High-yield synthesis of potentially ditopic coordinating cryptands and their metal complexes

Chaloner, Laura; Ottenwaelder, Xavier

doi:10.1016/j.tetlet.2013.04.074

Cited by 3 publications

(1 citation statement)

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“…Cryptands can influence the geometry and reactivity of metals centres, imparting new behaviours on old coordinating moieties. [23][24][25][26] In previous work, we reported a Cu(II) cryptate, [LCu(OAc)(MeOH)] + , based on a tris(2-aminoethyl)amine (Tren) cordinating moiety (Scheme 1). 27 The geometry of the Cu(II) centre is enforced by the cryptand to be square-pyramidal, unlike typical Tren-based complexes that adopt trigonalbipyramidal geometries.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular control of monooxygenase reactivity in a copper(ii) cryptate

et al. 2016

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We report a detailed investigation of the formation and self-decomposition of Cu(ii)-hydroperoxo intermediates under the influence of second-coordination-sphere features provided by a cryptand. In solution, an equilibrium between two copper complexes with square-planar and square-pyramidal geometries was identified. Upon addition of H2O2/Et3N, two copper(ii)-hydroperoxo intermediates formed at different rates. Their decomposition via self-oxidation was probed by deuterating select positions on the cryptand. This led to a small kinetic isotope effect of 1.5. Mass spectrometry analysis of the demetallated organic products is consistent with a direct oxygen-atom transfer to a tertiary amine on the cryptand, forming an N-oxide, unlike other models of copper mononuclear monooxygenase enzymes.

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