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Issue 40, 2016
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Ligand effects on the properties of Ni(iii) complexes: aerobically-induced aromatic cyanation at room temperature

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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

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Publication details

The article was received on 31 May 2016, accepted on 15 Jun 2016 and first published on 16 Jun 2016


Article type: Paper
DOI: 10.1039/C6DT02185A
Dalton Trans., 2016,45, 15886-15893

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    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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