Sonogashira Synthesis of New Porous Aromatic Framework-Entrapped Palladium Nanoparticles as Heterogeneous Catalysts for Suzuki–Miyaura Cross-Coupling

Abstract

Palladium nanoparticles entrapped in porous aromatic frameworks (PAFs) or covalent organic frameworks may promote heterogeneous catalytic reactions. However, preparing such materials as active nanocatalysts usually requires additional steps for palladium entrapment and reduction. This paper reports as a new approach, a simple procedure leading to the self-entrapment of Pd nanoparticles within the PAF structure. Thus, the selected Sonogashira synthesis affords PAF-entrapped Pd nanoparticles that can catalyze the C–C Suzuki–Miyaura cross-coupling reactions. Following this new concept, PAFs were synthesized via Sonogashira cross-coupling of the tetraiodurated derivative of tetraphenyladamantane or spiro-9,9′-bifluorene with 1,6-diethynylpyrene, then characterized them using powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, high-resolution scanning transmission electron microscopy, and textural properties (i.e., adsorption–desorption isotherms). The PAF-entrapped Pd nanocatalysts showed high catalytic activity in Suzuki–Miyaura coupling reactions (demonstrated by preserving the turnover frequency values) and stability (demonstrated by palladium leaching and recycling experiments). This new approach presents a new class of PAFs with unique structural, topological, and compositional complexities as entrapped metal nanocatalysts or for other diverse applications.

Stabilization of Palladium-Nanoparticle-Decorated Postsynthesis-Modified Zr-UiO-66 MOF as a Reusable Heterogeneous Catalyst in C–C Coupling Reaction

“…1−3 The C−C catalyzed cross-coupling reactions are generally promoted through fundamental transition-metalcatalyzed transformations, in particular, palladium-catalyzed reactions, which are a powerful route to construct carbon− carbon bonds and are currently applicable to the development of the synthesis of functional organic compounds. 4−9 It is noteworthy that synthetic organic chemistry has been expanded via palladium-catalyzed cross-coupling reactions such as Suzuki−Miyaura, 10,11 Sonogashira−Mizorogi, 12 Heck, Negishi, 13 Silence, 14 Kumada, 15,16 and Sonogashira reactions, 17 which have evolved in recent years. 18−21 The growth of a C−C bond is a consequence of a crosscoupling reaction, defined as the substitution of a heteroatom nucleophile for an alkyl, aryl, or vinyl halide.…”

“…Cross-couplings and related reactions are considered one of the most challenging and highly efficient synthetic protocols. − The C–C catalyzed cross-coupling reactions are generally promoted through fundamental transition-metal-catalyzed transformations, in particular, palladium-catalyzed reactions, which are a powerful route to construct carbon–carbon bonds and are currently applicable to the development of the synthesis of functional organic compounds. − It is noteworthy that synthetic organic chemistry has been expanded via palladium-catalyzed cross-coupling reactions such as Suzuki–Miyaura, , Sonogashira–Mizorogi, Heck, Negishi, Silence, Kumada, , and Sonogashira reactions, which have evolved in recent years. − …”

Carbon–Carbon Linked Organic Frameworks: An Explicit Summary and Analysis

“…[ 132 ] Recently, Căta et al effectively synthesized two PAFs (PAF‐SP and PAF‐AD) via the cross‐coupling of tetraiodurated derivative of tetraphenyladamantane or spiro‐9,9’‐bifluorene with 1,6‐diethynylpyrene. [ 133 ] The prepared materials exhibited excellent catalytic activity in the Suzuki–Miyaura cross‐coupling process after the entrapment of palladium.…”

Bottom-Up De Novo Synthesis of Porous Organic Polymers with Enone Functionalities as Supports for Pd and Cu Nanoparticles for Catalytic Tandem Synthesis

“…18,19 A wide variety of organic building blocks and a number of methodologies to synthesize POPs have been developed; some of the methodologies employed rely on the multistep synthesis and the use of heavy/transition metal-catalyzed reactions for polymerization, limiting their practical applications. 14,17 In our quest for the development of POPs in a cost-effective manner based on readily accessible starting compounds and facile synthetic transformations that preclude the use of metals, 20,21 we recently showed that the aldol condensation reaction can be diligently exploited for the construction of POPs. 20 The polymers obtained by aldol condensation as the reaction for polymerization possess α,β-unsaturated carbonyl functionalities that can be exploited for the stabilization of Pd(0) nanoparticles similar to that of Pd(0) in tris-(dibenzylideneacetone)-dipalladium(0) (Pd 2 (dba) 3 ), a catalyst applicable to a number of organic transformations.…”

“…Figure 3. 14,20,43,49 The porous attributes of Pd@ANT and Pd@NAP were investigated by their N 2 uptake capacities at 77 K and 1 bar. The sorption studies showed that incorporation of Pd(0) NPs does not influence N 2 uptake capacities; both polymers exhibited no affinity for adsorption of N 2 as those of their parent POPs, i.e., ANT and NAP.…”