A peroxonickel(III)complex bearing the Me6-trien ligand,an open-chain analogue of the macrocyclic 12-TMC ligand,was synthesized and characterized by several physical methods,such as UV-vis,resonance Raman,ESI-MS and E...A peroxonickel(III)complex bearing the Me6-trien ligand,an open-chain analogue of the macrocyclic 12-TMC ligand,was synthesized and characterized by several physical methods,such as UV-vis,resonance Raman,ESI-MS and EPR.Density functional theory calculations provide geometric and electronic configurations of peroxonickel(III)complexes.The reactivity of the peroxonickel(III)intermediate was examined in oxidative nucleophilic reactions(e.g.,aldehyde deformylation).By comparing the reactivities of the open-chain and macrocyclic peroxonickel(III)complexes under identical reaction conditions,we were able to demonstrate that the open-chain peroxonickel(III)complex is much more reactive than the macrocyclic analogue in aldehyde deformylation.This result provides intriguing aspects of the reactivity differences for open-chain vs.macrocyclic systems of metal complexes.展开更多
基金financial support from the NRF(2017R1A2B4005441 and 2018R1A5A1025511)the Ministry of Science,ICT and Future Planning(CGRC 2016M3D3A01913243)of Korea.T.O.acknowledges the support of“Strategic Young Researcher Overseas Visits Program for Accelerating Brain Circulation”.
文摘A peroxonickel(III)complex bearing the Me6-trien ligand,an open-chain analogue of the macrocyclic 12-TMC ligand,was synthesized and characterized by several physical methods,such as UV-vis,resonance Raman,ESI-MS and EPR.Density functional theory calculations provide geometric and electronic configurations of peroxonickel(III)complexes.The reactivity of the peroxonickel(III)intermediate was examined in oxidative nucleophilic reactions(e.g.,aldehyde deformylation).By comparing the reactivities of the open-chain and macrocyclic peroxonickel(III)complexes under identical reaction conditions,we were able to demonstrate that the open-chain peroxonickel(III)complex is much more reactive than the macrocyclic analogue in aldehyde deformylation.This result provides intriguing aspects of the reactivity differences for open-chain vs.macrocyclic systems of metal complexes.
