Carboxylate as a Non-innocent L-Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals

Carboxylate as a Non-innocent L-Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals Full article

Journal

Organic Letters
ISSN: 1523-7060 , E-ISSN: 1523-7052

Output data

Year: 2022, Volume: 24, Number: 21, Pages: 3817-3822 Pages count : 6 DOI: 10.1021/acs.orglett.2c01356

Authors

Kuhn Leah ¹ , Vil’ Vera A. ² , Barsegyan Yana A. ² , Terent’ev Alexander O. ² , Alabugin Igor V. ¹

Affiliations

1	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
2	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow, 119991, Russian Federation

We show that the carboxylate radical acts as an L-ligand with certain high-spin transition metal centers. Such coordination preserves the O-radical character needed for C–H activation via hydrogen atom transfer. Capture of the new C-radical by the metal and subsequent reductive elimination leads to formal C–H acyloxylation. Decarboxylation of the RCO2 radical is minimized through hybridization effects introduced by spiro-cyclopropyl moiety.

Kuhn L. , Vil’ V.A. , Barsegyan Y.A. , Terent’ev A.O. , Alabugin I.V.
Carboxylate as a Non-innocent L-Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals
Organic Letters. 2022. V.24. N21. P.3817-3822. DOI: 10.1021/acs.orglett.2c01356 WOS Scopus OpenAlex

Web of science:	WOS:000808582000013
Scopus:	2-s2.0-85131271122
OpenAlex:	W4282928318

DB	Citing
OpenAlex	16
Scopus	14
Web of science	13