Formation of hybrid guanidine-stabilized bis(μ-oxo)dicopper cores in solution: Electronic and steric perturbations.
Formation of hybrid guanidine-stabilized bis(μ-oxo)dicopper cores in solution: Electronic and steric perturbations.
复制标题
在溶液中形成混合胍稳定的双（μ-氧）二铜核：电子和空间扰动。
DOI：
10.1002/ejic.201500884
复制
发表时间：
2015
影响因子：
2.3
通讯作者：
Stack,TDanielP
中科院分区：
文献类型：
--
作者：
Herres-Pawlis,Sonja;Haase,Roxana;Verma,Pratik;Hoffmann,Alexander;Kang,Peng;Stack,TDanielP
A series of new hybrid peralkylated amine‐guanidine ligands based on a 1,3‐propanediamine backbone and their Cu‐O2chemistry is reported. The copper(I) complexes react readily with O2at low temperatures in aprotic solvents with weakly coordinating anions to form exclusively bis(μ‐oxo)dicopper species (O). Variation of the substituents on each side of the hybrid bidentate ligand reveal that less sterically demanding amine and guanidine substituents increase not only the thermal stability of the formedOcores but also enhance inner‐sphere phenolate hydroxylation pathways. TD‐DFT analysis on selected guanidine‐amineOspecies suggest that the additional visible‐wavelength feature observed is a guanidine π* → Cu2O2LMCT, which appears along with the classic oxo‐σu* → CuIIIand πσ* → CuIIILMCT transitions.
