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

Carlota Odena; Marina Perez-Jimenez; Ronghui Lin; Paul J. Chirik

doi:10.1021/acs.organomet.4c00421

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

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

Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English (US)
Pages (from-to)	3067-3073
Number of pages	7
Journal	Organometallics
Volume	43
Issue number	23
DOIs	https://doi.org/10.1021/acs.organomet.4c00421
State	Published - Dec 9 2024

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.organomet.4c00421

Cite this

@article{4a477c989a794a4dba95fe7afffcb197,

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

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.",

author = "Carlota Odena and Marina Perez-Jimenez and Ronghui Lin and Chirik, {Paul J.}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2024",

month = dec,

day = "9",

doi = "10.1021/acs.organomet.4c00421",

language = "English (US)",

volume = "43",

pages = "3067--3073",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Exploring the Site Selectivity of Arene Oxidation in [(η5-C5Me5)Ir(η6-arene)](OTf)2 Complexes

AU - Odena, Carlota

AU - Perez-Jimenez, Marina

AU - Lin, Ronghui

AU - Chirik, Paul J.

PY - 2024/12/9

Y1 - 2024/12/9

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85210305963&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85210305963&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.4c00421

DO - 10.1021/acs.organomet.4c00421

M3 - Article

AN - SCOPUS:85210305963

SN - 0276-7333

VL - 43

SP - 3067

EP - 3073

JO - Organometallics

JF - Organometallics

IS - 23

ER -

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

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this