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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.

Project description:The mixed-valence triiron complexes [Fe3(CO)7-x (PPh3) x (μ-edt)2] (x = 0-2; edt = SCH2CH2S) and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist only in the dibasal form in both the solid state and solution. The carbonyl on the central iron atom is semibridging, and this leads to a rotated structure between the bridged diiron center. IR studies reveal that all complexes are inert to protonation by HBF4·Et2O, but addition of acid to the pentacarbonyl complexes results in one-electron oxidation to yield the moderately stable cations [Fe3(CO)5(PPh3)2(μ-edt)2]+ and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2]+, species which also result upon oxidation by [Cp2Fe][PF6]. The electrochemistry of the formally Fe(I)-Fe(II)-Fe(I) complexes has been investigated. Each undergoes a quasi-reversible oxidation, the potential of which is sensitive to phosphine substitution, generally occurring between 0.15 and 0.50 V, although [Fe3(CO)5(PPh3)2(μ-edt)2] is oxidized at -0.05 V. Reduction of all complexes is irreversible and is again sensitive to phosphine substitution, varying between -1.47 V for [Fe3(CO)7(μ-edt)2] and around -1.7 V for phosphine-substituted complexes. In their one-electron-reduced states, all complexes are catalysts for the reduction of protons to hydrogen, the catalytic overpotential being increased upon successive phosphine substitution. In comparison to the diiron complex [Fe2(CO)6(μ-edt)], [Fe3(CO)7(μ-edt)2] catalyzes proton reduction at 0.36 V less negative potentials. Electronic structure calculations have been carried out in order to fully elucidate the nature of the oxidation and reduction processes. In all complexes, the HOMO comprises an iron-iron bonding orbital localized between the two iron atoms not ligated by the semibridging carbonyl, while the LUMO is highly delocalized in nature and is antibonding between both pairs of iron atoms but also contains an antibonding dithiolate interaction.

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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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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.