Photoelectric properties of aromatic triangular tri-palladium complexes and their catalytic applications in the Suzuki–Miyaura coupling reaction

Li, Xujun; Li, Jia; Wang, Xiaoshuang; Wu, Lingang; Wang, Yanlan; Maestri, Giovanni; Malacrìa, Max; Liu, Xiang

doi:10.1039/d1dt01597d

Cited by 10 publications

(14 citation statements)

References 80 publications

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“…Liu and co-workers synthesized a range of [Pd 3 (XPh) 3 (PAr 3 ) 3 ] + [SbF 6 ] − derivatives (X = S, Se), including those with novel bridging selenide groups in place of sulfide groups . In this study, these C 3 -symmetric catalysts were tested for the first time in SMCC reactions.…”

Section: Catalytic Activity Of Pd N Speciesmentioning

confidence: 99%

Well-Defined Pd_n Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

2022

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In recent studies it has been demonstrated that the privileged reactivity of higher-order metal clusters can be exploited in widely applied catalytic processes, particularly cross-coupling reactions and hydrogenative transformations. Relatively small, well-defined Pd n clusters have been known since the 1960s. Unique reactivity, reaction (product) selectivity, and catalyst behavior have been recently uncovered, from which there is much potential in catalyst design and application. Ligated Pd n clusters of a smaller size (where n is less than 6) may form upon degradation of mononuclear Pd species en route to larger particulate Pd (from <5 nm particles to large moribund forms in the >1 μm range). This review presents the catalytic applications of Pd n clusters. We pay particular attention to the underlying structure of the Pd n clusters, linked to their reactivity. A hypothesis that ligated Pd n clusters may constitute a mechanism by which higher-order Pd species may form (as a bridging point for monoligated Pd species through to PdNPs) is further discussed. Where appropriate, we mention other catalytic reaction processes that complement the discussion focused on cross-coupling and hydrogenation processes.

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Section: Catalytic Activity Of Pd N Speciesmentioning

confidence: 99%

Well-Defined Pd_n Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

2022

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“…In contrast to the established mechanism of coupling reactions catalyzed by mononuclear palladium complexes, preliminary studies on related tri-palladium clusters suggested alternative routes. [53,82] In particular, Schoenebeck and colleagues proposed that probably the bridging phosphorous ligands on the triangular clusters were replaced by iodine atom in the catalytic process. [83] However, in order to better understand the mechanism for our tri-palladium cation 1 catalyzed Sonogashira process, we tracked the experimental process by HRMS.…”

Section: Proposed Mechanism For Sonogashira Reactionmentioning

confidence: 99%

“…[46][47][48][49][50][51][52] Our group further studied the photoelectric properties of [Pd 3 ] + and their preliminary catalytic behaviors in the Suzuki coupling reaction and realized the gram-scale synthesis for the analogues cyclooxygenase-2 (COX-2) inhibitors with good yields (Scheme 1c). [53] In order to deeply investigate the reactivity, applicability and mechanisms of tri-palladium complex [Pd 3 ] + catalyzed CÀ C coupling processes and further explore their applications in organic syntheses, we carried out the [Pd 3 ] + mediated Sonogashira and Heck coupling reactions in this work. Thanks to the stabilizing aromatic bonding of these clusters, very low catalytic loadings could be employed.…”

Section: Introductionmentioning

confidence: 99%

C−I Selective Sonogashira and Heck Coupling Reactions Catalyzed by Aromatic Triangular Tri‐palladium

et al. 2022

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Aromatic triangular tri‐palladium cations 1–3, abbreviated as [Pd3]+, have shown interesting photoelectric properties, Lewis basic character, and excellent activities in catalytic hydrogenation. Herein, we report the highly efficient and C−I selective Sonogashira and Heck coupling reactions catalyzed by these tri‐palladium complexes. Benefiting from the moderate C−I bond association energy, these tri‐palladiums presented exclusive reactivities to aryl iodides over the brominated aromatics in coupling reactions. In the Sonogashira pathway, good to excellent isolated yields (71–95 %) were achieved. Gram‐scale reaction reached 93 % of yield with palladium loading as few as 0.06 mol %. We also explored the electronic and steric effects for phenyl alkynes and aryl iodides including heteroaromatics like thiophene, pyridine, pyrazole, and pyrazine. Similarly, yields of 71–96 % were obtained for palladium loading of 1.5 mol% through catalyzed Heck coupling of aryl iodides and alkenes. The HRMS monitoring revealed that [Pd3]+ maintained as whole entity during the catalytic process due to its robusness.

