期刊
ORGANOMETALLICS
卷 37, 期 19, 页码 3332-3341出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.8b00559
关键词
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资金
- Deutsche Forschungsgemeinschaft DFG [KL1194/15-1]
- DFG
New organonickel complexes [Ni((R)Ph(R')bpy)Br] carrying various substituted derivatives of the tridentate-(CNN)-N-Lambda-N-Lambda ligand 6-(phenyl-2-ide)-2,2'-bipyridine (-Phbpy) were synthesized from the precursor [Ni(COD)(2)] (COD = 1,5-cyclooctadiene) and the protoligands (ligand precursors) Br-(R)Ph(R')bpy. Several synthetic routes for the protoligands were studied and compared. All new compounds have been analyzed and spectroscopically characterized. From several complexes crystal and molecular structures Br were obtained from XRD experiments. UV-vis absorption spectroscopy and detailed electrochemical measurements reveal the impact of the various substituents on the electronic structure of the complexes. Quantum chemical DFT calculations illustrate the composition of highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) and support the assignment of the single-electron reduction and oxidation products as bpy-localized ligand radical species and transient nickel(III) intermediates, respectively.
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