| Structure Identification: |
| Inorg Chem. 2014 Apr 7;53(7):3832-8. | | Tribenzylamine C-H activation and intermolecular hydrogen transfer promoted by WCl6.[Pubmed: 24624963] |
METHODS AND RESULTS:
The 1:1 molar reaction of WCl6 with Tribenzylamine (tba), in dichloromethane, selectively afforded the iminium salt [(PhCH2)2N═CHPh][WCl6], 1, and the ammonium one [tbaH][WCl6], 2, in equimolar amounts. The products were fully characterized by means of spectroscopic methods, analytical methods, and X-ray diffractometry. Density functional theory calculations were carried out with the aim of comprehending the mechanistic aspects. | | J Org Chem. 2011 Mar 4;76(5):1418-24. | | Multiple hindered rotators in a gyroscope-inspired tribenzylamine hemicryptophane.[Pubmed: 21271707] | A gyroscope-inspired Tribenzylamine hemicryptophane provides a vehicle for exploring the structure and properties of multiple p-phenylene rotators within one molecule.
METHODS AND RESULTS:
The hemicryptophane was synthesized in three steps in good overall yield using mild conditions. Three rotator-forming linkers were cyclized to form a rigid cyclotriveratrylene (CTV) stator framework, which was then closed with an amine. The gyroscope-like molecule was characterized by (1)H NMR and (13)C NMR spectroscopy, and the structure was solved by X-ray crystallography. The rigidity of the two-component CTV-trismethylamine stator was investigated by (1)H variable-temperature (VT) NMR experiments and molecular dynamics simulations. These techniques identified gyration of the three p-phenylene rotators on the millisecond time scale at -93 °C, with more dynamic but still hindered motion at room temperature (27 °C). The activation energy for the p-phenylene rotation was determined to be ~10 kcal mol(-1). Due to the propeller arrangement of the p-phenylenes, their rotation is hindered but not strongly correlated.
CONCLUSIONS:
The compact size, simple synthetic route, and molecular motions of this gyroscope-inspired Tribenzylamine hemicryptophane make it an attractive starting point for controlling the direction and coupling of rotators within molecular systems. |
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