M. Dasgupta, Haregewine Tadesse, A. Blake
Oct 1, 2008
Citations
0
Influential Citations
25
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract Reaction of N-(4-R-phenyl)picolinamide (R = OCH3, CH3, H, Cl and NO2) with [Ir(PPh3)3Cl] in refluxing ethanol in the presence of a base (NEt3) affords two yellow complexes (1-R and 2-R). The 1-R complexes contain an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphines, a chloride and a hydride. The 2-R complexes contain an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphines and two hydrides. Similar reaction of N-(naphthyl)picolinamide with [Ir(PPh3)3Cl] affords two organometallic complexes, 3 and 4. In complex 3 the amide ligand is coordinated to the metal center, via C–H activation of the naphthyl ring at the 8-position, as a dianionic tridentate N,N,C donor, along with two triphenylphosphines and one chloride. Complex 4 is similar to complex 3, except a hydride is bonded to iridium instead of the chloride. Structures of the 1-OCH3, 2-Cl and 4 complexes have been determined by X-ray crystallography. All the complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a IrIII–IrIV oxidation within 0.50–1.16 V vs. SCE and a reduction of the coordinated amide ligand within −1.02 to −1.25 V vs. SCE.