Zirconium Metal-Organic Frameworks Assembled from Pd and Pt PNNNP Pincer Complexes: Synthesis, Postsynthetic Modification, and Lewis Acid Catalysis.

Carboxylic acid-functionalized Pd and Pt PNNNP pincer complexes were used for the assembly of two porous Zr metal-organic frameworks (MOFs), 2-PdX and 2-PtX. Powder X-ray diffraction analysis shows that the new MOFs adopt cubic framework structures similar to the previously reported Zr6O4(OH)4[(POCOP)PdX]3, [POCOP = 2,6-(OPAr2)2C6H3); Ar = p-C6H4CO2-, X = Cl-, I-] (1-PdX). Elemental analysis and spectroscopic characterization indicate the presence of missing linker defects, and 2-PdX and 2-PtX were formulated as Zr6O4(OH)4(OAc)2.4[M(PNNNP)X]2.4 [M = Pd, Pt; PNNNP = 2,6-(HNPAr2)2C5H3N; Ar = p-C6H4CO2-; X = Cl-, I-]. Postsynthetic halide ligand exchange reactions were carried out by treating 2-PdX with Ag(O3SCF3) or NaI followed by PhI(O2CCF3)2. The latter strategy proved to be more effective at activating the MOF for the catalytic intramolecular hydroamination of an o-substituted alkynyl aniline, underscoring the advantage of using halide exchange reagents that produce soluble byproducts.