A palladium(ii) triangle as building blocks of microporous molecular materials: structures and catalytic performance

Abstract

A porous molecular crystalline solid based on amide-containing Pd(II) triangles was created for size-selective heterogeneous catalysis of the Knoevenagel condensation reaction.

A Pd3L6 supramolecular cage incorporating photoactive [2.2]paracyclophane units

“…[20][21] More generally, only a handful of metallocages of stoichiometry M3L6 have been reported. [22][23][24] The Pd⋯Pd distance around the cavity is 7.7 Å, and the inner cavity diameter of the metallocage, determined from the distance between the centroid of the three palladiums, and a palladium, attains 8.8 Å. The longest external dimension of the cage is 18.0 Å ( Figure S7).…”

Metal Organic Frameworks as Solid Catalysts in Condensation Reactions of Carbonyl Groups

“…It has been postulated that the presence of the porosity in the crystalline MOF powder where the solvent was involved is one of the most important factors enhancing the activity of the amide groups in the solid MOF. Under the same experimental conditions, ECA reacted with SA negligibly (10%), and the conversions of EAA and diethyl malonate were about 20 and 13%, respectively 45. On the other hand, when the size of the SA derivatives increased, the relative conversions of MN decreased to 15% (Scheme ).…”

“…[39] PbA C H T U N G T R E N N U N G (cpna) 2 ·2 DMF·6 H 2 O B A M N C H 3 CN r.t. [40] A [42] ZIF-8 BA MN toluene r.t. [43] ZIF-9 BA MN toluene r.t. [44] Pd [45] POM@MIL-101(Cr) BA ECA toluene 40 [46] PTA@MIL-101(Cr) BA 2-naphthol -90 [47] Tb-tca SA MN -r.t. [48] A [50] Condensation reactions catalyzed through proposed base catalysis ED-MIL-101(Cr) BA ECA C 6 H 12 80 [35] DETA-MIL-101(Cr) BA MN toluene r.t. [51] NH 2 -MIL-101(Cr) BA ECA toluene 60 [52] NH 2 -MIL-101(Al) BA ECA toluene 40 [53] NH 2 -MIL-101(Fe) BA MN toluene 80 [54] Zn [55] IRMOF-3 BA ECA DMF 40 [34] IRMOF-3 re-examination BA ECA ethanol 60 [56] SIM [59] Friedländer, Henry, aldol, Claisen-Schmidt and Pechmann condensation [61] Cu 3 A C H T U N G T R E N N U N G (btc) 2 APD FPD toluene 40 [62] FeA C H T U N G T R E N N U N G (btc) BA AP toluene 110 [63] MIL-101(Cr) acetone --180 [64] MIL-101-SO 3 H-NH 2 BADA NM -90 [65] CuA C H T U N G T R E N N U N G (padi) BADA MN DMSO-d 6 50 [66] A [68] UiO-66A C H T U N G T R E N N U N G (NH 2 ) BA heptanal -120 [69] Cu convenient from the environmental point of view considering the high biotoxicity of this metal. [39] PbA C H T U N G T R E N N U N G (cpna) 2 ·2 DMF·6 H 2 O B A M N C H 3 CN r.t. [40] A [42] ZIF-8 BA MN toluene r.t. [43] ZIF-9 BA MN toluene r.t. [44] Pd [45] POM@MIL-101(Cr) BA ECA toluene 40 [46] PTA@MIL-101(Cr) BA 2-naphthol -90 [47] Tb-tca SA MN -r.t. [48] A [50] Condensation reaction...…”

“…[45] On the other hand, when the size of the SA derivatives increased, the relative conversions of MN decreased to 15% (Scheme 4). Under the same experimental conditions, ECA reacted with SA negligibly (10%), and the conversions of EAA and diethyl malonate were about 20 and 13%, respectively.…”

“…A palladium‐based MOF with the molecular formula Pd 3 (mpdm) 3 (NO 3 ) 6 ⋅34 CH 3 OH⋅8 H 2 O has been synthesized from palladium nitrate dehydrate and mpdm (Figure 2) as ligand and its catalytic activity was studied for the Knoevenagel condensation 45. The reaction between SA and MN in the presence of 4 mol% Pd‐MOF in C 6 H 6 resulted in 80% yield (Scheme ).…”