Kinetics and thermodynamics of alkene complexation in d0 metal-alkyl- alkene complexes

Journal of the American Chemical Society

Volumn 122, Issue 18, 2000, Pages 4320-4330

  Casey, Charles P ^a   Klein, Jennifer Fisher ^a   Fagan, Maureen A ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; METAL COMPLEX; YTTRIUM;

ARTICLE; CHELATION; CHEMICAL BOND; CHEMICAL REACTION KINETICS; COMPLEX FORMATION; DISSOCIATION; ENTHALPY; PROTON NUCLEAR MAGNETIC RESONANCE; TEMPERATURE; THERMODYNAMICS;

EID: 0034630836     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9931022     Document Type: Article

References (67)

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17. 1/2 = 44 Hz).
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19. 3).
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22. In contrast to chelate 1, in which one terminal vinyl hydrogen resonance shifts to higher frequency and the other shifts to lower frequency, both of the vinyl hydrogen resonances of chelate 6 shift to lower frequency.
23. See Supporting Information.
24. 12.
25. 1/2 = 28 Hz) for rapidly exchanging bound and free cis-2,5-dimethyl-THF and for rapidly exchanging bound and free trans-2,5-dimethyl-THF.
26. At higher temperatures, 2,5-dimethyl-THF binds to yttrium less well because the formation of the bimolecular complex is entropically disfavored. Intramolecular coordination of the tethered alkene is less entropically disfavored and competes with 2,5-dimethyl-THF for complexation at yttrium more effectively at higher temperature.
27. At -37 °C (236 K), we have excellent direct measurement of the equilibria between 7-on and 11. For equilibria between 6-on and 10, 6-on and 6-off, 7-on and 11, 8-on and 12, and 1-on and 13, data was obtained at temperatures below and above -37 °C and free energy and equilibrium constants can easily be interpolated to -37 °C.
28. 1/2 = 65 Hz) for rapidly exchanging bound and free cis-and trans-2,5-dimethyl-THF. At -122 °C, five resonances are seen for the a-hydrogens of THF, corresponding to decoalesced resonances for both free and bound 2,5-dimethyl-THF. The resonances for free cis-2,5-dimethyl-THF and for free trans-2,5-dimethyl-THF appear at δ 3.74 and 3.98. Three broad singlets for 2,5-dimethyl-THF complexed in 11 were seen at δ 4.16, 4.30, and 4.46 with relative intensity of 1:2:1. We assume that, like THF, 2,5-dimethyl-THF binds so that the plane of the THF ring coincides with the plane between the Cp* ligands. (Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325, Den Haan, K. H.; De Boer, J. L.; Teuben, J. H.; Smeets, W. J. J.; Spek, A. L. J. Organomet. Chem. 1987, 327, 31. Evans, W. J.; Dominguez, R.; Hanusa, T. P. Organometallics 1986, 5, 263.) At -122 °C, 2,5-dimethyl-THF does not rotate freely about the yttrium-oxygen bond and the two α-hydrogens of cis-2,5-dimethyl-THF are inequivalent. Similarly, the two α-hydrogens of complexed trans-2,5-dimethyl-THF are inequivalent. If cis- and trans-2,5-dimethyl-THF bind equally strongly, four equal intensity resonances are expected. The observed 1:2:1 intensity pattern is due to chemical shift degeneracy of two of the resonances. On warming, these three resonances coalesce with the free 2,5-dimethyl-THF resonances. These spectra are consistent with equal binding of the two isomers of 2,5- dimethyl-THF.
29. 1/2 = 65 Hz) for rapidly exchanging bound and free cis- and trans-2,5-dimethyl-THF. At -122 °C, five resonances are seen for the a-hydrogens of THF, corresponding to decoalesced resonances for both free and bound 2,5-dimethyl-THF. The resonances for free cis-2,5-dimethyl- THF and for free trans-2,5-dimethyl-THF appear at δ 3.74 and 3.98. Three broad singlets for 2,5-dimethyl-THF complexed in 11 were seen at δ 4.16, 4.30, and 4.46 with relative intensity of 1:2:1. We assume that, like THF, 2,5-dimethyl-THF binds so that the plane of the THF ring coincides with the plane between the Cp* ligands. (Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325, Den Haan, K. H.; De Boer, J. L.; Teuben, J. H.; Smeets, W. J. J.; Spek, A. L. J. Organomet. Chem. 1987, 327, 31. Evans, W. J.; Dominguez, R.; Hanusa, T. P. Organometallics 1986, 5, 263.) At -122 °C, 2,5-dimethyl-THF does not rotate freely about the yttrium-oxygen bond and the two α-hydrogens of cis-2,5-dimethyl-THF are inequivalent. Similarly, the two α-hydrogens of complexed trans-2,5-dimethyl-THF are inequivalent. If cis- and trans-2,5-dimethyl-THF bind equally strongly, four equal intensity resonances are expected. The observed 1:2:1 intensity pattern is due to chemical shift degeneracy of two of the resonances. On warming, these three resonances coalesce with the free 2,5-dimethyl-THF resonances. These spectra are consistent with equal binding of the two isomers of 2,5- dimethyl-THF.
30. 1/2 = 65 Hz) for rapidly exchanging bound and free cis- and trans-2,5-dimethyl-THF. At -122 °C, five resonances are seen for the a-hydrogens of THF, corresponding to decoalesced resonances for both free and bound 2,5-dimethyl-THF. The resonances for free cis-2,5-dimethyl- THF and for free trans-2,5-dimethyl-THF appear at δ 3.74 and 3.98. Three broad singlets for 2,5-dimethyl-THF complexed in 11 were seen at δ 4.16, 4.30, and 4.46 with relative intensity of 1:2:1. We assume that, like THF, 2,5-dimethyl-THF binds so that the plane of the THF ring coincides with the plane between the Cp* ligands. (Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325, Den Haan, K. H.; De Boer, J. L.; Teuben, J. H.; Smeets, W. J. J.; Spek, A. L. J. Organomet. Chem. 1987, 327, 31. Evans, W. J.; Dominguez, R.; Hanusa, T. P. Organometallics 1986, 5, 263.) At -122 °C, 2,5-dimethyl-THF does not rotate freely about the yttrium-oxygen bond and the two α-hydrogens of cis-2,5-dimethyl-THF are inequivalent. Similarly, the two α-hydrogens of complexed trans-2,5-dimethyl-THF are inequivalent. If cis- and trans-2,5-dimethyl-THF bind equally strongly, four equal intensity resonances are expected. The observed 1:2:1 intensity pattern is due to chemical shift degeneracy of two of the resonances. On warming, these three resonances coalesce with the free 2,5-dimethyl-THF resonances. These spectra are consistent with equal binding of the two isomers of 2,5-dimethyl-THF.
31. trans) = 1.05 ppm] were used as estimates for 1-off.
32. -4 M.
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67. See Supporting Information for General Procedures.