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 | 2021 Sep

REPOSITORIES: biostudies-literature