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Twist it! The acid-dependent isomerization of homoleptic carbenic iridium(iii) complexes
Jaroslaw G Osiak1, Tobias Setzer2, Peter G Jones3
1Institut für Hochfrequenztechnik, Technische Universität Braunschweig, Bienroder Weg 94, 38106, Braunschweig, Germany. h2.johannes@ihf.tu-bs.de.
Abstract:
The first successful meridional to facial isomerization of homoleptic carbenic iridium(iii) complexes is presented. The Brønsted-acid-mediated procedure allows the conversion of large amounts of material and additionally provides an in situ purification because of precipitation of the target material during the reaction. The pronounced acid-dependency of the reaction yield observed for tris(N-phenyl,N-methyl-benzimidazol-2-yl)iridium(iii) and tris(N-phenyl,N-benzyl-benzimidazol-2-yl)iridium(iii) was investigated by labelling experiments and quantum chemical calculations. The results reveal a subtle balance between the strength of the acid, the coordinating power of the corresponding base and steric effects of the ligand sphere. Based on these findings, general rules are given for a systematic and material-specific modification of the reaction conditions for the mer-fac isomerization of homoleptic carbenic Ir(iii) complexes.
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