Square-planar imido complexes of cobalt: synthesis, reactivity and computational study

• Published in: Dalton transactions : an international journal of inorganic chemistry 2024-07, Vol.53 (29), p.12128-12137
• Main Authors: Reyna, Jackson A, Krishnan, V. Mahesh, Silva Villatoro, Roberto, Arman, Hadi D, Stoian, Sebastian A, Tonzetich, Zachary J
• Format: Article
• Language: English
• Subjects: Catalytic activity; Chemical synthesis; Cobalt; Cobalt compounds; Crystallography; Density functional theory; Ferromagnetism; Hydrogen atoms; Substrates
• ISSN: 1477-9226; 1477-9234; 1477-9234
• DOI: 10.1039/d4dt01483a

Treatment of [Co(N 2 )( t Bu PNP)] ( t Bu PNP = anion of 2,5-bis(di- tert -butylphosphinomethyl)pyrrole) with one equivalent of an aryl azide generates the four-coordinate imido complexes [Co(NAr)( t Bu PNP)] (Ar = mesityl, phenyl, or 4- t Bu-phenyl). X-ray crystallographic analysis of the compounds shows an unusual square-planar geometry about cobalt with nearly linear imido units. In the presence of the hydrogen atom donor, TEMPOH, [Co(NPh)( t Bu PNP)] undergoes addition of the H atom to the imido nitrogen to generate the corresponding amido complex, [Co(NHPh)( t Bu PNP)], whose structure and composition were verified by independent synthesis. Despite the observation of H atom transfer reactivity with TEMPOH, the imido complexes do not show catalytic activity for C-H amination or aziridination for several substrates examined. In the case of [Co(NPh)( t Bu PNP)], addition of excess azide produced the tetrazido complex, [Co(N 4 Ph 2 )( t Bu PNP)], whose bond metrics were most consistent with an anionic Ph 2 N 4 ligand. Density Functional Theory (DFT) investigations of the imido and tetrazido species suggest that they adopt a ground state best described as possessing a low-spin cobalt( ii ) ion ferromagnetically coupled to an iminyl radical. Several square-planar cobalt imido complexes have been prepared by treatment of a Co( i ) precursor with aryl azides. The electronic structure and reactivity of the compounds is examined in the context of nitrene insertion reactivity.