Ligand effects on the properties of Ni(iii) complexes: aerobically-induced aromatic cyanation at room temperatureElectronic supplementary information (ESI) available: Synthetic details, spectroscopic characterization, reactivity studies, and crystallographic data. CCDC 1458980 (3), 1458981 (7) and 1458982 (8). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt02185a

• Main Authors: Zhou, Wen, Watson, Michael B, Zheng, Shuai, Rath, Nigam P, Mirica, Liviu M
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c6dt02185a

A series of organometallic Ni II and Ni III complexes supported by tertadendate R N3C − ligands were synthesized and fully characterized using X-ray crystallography, CV, and EPR. Based on the solid state structures, the substituents on the two amine N-donors significantly affect the coordination of the Ni III centers, while the para substituents of the phenyl C-donor have a reduced effect. This is further supported by electrochemical and spectroscopic measurements that suggest the presence of a less bulky N -substituent of the R N3C − ligand leads to a more accessible Ni III center. These results also suggest that the ( Np N3C)Ni system should be more reactive toward oxidation than the corresponding ( t Bu N3C)Ni and ( p OMe N3C)Ni systems. Indeed, aerobic oxidative aromatic cyanation was achieved with the ( Np N3C)Ni system at room temperature. Ligand effect studies on ( R N3C)Ni III L 2 complexes reveal aerobically-induced aromatic cyanation with t BuNC at room temperature for the ( Np N3C)Ni system.