Synthesis of hydroxo-bridged Dy(III) dimers supported by crown ethers through C-H activation and oxygen-atom transfer of Me3NO

Abstract

Me3NO is well known to undergo oxygen-atom transfer reaction, while the C-H activation of Me3NO with organometallic complexes is far less explored. Herein, we reported the synthesis and characterization of two hydroxo-bridged dinuclear complexes [Dy(12-crown-4)(µ-OH)(CH₃CN)I]2I2(CH₃CN)2 (3) and [Dy(15-crown-5)(µ-OH)(CH₃CN)]2I4 (4), which were formed by the reactions of different crown ether supported complexes [Dy(12-crown-4)₂(CH₃CN)]I₃ (1) and [Dy(15-crown-5)(CH₃CN)₂I]I₂ (2) with Me3NO, respectively. The observation of bridging hydroxo groups in complexes 3 and 4 indicates that Me3NO underwent C-H activation along with OAT during the reactions. In contrast, the reactions of 1 and 2 with H2O led to two hydrated adducts [Dy(12-crown-4)2(H2O)](CH3CN)3I3 ( 5) and [Dy(15-crown-5)(CH3CN)2(H2O)]I3 (6) ,respectively.