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

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. Reaction of 1-CoCl with [Rh(nbd)Cl] (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-CoCl with PtCl(SMe) in the presence of the mild reductant NEt 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.

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http://dx.doi.org/10.1021/acs.inorgchem.8b03318DOI Listing

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