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1
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For a review of low-valent transition metal alkoxide chemistry up to the late 1980s see: Bryndza, H. E.; Tam, W. Chem. Rev. 1988, 88, 1163.
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(b) Noyori, R.; Yamakawa, M.; Hashiguchi, S. J. Org. Chem. 2001, 66, 7931.
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(b) Stahl, S. S. Science 2005, 309, 1824.
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Stahl, S.S.1
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34547411958
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A variety of different mechanisms for the β-hydrogen elimination reactions of low-valent metal alkoxides have also been identified that would not necessarily be available for analogous alkyls. These include solventassisted methoxide dissociation followed by C-H bond activation6 as well as a binuclear decomposition pathway.7
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7
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12
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0000706580
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Bryndza, H. E.; Calabrese, J. C.; Marsi, M.; Roe, C. D.; Tam. W.; Bercaw, J. E. J. Am. Chem. Soc. 1986, 108, 4805.
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0001268859
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Bernard, K. A.; Rees, W. M.; Atwood, J. D. Organometallics 1986, 5, 390.
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(b) Dedieu, A. Chem. Rev. 2000, 100, 543.
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Itagaki, H.; Koga, N.; Morokuma, K.; Saito, Y. Organometallics 1993, 12, 1648.
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Yamakawa, M.; Ito, H.; Noyori, R. J. Am. Chem. Soc. 2000, 122, 1466.
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0037111738
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Ng, S. M.; Zhao, C.; Lin, Z. J. Organomet. Chem. 2002, 662, 120.
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Ng, S.M.1
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23
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2442596036
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See also studies where the energetics of β-H transfer have been defined: (a) Huo, C.-F.; Li, Y.-W.; Beller, M.; Jiao, H. Organometallics 2004, 23, 2168.
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See also studies where the energetics of β-H transfer have been defined: (a) Huo, C.-F.; Li, Y.-W.; Beller, M.; Jiao, H. Organometallics 2004, 23, 2168.
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25
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0030152598
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+ cation and entails a very high barrier of 37 kcal/mol. This was attributed to the high-spin state of the reactant (S = 5/2) and the consequent lack of vacant orbitais for interaction with the approaching C-H bond. Fiedler, A.; Schröder, D.; Schwarz, H.; Tjelta, B. L.; Armentrout, P. B. J. Am. Chem. Soc. 1996, 118, 5047.
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+ cation and entails a very high barrier of 37 kcal/mol. This was attributed to the high-spin state of the reactant (S = 5/2) and the consequent lack of vacant orbitais for interaction with the approaching C-H bond. Fiedler, A.; Schröder, D.; Schwarz, H.; Tjelta, B. L.; Armentrout, P. B. J. Am. Chem. Soc. 1996, 118, 5047.
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26
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3042643476
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Nielsen, R. J.; Keith, J. M. Stoltz, B. M.; Goddard, W. A., III. J. Am. Chem. Soc. 2004, 126, 7967.
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Nielsen, R.J.1
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Goddard III, W.A.4
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28
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0001146005
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2) and found each proceeded with similar small barriers of less than 2 kcal/mol. See: Versluis, L.; Ziegler, T.; Fan, L. Inorg. Chem. 1990, 29, 4530.
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2) and found each proceeded with similar small barriers of less than 2 kcal/mol. See: Versluis, L.; Ziegler, T.; Fan, L. Inorg. Chem. 1990, 29, 4530.
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29
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34547482439
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Frisch, M.; et al. Gaussian 98, Revision A. 11.4; Gaussian, Inc.: Pittsburgh, PA, 2001.
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Frisch, M.; et al. Gaussian 98, Revision A. 11.4; Gaussian, Inc.: Pittsburgh, PA, 2001.
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11744322674
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Andrae, D.; Häusserman, U.; Dolg, M.; Stall, H.; Preuss, H. Theor. Chim. Acta 1990, 77, 123.
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31
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43949164796
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Höllwarth, A.; Böhme, M.; Dapprich, S.; Ehlers, A. W.; Gobbi, A.; Jonas, V.; Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993, 208, 237.
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32
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0347170005
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(a) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
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0001537258
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Rees, W. M.; Churchill, M. R.; Fettinger, J. C.; Atwood, J. D. Organometallics 1985, 4, 2179.
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37
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0031209054
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Cancès, M. T.; Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 107, 3032.
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0000384893
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Riehl, J.-F.; Jean, Y.; Eisenstein, O.; Pélissier, M. Organometallics 1992, 11, 729.
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Riehl, J.-F.1
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40
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34547439768
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OMe are given as Supporting Information.
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OMe are given as Supporting Information.
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41
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34547404698
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2 ligand moved out of the metal coordination plane is 23 kcal/mol higher in energy.
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2 ligand moved out of the metal coordination plane is 23 kcal/mol higher in energy.
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42
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34547482940
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Manuscript in preparation
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Weller, A. S.; Brayshaw, S. K.; Douglas, T. M.; Moxham, G. L.; Macgregor, S. A.; Vadivelu, P.; Wondimagegn, T. Manuscript in preparation.
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Weller, A.S.1
Brayshaw, S.K.2
Douglas, T.M.3
Moxham, G.L.4
Macgregor, S.A.5
Vadivelu, P.6
Wondimagegn, T.7
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44
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34547418633
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In principle, isomerization of TPH3 3a′ Et to TCO 3b′Et could occur, and a transition state for this process was located with a YEt geometry very similar to 2OMe- In this case, however, the inability of the Et ligand to act as a π-donor results in a very high energy, 39.8 kcal/mol and hence a very high barrier to isomerization. Moreover, subsequent β-H transfer in 3b′Et also has a larger barrier than that in 3a′Et, and so β-H elimination via 3a′Et will be favored on both counts. Full details of the formation and reactivity of 3b′Et are given in the Supporting Information
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Et are given in the Supporting Information.
-
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45
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34547413419
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OMe (AG = +2.7 kcal/mol).
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OMe (AG = +2.7 kcal/mol).
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46
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34547472061
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Attempts to compute this alternative η2-form showed that this species did not correspond to a local minimum, as all geometries converged on the more stable η1-isomer
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1-isomer.
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47
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0001748864
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and references therein
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Helberg, L. E.; Gunnoe, T. B.; Brooks, B. C.; Sabat, M.; Harman, W. D. Organometallics 1999, 18, 573, and references therein.
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Helberg, L.E.1
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84876688889
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1-Formaldehyde: W. Saak, W.; Pohl, S. Z. Anorg. Allg. Chem. 1987, 552, 186.
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49
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34547476589
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2-Formaldehyde: (a) Brown, K. L.; Clark, G. R.; Headford, C. E. L.; Marsden, K.; Roper, W. R. J. Am. Chem. Soc. 1982, 104, 2019.
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2-Formaldehyde: (a) Brown, K. L.; Clark, G. R.; Headford, C. E. L.; Marsden, K.; Roper, W. R. J. Am. Chem. Soc. 1982, 104, 2019.
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3 ligands are in close contact. Vadivelu, P. Ph.D. Thesis, Heriot-Watt University, 2007.
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