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Reactivity of a Dinuclear Pd^I Complex [Pd₂(μ-PPh₂)(μ₂-OAc)(PPh₃)₂] with PPh₃: Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)₂/nPPh₃ Catalyst System.

ABSTRACT: [Pd^I ₂(μ-PPh₂)(μ₂-OAc)(PPh₃)₂] is the reduction product of Pd^II(OAc)₂(PPh₃)₂, generated by reaction of 'Pd(OAc)₂' with two equivalents of PPh₃. Here, we report that the reaction of [Pd^I ₂(μ-PPh₂)(μ₂-OAc)(PPh₃)₂] with PPh₃ results in a nuanced disproportionation reaction, forming [Pd⁰(PPh₃)₃] and a phosphinito-bridged Pd^I-dinuclear complex, namely [Pd^I ₂(μ-PPh₂){κ₂-P,O-μ-P(O)Ph₂}(κ-PPh₃)₂]. The latter complex is proposed to form by abstraction of an oxygen atom from an acetate ligand at Pd. A mechanism for the formal reduction of a putative Pd^II disproportionation species to the observed Pd^I complex is postulated. Upon reaction of the mixture of [Pd⁰(PPh)₃] and [Pd^I ₂(μ-PPh₂){κ₂-P,O-μ-P(O)Ph₂}(κ-PPh₃)₂] with 2-bromopyridine, the former Pd⁰ complex undergoes a fast oxidative addition reaction, while the latter dinuclear Pd^I complex converts slowly to a tripalladium cluster, of the type [Pd₃(μ-X)(μ-PPh₂)₂(PPh₃)₃]X, with an overall 4/3 oxidation state per Pd. Our findings reveal complexity associated with the precatalyst activation step for the ubiquitous 'Pd(OAc)₂'/nPPh₃ catalyst system, with implications for cross-coupling catalysis.

SUBMITTER: Scott NWJ

PROVIDER: S-EPMC8441971 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Direct C-H functionalization reactions have opened new avenues in catalysis, removing the need for prefunctionalization of at least one of the substrates. Although C-H functionalization catalyzed by palladium complexes in the presence of a base is generally considered to proceed by the CMD/AMLA-6 mechanism, recent research has shown that silver(I) salts, frequently used as bases, can function as C-H bond activators instead of (or in addition to) palladium(II). In this study, we examine the coupling of pentafluorobenzene 1 to 4-iodotoluene 2a (and its analogues) to form 4-(pentafluorophenyl)toluene 3a catalyzed by palladium(II) acetate with the commonplace PPh3 ligand, silver carbonate as base, and DMF as solvent. By studying the reaction of 1 with Ag2CO3/PPh3 and with isolated silver (triphenylphosphine) carbonate complexes, we show the formation of C-H activation products containing the Ag(C6F5)(PPh3)n unit. However, analysis is complicated by the lability of the Ag-PPh3 bond and the presence of multiple species in the solution. The speciation of palladium(II) is investigated by high-resolution-MAS NMR (chosen for its suitability for suspensions) with a substoichiometric catalyst, demonstrating the formation of an equilibrium mixture of Pd(Ar)(κ1-OAc)(PPh3)2 and [Pd(Ar)(μ-OAc)(PPh3)]2 as resting states (Ar = Ph, 4-tolyl). These two complexes react stoichiometrically with 1 to form coupling products. The catalytic reaction kinetics is investigated by in situ IR spectroscopy revealing a two-term rate law and dependence on [Pdtot/nPPh3]0.5 consistent with the dissociation of an off-cycle palladium dimer. The first term is independent of [1], whereas the second term is first order in [1]. The observed rates are very similar with Pd(PPh3)4, Pd(Ph)(κ1-OAc)(PPh3)2, and [Pd(Ph)(μ-OAc)(PPh3)]2 catalysts. The kinetic isotope effect varied significantly according to conditions. The multiple speciation of both AgI and PdII acts as a warning against specifying the catalytic cycles in detail. Moreover, the rapid dynamic interconversion of AgI species creates a level of complexity that has not been appreciated previously.

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Reactivity of a Dinuclear Pd^I Complex [Pd₂(μ-PPh₂)(μ₂-OAc)(PPh₃)₂] with PPh₃: Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)₂/nPPh₃ Catalyst System.

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Reactivity of a Dinuclear PdI Complex [Pd2(μ-PPh2)(μ2-OAc)(PPh3)2] with PPh3: Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)2/nPPh3 Catalyst System.

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OmicsDI is part of the ELIXIR infrastructure

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Reactivity of a Dinuclear Pd^I Complex [Pd₂(μ-PPh₂)(μ₂-OAc)(PPh₃)₂] with PPh₃: Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)₂/nPPh₃ Catalyst System.