A heterometal (Pd–Pb) organic framework: synthesis, structure and heterogeneous catalytic application

Abstract

A heterometallic organic framework {Pb[Pd(bpydc)Cl 2 ]DMF} n (1) (H 2 bpydc = 2,2′-bipyridine-5,5′-dicarboxylic acid) was synthesized via a one-pot solvothermal method and characterized using thermogravimetric analysis, X-ray photoelectron spectroscopy as well as powder and single-crystal X-ray diffraction. The crystal structure of 1 indicates that, in metalloligand Pd(bpydc)Cl 2 , every Pd atom adopts a square planar coordination mode with two chloride ions and two nitrogen atoms from bpydc, and the carboxyl groups of Pd(bpydc)Cl 2 connect Pb atoms to form a one-dimensional chain along the crystallographic a-axis, which is interlinked via metalloligands to form a two-dimensional layer structure. This complex is highly active, stable and recyclable as a catalyst for the Suzuki-Miyaura and Heck reactions of a wide range of aryl halides including electron-rich and electron-poor aryl iodides/bromides, affording the corresponding products in good to excellent yields.

Discrete Air-Stable Nickel(II)–Palladium(II) Complexes as Catalysts for Suzuki–Miyaura Reactions

“…As one of the most widely applied methods for constructing a C–C bond, extensive studies have focused on palladium and the selection of appropriate ligands for specific reactions. Multimetallic complexes have found application in catalysis, either as biomimetic complexes of enzyme active sites − or as catalysts in organic reactions. , For the latter, most of the reported multimetallic catalysts are in the form of nanoparticles and metal–organic frameworks. − There are a few examples of discrete, molecular heterobimetallic complexes such as N-heterocyclic carbene-supported Ir–Pd, Ir–Ir, and Pd–Pd complexes that were found to catalyze tandem dehalogenation/transfer hydrogenation or Suzuki/transfer hydrogenation reactions . An impressive hydrodefluorination of organic molecules was found to require both Rh and Pd in a discrete heterobimetallic catalyst .…”

Pore engineering of metal-organic frameworks with coordinating functionalities

“…Pt(II) [68], Pd(II) [70] Pb(II) Pd(II) [75] Ni (II) Ni(II) [62] La(III) Pd(II) [76] Co(II) Co(II) [62,63] Ce(IV) Pd(II) [76] Sm(III) Pd(II) [71] Nd(IV) Pd(II) [76] alytic reaction catalysts based on the successful demonstration of homogeneous catalysts. The solvothermal synthesis was carried out at 100°C under the combination of ligand, DMF and ZrCl 4 .…”

Modified electrodes: Utilizing Cu‐modified graphene oxide nanosheets as a cathode in electro‐oxidation synthesis of mild Suzuki–Miyaura cross‐coupling reaction under green and sustainable conditions

“…4,5 In the realm of organic synthesis, the Suzuki-Miyaura cross-coupling reaction holds a pivotal position for creating carbon-carbon bonds. However, the conventional processes associated with this reaction often involve the use of hazardous reagents, [6][7][8] the elevated expense associated with palladium, high temperatures, 9 long reaction time, 10 and heavy metal catalysts, 11 which raise environmental and sustainability concerns. In response to these challenges, there is a growing urgency to develop greener and more sustainable methodologies for conducting Suzuki-Miyaura cross-couplings.…”