Origin and Regioselectivity of Direct Hydrogen Atom Transfer Mechanism of C(sp3)-H Arylation by [W10O32]4-/Ni Metallaphotoredox Catalysis

Abstract

Polyoxometalates (POMs) have a broad array of applied platforms with well-characterized catalysis including photocatalysis to achieve aliphatic C(sp³)-H bond functionalization. However, the reaction mechanism of POMs in organic transformation remains unknown due to the complexity of POM structures. Here, a challenging [W₁₀O₃₂]^4-/Ni metallaphotoredox-catalyzed C(sp³)-H arylation of alkane has been investigated by density functional theory (DFT) calculations. The calculation revealed that the superficial active center located in bridged oxygen of *[W₁₀O₃₂]^4- is responsible for the abstraction of a foreign hydrogen atom and the activation of a C(sp³)-H bond. Furthermore, we discussed this activated process using the direct activation model of the C(sp³)-H σ-bond to deepen our mechanistic understanding of POM mediated C-H bond activation via the hydrogen atom transfer (HAT) pathway. Specifically, comparing three common mechanisms for nickel catalysis inducing by Ni⁰, Ni^I, and Ni^II to construct a C-C bond, the nickel catalytic cycle induced by the Ni^I active catalyst is profitable in kinetics and thermodynamics. Finally, a radical mechanism merging the ([W₁₀O₃₂]^4--*[W₁₀O₃₂]^4--[HW₁₀O₃₂]^4--[W₁₀O₃₂]^4-) decatungstate reductive quenching cycle, ([HW₁₀O₃₂]^4--[H₂W₁₀O₃₂]^4--[HW₁₀O₃₂]^4-) electron relay, and (Ni^I-Ni^II-Ni^I-Ni^III-Ni^I) nickel catalytic cycle is proposed to be favorable. We hope that this work would provide a better understanding of the unique catalytic activity of decatungstate anions for the direct functionalization of the C(sp³)-H bond.