Synthesis and Reactivity of Zr MOFs Assembled from PNNNP-Ru Pincer Complexes

Author(s)
Abebu Kassie , Pu Duan , Eric T. McClure , Klaus Schmidt-Rohr , Patrick M. Woodward and Casey R. Wade
Publisher
Organometallics
Year
2019
Volume
38
Pages
3419-3428
DOI
10.1021/acs.inorgchem.8b03318

Abstract

A Zr metal–organic framework (MOF) 1-CoCl3 has been synthesized by solvothermal reaction of ZrCl4 with a carboxylic acid-functionalized CoIII-PNNNP 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 PdII- and PtII-PNNNP pincer complexes. The Co-PNNNP pincer species readily demetallate upon reduction of CoIII to CoII, 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.