Three-Dimensional Phosphine Metal–Organic Frameworks Assembled from Cu(I) and Pyridyl Diphosphine

Abstract

Metal–organic frameworks (MOFs) with phosphine based ligands are extremely attractive for catalysis. In this paper, phosphine has been successfully incorporated for the first time into three-dimensional (3D) MOFs. The MOFs are based on rigid L2M2 dimeric secondary building blocks assembled from Cu(I) and a pyridyl diphosphine ligand, 4-(3,5-bis(diphenylphosphino)phenyl)pyridine, with Br– (CuL-Br), Cl– (CuL-Br), or PF6 – (CuL-PF 6 ) as counteranions. The structures have a 4.122 net topology, which can be further simplified to 64.82-qtz. The MOFs contain 1D homochiral channels. The PF6 – anions hosted in the 1D channel of CuL-PF 6 can be readily exchanged with Br– or Cl– while keeping the framework intact. The materials show anion-tunable flexible porosity. CuL-Br reveals gradual uptake of MeOH, while CuL-PF 6 exhibits stepwise sorption for MeOH. The heterogeneous Lewis acid catalytic activity of the MOFs has been shown in ketalization reaction. CuL-Br and CuL-PF 6 are active in the reactions between ethylene glycol and 2-butanone/cyclohexanone, up to 93% yield with 0.2 mol % catalyst loading. In contrast, no reaction happens between ethylene glycol and bulky benzophenone, suggesting profound size selectivity. The catalysts can be reused with the framework left intact for three runs without loss of activity.

New Functional Cyclic Aminomethylphosphine Ligands for the Construction of Catalysts for Electrochemical Hydrogen Transformations

“…Complexes 10 and 11 are very similar and show square-planar geometry around the metal center with a cis arrangement of the two coordinating Cl atoms ( Figure 3). The P-M-P bite angles are 83.5(2) (10) and 82.7(4)8 (11). The heterocyclic ligands in 10 and 11 have a different conformation than the chair-chair conformation of the free heterocycle (5).…”

“…The X-ray data for 4, 5, and 7 a were collected on a Gemini diffractometer (Agilent Technologies) at T = 130(2) K and the data for 3, 8 a, 10-13, 16, 18, and 19 were collected on Bruker Smart Apex II CCD diffractometer at T = 296(2) [3,11,13,18,19], 293(2) [8 a, 10,12], and 150(2) K (16), by using Mo Ka radiation (l = 0.71073 ). Data reduction of 4, 5, and 7 a was performed with CrysAlis Pro software, [54] and included the program SCALE3 ABSPACK [55] for empirical absorption correction.…”

“…[9,10] Moreover, the ability of the phosphorus and nitrogen atoms of pyridyl diphosphine to form coordinate bonds to Cu I has recently been used in the self-assembly of metal-organic frameworks (MOFs). [11] Complexes of pyridylphosphines with a noncoordinated nitrogen atom from the pyridyl substituent are examples of functionalized systems in which the pyridyl group exhibits basic properties and is capable of secondary interactions, such as hydrogen bonding or proton transfer in the coordination sphere. [12] The ability of the pendant pyridyl groups to interact with weak proton donors suggests the possibility for use of the hydride complexes as catalyst precursors for a number of transformations in polar media, such as nitrile hydration reactions.…”

Phosphine and phosphine oxide groups in metal–organic frameworks detected by P K-edge XAS

“…These materials are very popular thanks to their potential in gas adsorption technologies, 1 biomedical applications, 2,3 and catalysis. [8][9][10][11][12] Incorporation of phosphine functional groups inside structures with new and existing topologies is achieved using direct solvothermal synthesis, postsynthetic modification 13 or the co-crystallization of organic linkers with similar connectivity, 14 We and other groups foresee new applications for such materials in transition metal immobilization and catalysis. 7 Organophosphine moieties were recently introduced to yield crystalline phosphine MOFs (P-MOFs).…”

Coordination‐Driven Terpyridyl Phosphine Pd(II) Gels

“…4,2':6',4"-Terpyridyl is incorporated in the phosphines considering that its coordination behavior is controllable to some extent in comparison with phosphine groups, thus potentially leading to more predictable supramolecular assembly. [35,44,53] The resulting gels were subjected to catalytic study in the Suzuki-Miyaura coupling. …”