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“…Reported examples include Suzuki-type arylation methods using boronic acids and aryl bromides 53 or iodides. 54 The group of Schoenebeck reported an elegant method for Kumada-type coupling that has a chirurgical selectivity for the activation of C(sp 2 )−I bonds, leaving the corresponding C−Br and C−Cl ones completely untouched. 55 Once more, this feature is usually inaccessible using popular mononuclear palladium complexes.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Related aromatic tripalladium complexes could also catalyze various cross-coupling sequences. Reported examples include Suzuki-type arylation methods using boronic acids and aryl bromides or iodides . The group of Schoenebeck reported an elegant method for Kumada-type coupling that has a chirurgical selectivity for the activation of C(sp 2 )–I bonds, leaving the corresponding C–Br and C–Cl ones completely untouched .…”

Section: Introductionmentioning

confidence: 99%

Is Aromaticity a Driving Force in Catalytic Cycles? A Case from the Cycloisomerization of Enynes Catalyzed by All-Metal Aromatic Pd₃⁺ Clusters and Carboxylic Acids

et al. 2021

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The work details a mechanistic study based on density functional theory modeling on the cycloisomerization of polyunsaturated substrates catalyzed by all-metal aromatic tripalladium complexes and carboxylic acids. These clusters are an emerging class of catalysts for a variety of relevant transformations, including C–C forming processes that occur under mild conditions and display synthetic features complementary to those of established mononuclear complexes. This study is the first computational one devoted to the comprehension of the series of elementary steps involved in a synthetic transformation catalyzed by an all-metal aromatic complex. Present results confirm previous experimental hints on the striking mechanistic differences exerted by these clusters with respect to the usual cyclization pathways of related substrates. Moreover, the catalytic cycle involving present all-metal aromatic clusters closely parallels the mechanism of the aromatic substitution of regular arenes.

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Photoelectric properties of aromatic triangular tri-palladium complexes and their catalytic applications in the Suzuki–Miyaura coupling reaction

Abstract: The photoelectric properties and catalytic activities of substituted triphenylphosphine and sulfur/selenium ligands supported aromatic triangular tri-palladium complexes 1-4, abbreviated as [Pd3]+, were investigated. The cyclic voltammogram of [Pd3]+ in CH3CN-nBu4NPF6...

Cited by 10 publications

References 80 publications

Well-Defined Pd_n Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

Well-Defined Pd_n Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

C−I Selective Sonogashira and Heck Coupling Reactions Catalyzed by Aromatic Triangular Tri‐palladium

Is Aromaticity a Driving Force in Catalytic Cycles? A Case from the Cycloisomerization of Enynes Catalyzed by All-Metal Aromatic Pd₃⁺ Clusters and Carboxylic Acids

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Photoelectric properties of aromatic triangular tri-palladium complexes and their catalytic applications in the Suzuki–Miyaura coupling reaction

Abstract: The photoelectric properties and catalytic activities of substituted triphenylphosphine and sulfur/selenium ligands supported aromatic triangular tri-palladium complexes 1-4, abbreviated as [Pd3]+, were investigated. The cyclic voltammogram of [Pd3]+ in CH3CN-nBu4NPF6...

Cited by 10 publications

References 80 publications

Well-Defined Pdn Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

Well-Defined Pdn Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

C−I Selective Sonogashira and Heck Coupling Reactions Catalyzed by Aromatic Triangular Tri‐palladium

Is Aromaticity a Driving Force in Catalytic Cycles? A Case from the Cycloisomerization of Enynes Catalyzed by All-Metal Aromatic Pd3+ Clusters and Carboxylic Acids

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Well-Defined Pd_n Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

Well-Defined Pd_n Clusters for Cross-Coupling and Hydrogenation Catalysis: New Opportunities for Catalyst Design

Is Aromaticity a Driving Force in Catalytic Cycles? A Case from the Cycloisomerization of Enynes Catalyzed by All-Metal Aromatic Pd₃⁺ Clusters and Carboxylic Acids