Investigation of the reactivity of a palladium amido complex with organic halides shows distinct mechanisms, suggesting novel pathways for bond cleavage and formation.
Structurally well‐defined mononuclear Pd(I) complexes are exceedingly rare and their reactivity remains poorly understood. Herein, the reactivity of the Pd(I) amido complex [(BINAP)Pd(NHAr Trip )] ( 1 , BINAP = 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthalene, Ar Trip = 2,6‐bis(2′,4′,6′‐triisopropylphenyl)phenyl) toward organic halides has been investigated. Complex 1 reacts with benzyl bromides in single‐electron redox reaction mechanism to furnish the Pd(II) amido complex [(BINAP)Pd(Br)(NHAr Trip )] ( 2 ) along with benzyl radical, whereas its reactions with aryl and alkyl iodides result in PdN bond cleavage, generating the aminyl radical [NHArTrip]• and Pd(0) species that subsequently performs oxidative addition reactions with organic iodides to yield organo‐Pd(II) species.
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Li et al. (2025) studied this question.
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