Carlota Odena, Marina Perez-Jimenez, Ronghui Lin and Paul J. Chirik*,
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Exploring the Site Selectivity of Arene Oxidation in [(η5-C5Me5)Ir(η6-arene)](OTf)2 Complexes
The oxidation selectivity of the η6-arene ligand in a series of [(η5-C5Me5)Ir(η6-arene)](OTf)2 complexes to the corresponding [(η5-C5Me5)Ir(η5-phenoxo)](OTf) derivatives was studied as a complementary protocol to metal-catalyzed borylation-oxidation. A series of representative [(η5-C5Me5)Ir(η6-arene)](OTf)2 compounds was prepared with mono-, di-, and trisubstituted arenes as well as two examples with biphenyls to rationally explore the site selectivity of C(sp2)–H oxidation. The isolated organometallic arene complexes were treated with NaClO2 and formed the desired iridium η5-phenoxo products. While site-selective oxidation was observed for some compounds, most of the iridium complexes yielded a mixture of regioisomers. Regioselectivity was primarily determined by electronic factors, while sterics influenced sites that were electronically similar.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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