Postsynthetic Metal Exchange in a Metal-Organic Framework Assembled from Co(III) Diphosphine Pincer Complexes.

A Zr metal-organic framework (MOF) 1-CoCl has been synthesized by solvothermal reaction of ZrCl with a carboxylic acid-functionalized Co-PNP pincer complex H(L-CoCl) ([L-CoCl] = [(2,6-(NHPAr)CH)CoCl], Ar = p-CHCO). The structure of 1-CoCl has been determined by X-ray powder diffraction and exhibits a csq topology that differs from previously reported ftw-net Zr MOFs assembled from related Pd- and Pt-PNP pincer complexes. The Co-PNP pincer species readily demetallate upon reduction of Co to Co, allowing for transmetalation with late second and third row transition metals in both the homogeneous complex and 1-CoCl.

Unveiling reactive metal sites in a Pd pincer MOF: insights into Lewis acid and pore selective catalysis.

A porous Zr metal-organic framework, 1-PdBF4 [Zr6O4(OH)4(OAc)2.4{(PNNNP)Pd(MeCN)}2.4(BF4)2.

Improved Catalytic Activity and Stability of a Palladium Pincer Complex by Incorporation into a Metal-Organic Framework.

A porous metal-organic framework Zr6O4(OH)4(L-PdX)3 (1-X) has been constructed from Pd diphosphinite pincer complexes ([L-PdX](4-) = [(2,6-(OPAr2)2C6H3)PdX](4-), Ar = p-C6H4CO2(-), X = Cl, I). Reaction of 1-X with PhI(O2CCF3)2 facilitates I(-)/CF3CO2(-) ligand exchange to generate 1-TFA and I2 as a soluble byproduct. 1-TFA is an active and recyclable catalyst for transfer hydrogenation of benzaldehydes using formic acid as a hydrogen source.