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

A Zr metal-organic framework (MOF) 1-CoCl₃ has been synthesized by solvothermal reaction of ZrCl₄ with a carboxylic acid-functionalized Co^III-P^NN^NP pincer complex H₄(L-CoCl₃) ([L-CoCl₃]^4- = [(2,6-(NHPAr₂)₂C₆H₃)CoCl₃]^4-, Ar = p-C₆H₄CO₂^-). The structure of 1-CoCl₃ 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^II- and Pt^II-P^NN^NP pincer complexes. The Co-P^NN^NP pincer species readily demetallate upon reduction of Co^III to Co^II, allowing for transmetalation with late second and third row transition metals in both the homogeneous complex and 1-CoCl₃. Reaction of 1-CoCl₃ with [Rh(nbd)Cl]₂ (nbd = 2,5-nobornadiene) results in complete Rh/Co metal exchange at the supported diphosphine pincer complexes to generate 1-RhCl, which has been inaccessible by direct solvothermal synthesis. Treating 1-CoCl₃ with PtCl₂(SMe₂)₂ in the presence of the mild reductant NEt₃ resulted in nearly complete Co substitution by Pt. In addition, a mixed metal pincer MOF, 1-PtRh, was generated by sequential substitution of Co with Pt followed by Rh.