Year: 2023
Type: article
Abstract: This report describes the synthesis of a pseudo-tetrahedral chromium alkyne complex supported by a bidentate phosphinimide ligand and its reactivity with an azobenzene derivative. Characterization of the former by structural and computational methods reveals an unprecedented extent of alkyne activation by a formal chromium(II) center, suggesting that this complex is best described as a chromium(IV)-metallocyclopropene. Exposure of this compound to 4,4'-difluoroazobenzene results in the formation of a chromium(VI) diimido complex, which constitutes a rare 4-electron oxidative addition of an N=N double bond. The isolation of a chromium(IV)-hydrazido intermediate enabled mechanistic investigations of this challenging bond cleavage process. This work substantiates the notion that terminal phosphinimide ligands can engender first-row transition metal ions with exceptional reactivity.
Authors: Paul Rathke, Jonathan Rittle
Institution: University of California, Berkeley
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,250
Awards: G1079818582, Acquisition of a Cryoprobe and Related Accessories for a 600 MHz NMR Spectrometer to Support Health Research Activities at the University of California, Berkeley, G1143651532, G1286236842, G1286251239, G1414775356, G1445641779, G1816284028, G2618837358, G2857863752, G30714459, G3083819904, G365575497, G382641700, G419881185, G42916606, G4501827968, G498139845, G5849692847, G650090426, G654302390, G6652958823, G7354628648, G805243471, G969889393
OpenAlex ID: W4386357090