Work

Reversible C−C Bond Cleavage of a Cobalt Diketimide into an Elusive Cobalt Aryl Nitrenoid Complex

Year: 2022

Type: article

Abstract: The reactivity of (TrL)Co (TrL=5‐mesityl‐1,9‐(trityl)dipyrrin) toward various aryl azides was examined to elucidate the electronic structure and reactivity of dipyrrinato cobalt aryl nitrenoid complexes. Herein, we demonstrate the synthesis of a CoII diketimide complex [(TrL)Co(NC6F5)]2 and its reversible C−C bond cleavage to yield a monomeric Co nitrenoid complex (TrL)Co(NC6F5). Exposure of [(TrL)Co(NC6F5)]2 to an excess amount of an H‐atom donor cleanly affords the CoII anilide complex (TrL)Co(NHC6F5). The half‐order decay of [(TrL)Co(NC6F5)]2 via H‐atom abstraction (HAA) reveals saturation kinetic behavior indicating a pre‐equilibrium between [(TrL)Co(NC6F5)]2 and (TrL)Co(NC6F5) prior to HAA. Furthermore, (TrL)Co(NC6F5) undergoes reductive coupling with another equivalent of azide to furnish the four‐coordinate tetrazido complex (TrL)Co(κ2‐N4(C6F5)2), expulsion of a fluorine atom to afford (TrL)CoF, and N‐group transfer reactivity to PPh3.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202115437

Authors: Yunjung Baek, Theodore A. Betley

Institution: Harvard University

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Foundation for the National Institutes of Health, Camille and Henry Dreyfus Foundation, Kwanjeong Educational Foundation, National Institute of General Medical Sciences

Awards: Correlation of electronic structure to iron catalyzed C-H bond functionalization, G2798164012