期刊
NEW JOURNAL OF CHEMISTRY
卷 47, 期 9, 页码 4321-4336出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2nj03355k
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Two configurationally isomeric maleonitrile-tethered, N-atom-donor tridentate ligands, HL1-Ar and HL2-Ar, were synthesized and characterized. Co(ii) and Ni(ii) metal ions reacted differently with these ligands, with Ni(ii) being effective in the transformation of HL1-Ar to HL2-Ar. The electronic effects of the ligands and the type of metal ion played a crucial role in their reactivity. The complexes formed were fully characterized and their spectral data explained based on the different electronic environments of the ligands. The redox instability of Co(ii) complexes with HL2-Ar was studied, and a proposed mechanism for the amine-imine interconversion process was supported by experimental and computational data.
Two sets of maleonitrile-tethered, N-atom-donor tridentate ligands which are configurationally isomeric, 2-((E)-(aryl-methylene)amino)-3-((pyridin-2-ylmethyl)amino)maleonitrile (HL1-Ar) and 2-((aryl-methyl)amino)-3-((E)-(pyridin-2-ylmethylene)amino)maleonitrile (HL2-Ar) have been synthesized and fully characterized (where the aryl groups are 4-methoxyphenyl (HL1-OMe/HL2-OMe), 4-(trifluoromethyl)phenyl (HL1-CF3/HL2-CF3) and 2,4,6-trimethylphenyl (HL1-Mes/HL2-Mes)). The competitive role of the ligand's electronic effect and the type of metal ion were explored on the reactivity of Co(ii) and Ni(ii) metal ions with differently electronically tuned ligands. An Ni(ii) metal ion was found to be effective towards the irreversible transformation of HL1-Ar to HL2-Ar (for all substitutions on the aryl group) where the simultaneous oxidation of amine and reduction of imine take place within a single conjugated maleonitrile-tethered ligand. Whereas, Co(ii) interacted differently with each member of HL1-Ar. With the presence of an electron-donating group (EDG), a methyl group (at ortho and para positions) in the phenyl ring of HL1-Mes, Co(ii) could selectively perform the ligand transformation. On the other hand, HL1-CF3 and HL1-OMe (with the presence of less EDG in the phenyl ring in comparison to HL1-Mes) did not respond to the amine-imine interconversion process. The isolated Co(ii) and Ni(ii) complexes were fully characterized using crystallography, cyclic voltammetry, NMR and UV-Vis spectroscopy and the correlation of spectral data changes with the different electronic environments of the ligands was well explained. The redox instability of Co(ii) complexes with HL2-Ar towards aerobic oxidation was studied using spectro-electrochemical analysis. Finally, a mechanism for the amine-imine interconversion process was proposed based on experimentally identified intermediates as well as DFT calculations.
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