Dioxygen Activation by a Macrocyclic Copper Complex Leads to a Cu2O2 Core with Unexpected Structure and Reactivity
- 주제(키워드) Bioinorganic chemistry , Copper , Dioxygen reduction , Macrocyclic ligands , Metal-peroxo complexes
- 등재 SCIE, SCOPUS
- 발행기관 Wiley-VCH Verlag
- 발행년도 2016
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000125468
- 본문언어 영어
- Published As http://dx.doi.org/10.1002/chem.201600551
- 저작권 이화여자대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
We report the CuI/O2 chemistry of complexes derived from the macrocylic ligands 14-TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and 12-TMC (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). While [(14-TMC)CuI]+ is unreactive towards dioxygen, the smaller analog [(12-TMC)CuI(CH3CN)]+ reacts with O2 to give a side-on bound peroxo-dicopper(II) species (SP), confirmed by spectroscopic and computational methods. Intriguingly, 12-TMC as a N4 donor ligand generates SPspecies, thus in contrast with the previous observation that such species are generated by N2 and N3 ligands. In addition, the reactivity of this macrocyclic side-on peroxo-dicopper(II) differs from typical SPspecies, because it reacts only with acid to release H2O2, in contrast with the classic reactivity of Cu2O2 cores. Kinetics and computations are consistent with a protonation mechanism whereby the TMC acts as a hemilabile ligand and shuttles H+ to an isomerized peroxo core. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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