1-D and 2-D phosphine coordination materials based on a palladium(II) PCP pincer metalloligand

Isolating reactive metal-based species in Metal–Organic Frameworks – viable strategies and opportunities

“…A related approach to include reactive organometallic complexes was pursued by Humphrey et al 112,113 Seeking to achieve air and moisture stability, the researchers used a tetra(carboxylated) P-C-P pincer ligand to target highly connected, robust MOFs. Cyclometalation of the P-C-P pincer with Pd 2+ gave a metalloligand which could be used to prepare a crystalline 3D MOF (PCM-36, Phosphorus Coordination Material) with Co 2+ ions.…”

A Metal–Organic Framework with Cooperative Phosphines That Permit Post‐Synthetic Installation of Open Metal Sites

“…Instead, we explored the use of pre‐formed phosphine coordination complexes decorated with ancillary carboxylic acids (namely, approach 3). We showed that Pd II or Pt II complexes of carboxylated bis(phosphines) and PCP‐pincers, could be used to prepare porous PCMs with unique solid‐state reactivity. However, the multi‐step routes to prepare the precursors are complicated and large quantities are usually required in the search for optimal MOF‐forming conditions.…”

“…[5] Adownfall of this approach is that such modifications can cause loss of crystallinity,p reventing full structural determination of the products.T he third is by the use of pre-formed, molecular complexes as MOF building blocks. [6] This direct method can provide crystalline products that permit full structural elucidation by X-ray diffraction, but precursor complexes can undergo decomposition (for example,leaching) under MOFforming conditions.A ss uch, chelated complexes are preferred, but their preparation can be arduous and low-yielding.…”

Halide exchange studies of novel Pd(ii) NNN-pincer complexes

“…Pincer metal complexes in which three donor sites of the ligand stabilize a planar metal center have been studied extensively. Variations to the so-called ECE type ligand (Chart 1) where E symbolizes coordination through anking NR 2 , PR 2 , SR, SeR or OR groups afford complexes with applications especially in catalysis [1][2][3][4][5][6][7][8] but also in other elds including sensing, 6,9-12 materials science [13][14][15][16][17][18][19] and medicinal chemistry. 18,20 Among various metals, palladium is one of the most studied owing mainly to its importance in organic synthesis.…”