Metalation
of a Thiocatechol-Functionalized Zr(IV)-Based
Metal–Organic Framework for Selective C–H Functionalization
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Abstract
The
incorporation of 2,3-dimercaptoterephthalate (thiocatecholate,
tcat) into a highly robust UiO-type metal–organic framework
(MOF) has been achieved via postsynthetic exchange (PSE). The anionic,
electron-donating thiocatecholato motif provides an excellent platform
to obtain site-isolated and coordinatively unsaturated soft metal
sites in a robust MOF architecture. Metalation of the thiocatechol
group with palladium affords unprecedented Pd-mono(thiocatecholato)
moieties within these MOFs. Importantly, Pd-metalated MOFs are efficient,
heterogeneous, and recyclable catalysts for regioselective functionalization
of sp<sup>2</sup> C–H bond. This material is a rare example
of chelation-assisted C–H functionalization performed by a
MOF catalyst
