Spectroscopic and Computational Characterization of CuII-OOR (R = H or Cumyl) Complexes Bearing a Me6-tren Ligand

Abstract

The copper(II)-hydroperoxo, [Cu(Me6-tren)(OOH)]+(2), and copper(II)-cumylperoxo, [Cu(Me6-tren)(OOC(CH3)2Ph)]+ (3), complexes were synthesized by reacting [Cu(Me6-tren)(CH3CN)]2+ (1) with H2O2 and cumyl-OOH, respectively, in the presence of triethylamine. The 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 Cu(II)-OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configuration of 2 and 3, showing trigonal bipyramidal copper(II)-OOR geometries. The copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.;구리(II)-OOH와 구리(II)-Cumylperoxo 에 대한 연구를 하였다. CuII(Me6-Tren)(ClO4)2를 합성하여 H2O2와 Cumyl-OOH를 TEA와 함께 넣어 단핵 구리(II)-OOH 와 구리(II)-Cumylperoxo 를 생성시켰다.이 복합체를 UV/vis spectrophotometer, electon paramagnetic resonance(EPR), electrospray ionization mass spectrometer(ESI-MS), Resonance RAMAN 등의 물리 화학적인 방법을 통해 특성을 확인하였다. 복합체의 구조와 전자 배치를 나타낸 Density functional theory (DFT)를 통해 trigonal-bipyramidal 구조를 가지는 구리(II)-OOR 복합체라는 것을 확인하였다. 또 구리(II)-OOH와 구리(II)-Cumylperoxo 반응성 실험을 하였을 때 electrophilic 과 nucleophilic 산화 반응이 일어나지 않음을 확인하였다.