Insertion of O2 into a Pd(i)–Pd(i) dimer and subsequent C–O bond formation by activation of a C–H bond

Durà-Vilà, Víctor; Mingos, D. Michael P.; Vilar, Ramón; White, Andrew J. P.; Williams, David J.

doi:10.1039/b004537n

Cited by 51 publications

(28 citation statements)

References 12 publications

(5 reference statements)

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“…18 To investigate Pd−Pd interactions in complex 3, a computational study was performed using DFT [BP86, def2-SV(P)] using a slightly simplified model of ligand 1 (having R = Me instead of para-n Bu-Ph; see Figure 3). The DFT structure is very similar to the molecular structure determined by X-ray diffraction (Figure 4).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Well-Defined BisMETAMORPhos Pd^I–Pd^I Complex: Synthesis, Structural Characterization, and Reactivity

et al. 2014

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The formation of a bisMETAMORPhos PNbridged dimeric Pd I complex (3) from ligand 1 and Pd(dba) 2 is described. The addition of 1 to Pd(dba) 2 initially leads to the formation of Pd 0 complex 2, which has a highly distorted tetrahedral environment and binds two neutral ligands 1. Complex 2 converts to {Pd I } 2 complex 3 upon heating. Complex 3 consists of a completely flat Pd−Pd core, with a Pd−Pd bond length of 2.6199(4) Å, and the Pd centers display a highly distorted square planar coordination environment. The formation of complex 3 from 2 is suggested to proceed via an in situ comproportionation pathway. Initial decoordination of one ligand from 2 followed by oxidative addition of one neutral coordinated ligand arm leads to a 1-Pd II H complex. Insertion of free dba into the Pd−H bond generates a 1-Pd II dba complex that releases 1,5-diphenylpent-1-en-3-one via intra-or intermolecular protonolysis. Concomitantly, comproportionation with 1-Pd 0 yields 3. Complex 3 was found to function as a precatalyst in the Suzuki−Miyaura cross-coupling of p-chloroacetophenone with good conversions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Well-Defined BisMETAMORPhos Pd^I–Pd^I Complex: Synthesis, Structural Characterization, and Reactivity

et al. 2014

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“…Vilar et al showed that exposure of [Pd 2 (m-Br) 2 (P(tBu) 3 ) 2 ] (28, Scheme 6) to O 2 resulted in formation of 29. [61] Complex 29 was characterized spectroscopically and crystallographically; however, no yield was reported and the fate of the hydrogen atoms from the cleaved CÀH bond was not identified. Of note, when the bromides in 28 were replaced with iodides, no reaction with O 2 occurred.…”

Section: Stoichiometric Reactions Of Pdmentioning

confidence: 99%

Reactions of Pd and Pt Complexes with Molecular Oxygen

Scheuermann

Goldberg

2014

Chemistry A European J

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Knowledge of exactly how metal complexes react with molecular oxygen is still limited and this has hampered efforts to develop catalysts for oxidation reactions using O2 as the oxidant and/or oxygen-atom source. A better understanding of the reactions of different types of metal complexes with O2 will be of great utility in rational catalyst development. Reactions between molecular oxygen and Pd(0-II) and Pt(0-IV) complexes are reviewed here.

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“…[19,21] We speculate that O 2 reacts with the reversibly generated Pd 0 species; however, direct reaction of O 2 with the Pd I dimer cannot be excluded and will be the focus of future studies. [22] …”

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confidence: 99%

Detection of Palladium(I) in Aerobic Oxidation Catalysis

et al. 2017

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PdII-catalyzed oxidation reactions exhibit broad utility in organic synthesis; however, they often feature high catalyst loading and low turnover numbers relative to non-oxidative cross-coupling reactions. Insights into the fate of the Pd catalyst during turnover could help to address this limitation. Here, we report the identification and characterization of a dimeric PdI species in two prototypical Pd-catalyzed aerobic oxidation reactions: allylic C–H acetoxylation of terminal alkenes and intramolecular aza-Wacker cyclization. Both reactions employ 4,5-diazafluoren-9-one (DAF) as an ancillary ligand. The dimeric PdI complex, [PdI(μ-DAF)(OAc)]2, which features two bridging DAF ligands and two terminal acetate ligands, has been characterized by several spectroscopic methods, as well as single-crystal X-ray crystallography. The origin of this PdI complex and its implications for catalytic reactivity are discussed.

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Insertion of O2 into a Pd(i)–Pd(i) dimer and subsequent C–O bond formation by activation of a C–H bond

Cited by 51 publications

References 12 publications

Well-Defined BisMETAMORPhos Pd^I–Pd^I Complex: Synthesis, Structural Characterization, and Reactivity

Well-Defined BisMETAMORPhos Pd^I–Pd^I Complex: Synthesis, Structural Characterization, and Reactivity

Reactions of Pd and Pt Complexes with Molecular Oxygen

Detection of Palladium(I) in Aerobic Oxidation Catalysis

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Insertion of O2 into a Pd(i)–Pd(i) dimer and subsequent C–O bond formation by activation of a C–H bond

Cited by 51 publications

References 12 publications

Well-Defined BisMETAMORPhos PdI–PdI Complex: Synthesis, Structural Characterization, and Reactivity

Well-Defined BisMETAMORPhos PdI–PdI Complex: Synthesis, Structural Characterization, and Reactivity

Reactions of Pd and Pt Complexes with Molecular Oxygen

Detection of Palladium(I) in Aerobic Oxidation Catalysis

Contact Info

Product

Resources

About

Well-Defined BisMETAMORPhos Pd^I–Pd^I Complex: Synthesis, Structural Characterization, and Reactivity

Well-Defined BisMETAMORPhos Pd^I–Pd^I Complex: Synthesis, Structural Characterization, and Reactivity