Synergistic cross-coupling catalysis: a trialkylphosphine/Pd catalyst tethered to MOF-808(Hf) is very effective for Suzuki-Miyaura coupling of problematic nucleophiles

Hafnium and zirconium forms of the benzene-1,3,5-tricarboxylate metal organic framework MOF-808 were prepared from aqueous solution and modified post-synthetically with 3-{(4-methoxy-phenyl)thio}propane-1-sulfonate (MPTPS) and 3-(di-tert-butylphosphino)propane-1-sulfonate (DTBPPS). Their ligands were stoichiometrically loaded with Pd²⁺. Pd@DTBPPS-MOF-808 is found to be a good catalyst for the Suzuki–Miyaura coupling of functionalised aryl boronic acid derivatives with aryl bromides and unactivated aryl chlorides and the MOF-808(Hf)-based catalysts show significant promise for some highly demanding cross-coupling combinations featuring electron deficient nucleophiles that suffer from poor transmetalation and significant protodeborylation. Remarkably, these led to strongly improved conversions over those based on MOF-808(Zr).