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In light of these results, it is noteworthy that Schafer and co-workers recently reported the first example of Ti and Zr imido complexes bearing ancillary amidate ligands. The lack of amidine formation from these complexes, even at elevated temperatures (up to 140°C), presumably reflects the presence of the extremely bulky 2,6-diisopropylphenyl substituents on the amidate nitrogen atoms. See: Thomson, R. K.; Bexrud, J. A.; Schafer, L. L. Organometallics 2006, 25, 4069-4071.
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In light of these results, it is noteworthy that Schafer and co-workers recently reported the first example of Ti and Zr imido complexes bearing ancillary amidate ligands. The lack of amidine formation from these complexes, even at elevated temperatures (up to 140°C), presumably reflects the presence of the extremely bulky 2,6-diisopropylphenyl substituents on the amidate nitrogen atoms. See: Thomson, R. K.; Bexrud, J. A.; Schafer, L. L. Organometallics 2006, 25, 4069-4071.
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As noted by a reviewer, we observed catalyst-dependent chemoselectivity in our initial discovery of transamidation (ref 6) - namely, alkylamide substrates are more reactive with Al catalysts, whereas arylamides are more reactive with Ti complexes. The present study focuses exclusively on Ti chemistry and, therefore, does not address the origin of transamidation chemoselectivity. The latter issue will be the focus of future work.
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As noted by a reviewer, we observed catalyst-dependent chemoselectivity in our initial discovery of transamidation (ref 6) - namely, alkylamide substrates are more reactive with Al catalysts, whereas arylamides are more reactive with Ti complexes. The present study focuses exclusively on Ti chemistry and, therefore, does not address the origin of transamidation chemoselectivity. The latter issue will be the focus of future work.
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After these reactions were complete, a small amount of water was added to quench the Ti catalyst, and the organic layer was analyzed by gas chromatography. No evidence for the presence of free Cp*H ligand was found. We conclude from this result that a [Cp*Ti]-based complex accounts for the observed transamidation, not a small amount of a Cp*-free Ti complex that forms under the reaction conditions.
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After these reactions were complete, a small amount of water was added to quench the Ti catalyst, and the organic layer was analyzed by gas chromatography. No evidence for the presence of free Cp*H ligand was found. We conclude from this result that a [Cp*Ti]-based complex accounts for the observed transamidation, not a small amount of a Cp*-free Ti complex that forms under the reaction conditions.
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