. A.; Vol'pin, M. E. Dokl. Akad. Nauk SSSR 1968, 179, 875-878.
72. Dvorak, J.; O'Brien, R. J.; Santo, W. J. Chem. Soc., Chem. Commun. 1970, 411-412.
73. Kolomnikov, I. S.; Lobeeva, T. S.; Gorbachevskaya, V. V.; Aleksandrov, G. G.; Struchkov, Y. T.; Vol'pin, M. E. J. Chem. Soc., Chem. Commun. 1971, 972-973.
74. Shur, V. B.; Berkovitch, E. G.; Vasiljeva, L. B.; Kudryatsev, R. V.; Vol'pin, M. E. J. Organomet. Chem. 1974, 78, 127-132.
75. Boekel, C. P.; Teuben, J. H.; de Liefde Meijer, H. J. J. Organomet. Chem. 1974, 81, 371-377.
76. Boekel, C. P.; Teuben, J. H.; de Liefde Meijer, H. J. J. Organomet. Chem. 1975, 102, 161-165.
77. Erker, G. J. Organomet. Chem. 1977, 134, 189-202.
78. Buchwald, S. L.; Nielsen, R. B. Chem. Rev. 1988, 88, 1047-1058.
79. Mattia, M. B.; Humphrey, M. B.; Rogers, R. D.; Atwood, J. L.; Rausch, M. D. Inorg. Chem. 1978, 17, 3257-3264.
80. Rausch, M. D.; Mintz, E. A. J. Organomet. Chem. 1980, 190, C65-C72.
81. 4 because fewer deuterated sites are involved, and because the four sites that are 100% hydrogen labeled dominate the thermolysis process. For a discussion of the effect of residual hydrogen on the isotopologs generated upon thermolysis of "perdeuterated" compounds, see ref 17.
82. Fendrick, C. M.; Marks, T. J. J. Am. Chem. Soc. 1984, 106, 2214-2216.
83. Fendrick, C. M.; Marks, T. J. J. Am. Chem. Soc. 1986, 108, 425-437.
84. Bruno, J. W.; Marks, T. J.; Morss, L. R. J. Am. Chem. Soc. 1983, 105, 6824-6832.
85. 4 in fluorocarbons.
86. Wu, Y.-D.; Peng, Z.-H.; Xue, Z. J. Am. Chem. Soc. 1996, 118, 9772-9777.
87. Kruse, W. M. U.S. Patent 3 712 874, Jan 23, 1973.
88. Mowat, W.; Wilkinson, G. J. Chem. Soc., Dalton Trans. 1973, 1120-1124.
89. Hepburn, D. R.; Hudson, H. R. Chem. Ind. (London) 1974, 664-665.
90. Steigel, A.; Sauer, J.; Kleier, D. A.; Binsch, G. J. Am. Chem. Soc. 1972, 94, 2770-2779.
91. Mathot, V.; Desmyter, A. J. Chem. Phys. 1953, 21, 782-788.
92. Bowden, W. W.; Staton, J. C.; Smith, B. D. J. Chem. Eng. Data 1966, 11, 296-303.
93. Lide, D. R.; Kehiaian, H. V. CRC Handbook of Thermophysical and Thermochemical Data, CRC Press: Boca Raton, FL, 1994; Table 2.1.3.
94. Kolman, B. Introductory Linear Algebra with Applications; Macmillan: New York, 1976; pp 36-39.
95. MacCamy, R. C.; Mizel, V. J. Linear Analysis and Differential Equations; Macmillan: New York, 1969; pp 159-168.
96. 0, see: Stenhagen, E.; Abrahamsson, S.; McLafferty, F. W., Eds. Atlas of Mass Spectral Data; Wiley Interscience: New York, 1961; Vol. 1.