Issue 40, 2016

Ligand effects on the properties of Ni(iii) complexes: aerobically-induced aromatic cyanation at room temperature

Abstract

A series of organometallic NiII and NiIII complexes supported by tertadendate RN3C 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 NiIII 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 RN3C ligand leads to a more accessible NiIII center. These results also suggest that the (NpN3C)Ni system should be more reactive toward oxidation than the corresponding (tBuN3C)Ni and (pOMeN3C)Ni systems. Indeed, aerobic oxidative aromatic cyanation was achieved with the (NpN3C)Ni system at room temperature.

Graphical abstract: Ligand effects on the properties of Ni(iii) complexes: aerobically-induced aromatic cyanation at room temperature

Supplementary files

Article information

Article type
Paper
Submitted
31 พ.ค. 2559
Accepted
15 มิ.ย. 2559
First published
16 มิ.ย. 2559

Dalton Trans., 2016,45, 15886-15893

Ligand effects on the properties of Ni(III) complexes: aerobically-induced aromatic cyanation at room temperature

W. Zhou, M. B. Watson, S. Zheng, N. P. Rath and L. M. Mirica, Dalton Trans., 2016, 45, 15886 DOI: 10.1039/C6DT02185A

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