Exploring the Site Selectivity of Arene Oxidation in [(η5-C5Me5)Ir(η6-arene)](OTf)2 Complexes

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-11-26 DOI:10.1021/acs.organomet.4c0042110.1021/acs.organomet.4c00421

Carlota Odena, Marina Perez-Jimenez, Ronghui Lin and Paul J. Chirik*,

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Abstract

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.

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

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.