title: Ligand effects on the properties of Ni(iii) complexes: aerobically-induced aromatic cyanation at room temperature.
abstract: A series of organometallic NiIIand NiIIIcomplexes supported by tertadendateRN3C-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 NiIIIcenters, 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 theRN3C-ligand leads to a more accessible NiIIIcenter. 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.
authors.affiliation: Department of Chemistry, Washington University, One Brookings Drive, St. Louis, Missouri 63130-4899, USA. mirica@wustl.edu.
authors.forename: Wen
authors.initials: W
authors.lastname: Zhou
authors.affiliation: Department of Chemistry, Washington University, One Brookings Drive, St. Louis, Missouri 63130-4899, USA. mirica@wustl.edu.
authors.forename: Michael B
authors.initials: MB
authors.lastname: Watson
authors.affiliation: Department of Chemistry, Washington University, One Brookings Drive, St. Louis, Missouri 63130-4899, USA. mirica@wustl.edu.
authors.forename: Shuai
authors.initials: S
authors.lastname: Zheng
authors.affiliation: Department of Chemistry and Biochemistry, University of Missouri-St. Louis, One University Boulevard, St. Louis, Missouri 63121-4400, USA.
authors.forename: Nigam P
authors.initials: NP
authors.lastname: Rath
authors.affiliation: Department of Chemistry, Washington University, One Brookings Drive, St. Louis, Missouri 63130-4899, USA. mirica@wustl.edu.
authors.forename: Liviu M
authors.initials: LM
authors.lastname: Mirica