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Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.

ABSTRACT: A copper(II)-hydroperoxo complex, [Cu(Me(6)-tren)(OOH)](+) (2), and a copper(ii)-cumylperoxo complex, [Cu(Me(6)-tren)(OOC(CH(3))(2)Ph)](+) (3), were synthesized by reacting [Cu(Me(6)-tren)(CH(3)CN)](2+) (1) with H(2)O(2) and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)-OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configurations of 2 and 3, showing trigonal bipyramidal copper(II)-OOR geometries. These copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.

SUBMITTER: Choi YJ

PROVIDER: S-EPMC3318924 | biostudies-literature | 2011 Mar

REPOSITORIES: biostudies-literature

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Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.

Choi Yu Jin YJ Cho Kyung-Bin KB Kubo Minoru M Ogura Takashi T Karlin Kenneth D KD Cho Jaeheung J Nam Wonwoo W

Dalton transactions (Cambridge, England : 2003) 20110124 10

A copper(II)-hydroperoxo complex, [Cu(Me(6)-tren)(OOH)](+) (2), and a copper(ii)-cumylperoxo complex, [Cu(Me(6)-tren)(OOC(CH(3))(2)Ph)](+) (3), were synthesized by reacting [Cu(Me(6)-tren)(CH(3)CN)](2+) (1) with H(2)O(2) and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)-OOR spec ...[more]

PMID: 21258722

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Dataset Information

Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.

Publications

Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.

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