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1
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79959906769
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For selected examples of catalytic C-H activation in the α position to a nitrogen atom, see
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28
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79959913923
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For details, see the Supporting Information.
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For details, see the Supporting Information.
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-
-
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29
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79959895431
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2 group of 1 -H are shown in the Supporting Information.
-
2 group of 1 -H are shown in the Supporting Information.
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-
-
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30
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79959897840
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All plots can be found in the Supporting Information.
-
All plots can be found in the Supporting Information.
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-
-
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31
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79959891492
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-
-1] confirmed that the rate does not depend on the concentration of 1 -H.
-
-1] confirmed that the rate does not depend on the concentration of 1 -H.
-
-
-
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32
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79959874592
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For examples of complexes with Ti-N-Ti moieties, see
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For examples of complexes with Ti-N-Ti moieties, see
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33
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79959864113
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6 are presented in the Supporting Information.
-
6 are presented in the Supporting Information.
-
-
-
-
37
-
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79959880231
-
-
4] also suggest that Ti compounds of increased molecular weight are formed. The corresponding spectra are shown in the Supporting Information. In addition, the isolation of a dimeric, bridging imido-titanium complex from a mixture of a monomeric amido-titanium complex and benzylamine by Schafer and co-workers (see Ref. [9]) and its catalytic activity in a hydroaminoalkylation reaction strongly support the possible formation of amido titanium oligomers.
-
4] also suggest that Ti compounds of increased molecular weight are formed. The corresponding spectra are shown in the Supporting Information. In addition, the isolation of a dimeric, bridging imido-titanium complex from a mixture of a monomeric amido-titanium complex and benzylamine by Schafer and co-workers (see Ref. [9]) and its catalytic activity in a hydroaminoalkylation reaction strongly support the possible formation of amido titanium oligomers.
-
-
-
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38
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78649918300
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-
An analogous explanation was recently proposed for the comparably sharp decrease in reaction order from one to zero that was observed during a copper-catalyzed reaction.
-
An analogous explanation was recently proposed for the comparably sharp decrease in reaction order from one to zero that was observed during a copper-catalyzed reaction:, P.-F. Larsson, C. Bolm, P.-O. Norrby, Chem. Eur. J. 2010, 16, 13613-13616.
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39
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53849120585
-
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The inhibition of closely related titanium-catalyzed hydroamination reactions by dimethylamine is described in detail in.
-
The inhibition of closely related titanium-catalyzed hydroamination reactions by dimethylamine is described in detail in:, K. Gräbe, F. Pohlki, S. Doye, Eur. J. Org. Chem. 2008, 4815-4823.
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40
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79959888236
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-
All calculations were performed with the program package Gaussian 03 (M. J. Frisch et al., Gaussian 03, Inc., Wallingford, CT, 2009). For technical details, see the Supporting Information.
-
All calculations were performed with the program package Gaussian 03 (M. J. Frisch et al., Gaussian 03, Inc., Wallingford, CT, 2009). For technical details, see the Supporting Information.
-
-
-
-
41
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79959896049
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The results of the DFT calculations are only discussed qualitatively because they were obtained for the gas-phase reaction only. Although it is possible to apply them to reactions in nonpolar solvents, one should keep in mind that the presence of large amounts of highly polar amines and amido derivatives in the reaction mixture as well as their aggregation processes are expected to significantly influence the experimentally observed kinetic parameters. For technical reasons, this influence could not be considered during the calculations.
-
The results of the DFT calculations are only discussed qualitatively because they were obtained for the gas-phase reaction only. Although it is possible to apply them to reactions in nonpolar solvents, one should keep in mind that the presence of large amounts of highly polar amines and amido derivatives in the reaction mixture as well as their aggregation processes are expected to significantly influence the experimentally observed kinetic parameters. For technical reasons, this influence could not be considered during the calculations.
-
-
-
-
42
-
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71549116080
-
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Calculated from the following standard bond lengths: C-H 107 pm, N-H 103.
-
Calculated from the following standard bond lengths: C-H 107 pm, N-H 103;, P. Pyykkö, M. Atsumi, Chem. Eur. J. 2009, 15, 12770-12779.
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Pyykkö, P.1
Atsumi, M.2
|