Synthesis of novel tantalacalixarene complexes: first example of intramolecular CH activation of monodepleted aromatic ring

Abstract : The alkylation of (dichlorotantala)-p-tert-butylcalix[4]arenes 1 and 3 by two equivalents of NpMgCl (Np = neopentyl) affords the corresponding unreported (bisneopentyltantala)-p-tert-butylcalix[4]arenes 4 and S. These complexes can undergo dealkylation by modest increase of the temperature to yield 6 and 7. The characterization and structural conformation of the complexes 6 and 7 were determined by H-1, C-13, NOESY, and COSY spectroscopic studies and single-crystal X-ray diffraction. 7 exhibits unprecedented use of an intramolecular C H activation of an aromatic ring and simultaneously releases of one equivalent of neopentane. DFT calculation supports a mechanism in which the metal passes through a transition state involving a coplanar arrangement with its three ligands (C-Ar, H-Ar., C-Np).
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Jeff Espinas, Jérémie Pelletier, Erwan Jeanneau, Ulrich Darbost, Kai C. Szeto, et al.. Synthesis of novel tantalacalixarene complexes: first example of intramolecular CH activation of monodepleted aromatic ring. Organometallics, American Chemical Society, 2011, 30 (13), pp.3512-3521. ⟨10.1021/om200140u⟩. ⟨hal-00877430⟩

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