C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects

Bojer D, Venugopal A, Mix A, Neumann B, Stammler H-G, Mitzel NW (2011)
Chemistry 17(22): 6248-6255.

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Abstract
The reaction of 1,3,5-triisopropyl- 1,3,5-triazacyclohexane (TiPTAC) with [Y(AlMe4)(3)] resulted in the formation of [(TiPTAC) Y(Me3AlCH2AlMe3)(mu-MeAlMe3)] by C-H activation and methane extrusion. In contrast, the presence of bulkier cyclohexyl groups on the nitrogen atoms in 1,3,5-tricyclohexyl-1,3,5-triazacyclohexane (TCyTAC) led to the formation of the cationic dimethyl complex [(TCyTAC)(2)YMe2][AlMe4]. The investigations reveal a dependency of the reaction mechanism on the steric bulk of the N-alkyl entity and the solvent employed. In toluene C-H activation was observed in reactions of [Y(AlMe4)(3)] with 1,3,5-trimethyl-1,3,5-triazacyclohexane (TMTAC) and TiPTAC. In THF molecular dimethyl cations, such as [(TCyTAC)(2)YMe2] [AlMe4], [(TMTAC)(2)YMe2][AlMe4] and [(TiPTAC)(2)YMe2][AlMe4], could be synthesised by addition of the triazacyclohexane at a later stage. The THF-solvated complex [YMe2(thf)(5)][AlMe4] could be isolated and represents an intermediate in these reactions. It shows that cationic methyl complexes of the rare-earth metals can be formed by donor-induced cleavage of the rare-earth-metal tetramethylaluminates. The compounds were characterised by single-crystal X-ray diffraction or multinuclear and variable-temperature NMR spectroscopy, as well as elemental analyses. Variable-temperature NMR spectroscopy illustrates the methyl group exchange processes between the cations and anions in solution.
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Bojer D, Venugopal A, Mix A, Neumann B, Stammler H-G, Mitzel NW. C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects. Chemistry. 2011;17(22):6248-6255.
Bojer, D., Venugopal, A., Mix, A., Neumann, B., Stammler, H. - G., & Mitzel, N. W. (2011). C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects. Chemistry, 17(22), 6248-6255. doi:10.1002/chem.201003317
Bojer, D., Venugopal, A., Mix, A., Neumann, B., Stammler, H. - G., and Mitzel, N. W. (2011). C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects. Chemistry 17, 6248-6255.
Bojer, D., et al., 2011. C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects. Chemistry, 17(22), p 6248-6255.
D. Bojer, et al., “C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects”, Chemistry, vol. 17, 2011, pp. 6248-6255.
Bojer, D., Venugopal, A., Mix, A., Neumann, B., Stammler, H.-G., Mitzel, N.W.: C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects. Chemistry. 17, 6248-6255 (2011).
Bojer, Daniel, Venugopal, Ajay, Mix, Andreas, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. “C-H Activation versus Yttrium-Methyl Cation Formation from [Y(AlMe4)(3)] Induced by Cyclic Polynitrogen Bases: Solvent and Substituent-Size Effects”. Chemistry 17.22 (2011): 6248-6255.
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