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Elucidating the reaction mechanism of a palladium-palladium dual catalytic process through kinetic studies of proposed elementary steps.

ABSTRACT: In the synergistic dual catalytic process, the kinetics of the catalytic cycles must be balanced for the successful outcome of the reaction. Therefore, the analysis of the kinetics of the independent catalytic cycles is essential for such reactions, as it enables their relational optimization as well as their design. Here we describe an analysis of the mechanism of a catalytic synergistic bimetallic reaction through the experimental study of a palladium-catalysed cross-coupling of aryl halides with terminal alkynes, an example of a monometallic dual catalytic process. The proposed mechanism of the investigated reaction was disassembled into two palladium catalytic cycles and further into elementary reactions, and each step was studied independently. The described mechanistic analysis allowed us to identify the rate-determining step of the catalytic process by comparing the rates of the elementary reactions under similar reaction conditions, balanced kinetics of the palladium catalytic cycles, and also in which step which reagent enters the catalytic cycle and how.

SUBMITTER: Ivancic A

PROVIDER: S-EPMC10024772 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Elucidating the reaction mechanism of a palladium-palladium dual catalytic process through kinetic studies of proposed elementary steps.

Ivančič Anže A Košmrlj Janez J Gazvoda Martin M

Communications chemistry 20230318 1

In the synergistic dual catalytic process, the kinetics of the catalytic cycles must be balanced for the successful outcome of the reaction. Therefore, the analysis of the kinetics of the independent catalytic cycles is essential for such reactions, as it enables their relational optimization as well as their design. Here we describe an analysis of the mechanism of a catalytic synergistic bimetallic reaction through the experimental study of a palladium-catalysed cross-coupling of aryl halides w ...[more]

PMID: 36934172

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Project description:Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-(t)Bu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower than those required for the reactions catalyzed by a combination of palladium precursors and CyPF-(t)Bu. To explain these differences in rates between the catalytic and stoichiometric reactions, studies were conducted to identify the resting state of the catalyst of the reactions catalyzed by a combination of Pd(OAc)(2) and CyPF-(t)Bu, a combination of Pd(dba)(2) and CyPF-(t)Bu, or the likely intermediate Pd(CyPF-(t)Bu)(Ar)(Br). These data show that the major palladium complex in each case lies off of the catalytic cycle. The resting state of the reactions catalyzed by Pd(OAc)(2) and CyPF-(t)Bu was the palladium bis-thiolate complex [Pd(CyPF-(t)Bu)(SR)(2)] (R = alkyl or aryl). The resting state in reactions catalyzed by Pd(2)(dba)(3) and CyPF-(t)Bu was the binuclear complex [Pd(CyPF-(t)Bu)](2)(mu(2),eta(2)-dba) (9). The resting states of reactions of both aromatic and aliphatic thiols catalyzed by [Pd(CyPF-(t)Bu)(p-tolyl)(Br)] (3a) were the hydridopalladium thiolate complexes [Pd(CyPF-(t)Bu)(H)(SR)] (R= alkyl and aryl). All these palladium species have been prepared independently, and the mechanisms by which they enter the catalytic cycle have been examined in detail. These features of the reaction catalyzed by palladium and CyPF-(t)Bu have been compared with those of reactions catalyzed by the alkylbisphosphine DiPPF and Pd(OAc)(2) or Pd(dba)(2). Our data indicate that the resting states of these reactions are similar to each other and that our mechanistic conclusions about reactions catalyzed by palladium and CyPF-(t)Bu can be extrapolated to reactions catalyzed by complexes of other electron-rich bisphosphines.

Dataset Information

Elucidating the reaction mechanism of a palladium-palladium dual catalytic process through kinetic studies of proposed elementary steps.

Publications

Elucidating the reaction mechanism of a palladium-palladium dual catalytic process through kinetic studies of proposed elementary steps.

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