Experimental and Theoretical Study of Ni^II - and Pd^II -Promoted Double Geminal C(sp³ )-H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism.

ABSTRACT: We report the first examples of metal-promoted double geminal activation of C(sp³ )-H bonds of the N-CH₂ -N moiety in an imidazole-type heterocycle, leading to nickel and palladium N-heterocyclic carbene complexes under mild conditions. Reaction of the new electron-rich diphosphine 1,3-bis((di-tert-butylphosphaneyl)methyl)-2,3-dihydro-1H-benzo[d]imidazole (1) with [PdCl₂ (cod)] occurred in a stepwise fashion, first by single C-H bond activation yielding the alkyl pincer complex [PdCl(PC sp3 ^H P)] (3) with two trans phosphane donors and a covalent Pd-C sp3 bond. Activation of the C-H bond of the resulting α-methine C sp3 H-M group occurred subsequently when 3 was treated with HCl to yield the NHC pincer complex [PdCl(PC^NHC P)]Cl (2). Tr

SUBMITTER: He F 

PROVIDER: S-EPMC9401054 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature