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1.
J Am Chem Soc ; 144(37): 16905-16915, 2022 09 21.
Artigo em Inglês | MEDLINE | ID: mdl-36083845

RESUMO

In this research article, we describe a 4H+/4e- electron-coupled-proton buffer (ECPB) based on Cu and a redox-active ligand. The protonated/reduced ECPB (complex 1: [Cu(8H+/14e-)]1+), consisting of CuI with 2 equiv of the ligand (catLH4: 1,1'-(4,5-dimethoxy-1,2-phenylene)bis(3-(tert-butyl)urea)), reacted with H+/e- acceptors such as O2 to generate the deprotonated/oxidized ECPB. The resulting compound, (complex 5: [Cu(4H+/10e-)]1+), was characterized by X-ray diffraction analysis, nuclear magnetic resonance (1H-NMR), and density functional theory, and it is electronically described as a cuprous bis(benzoquinonediimine) species. The stoichiometric 4H+/4e- reduction of 5 was carried out with H+/e- donors to generate 1 (CuI and 2 equiv of catLH4) and the corresponding oxidation products. The 1/5 ECPB system catalyzed the 4H+/4e- reduction of O2 to H2O and the dehydrogenation of organic substrates in a decoupled (oxidations and reductions are separated in time and space) and a coupled fashion (oxidations and reductions coincide in time and space). Mechanistic analysis revealed that upon reductive protonation of 5 and oxidative deprotonation of 1, fast disproportionation reactions regenerate complexes 5 and 1 in a stoichiometric fashion to maintain the ECPB equilibrium.


Assuntos
Elétrons , Prótons , Cobre/química , Ligantes , Oxirredução , Ureia
2.
J Coord Chem ; 72(8): 1346-1357, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-34113052

RESUMO

In this research article, we report the synthesis and structural characterization of a family of first-row metal complexes bearing redox-active ligands with tunable H-bonding donors. We observed that these coordination complexes can adopt three different geometries and that they are stabilized by intramolecular multicenter H-bonding interactions, which are systematically modified by changing the metal ion (Co, Ni, Cu, Zn), the ligand scaffold (variations in the diamine and ureanyl substituents used) and the solvent of crystallization.

3.
J Am Chem Soc ; 140(48): 16625-16634, 2018 12 05.
Artigo em Inglês | MEDLINE | ID: mdl-30400740

RESUMO

In this research article, we describe the structure, spectroscopy, and reactivity of a family of copper complexes bearing bidentate redox-active ligands that contain H-bonding donor groups. Single-crystal X-ray crystallography shows that these tetracoordinate complexes are stabilized by intramolecular H-bonding interactions between the two ligand scaffolds. Interestingly, the Cu complexes undergo multiple reversible oxidation-reduction processes associated with the metal ion (CuI, CuII, CuIII) and/or the o-phenyldiamido ligand (L2-, L•-, L). Moreover, some of the CuII complexes catalyze the aerobic oxidation of alcohols to aldehydes (or ketones) at room temperature. Our extensive mechanistic analysis suggests that the dehydrogenation of alcohols occurs via an unusual reaction pathway for galactose oxidase model systems, in which O2 reduction occurs concurrently with substrate oxidation.


Assuntos
Álcoois/química , Complexos de Coordenação/química , Cobre/química , Aldeídos/síntese química , Materiais Biomiméticos/síntese química , Materiais Biomiméticos/química , Catálise , Complexos de Coordenação/síntese química , Glucose Oxidase/química , Ligação de Hidrogênio , Cetonas/síntese química , Ligantes , Modelos Químicos , Estrutura Molecular , Oxirredução , Oxigênio/química
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