Selective hydroboration of alkynes via multisite synergistic catalysis by PCN-222(Cu)

• PCN-222 (Cu, 1200 nm) shows superior catalytic ability in the regio- and stereo-selective hydroboration of alkynes as multifunctional heterogeneous catalyst. • The deuterium labelling experiments show that proton source come from the H 2 O molecule of solvents. • DFT calculations and the control experiments demonstrate that the excellent catalytic activity of PCN-222(Cu) is originated from the synergistic effect of Cu (II) ions, N atoms of porphyrin rings and terminal –OH groups on Zr-nodes. • Five-membered ring centering on “Cu-N-B-C-C” skeleton is the key species. Zirconium-based porphyrinic MOFs (PMOFs, MOF = metal-organic framework) have gained considerable attention in the field of electric/thermo/photo-catalysis as heterogeneous single-site catalysts; however, the study on multisite synergistic catalysis of PMOFs are rare. Herein, we have successfully developed a highly regio- and stereo-selective synthetic method of ( E )- β -vinylboronates through hydroboration of alkynes using PCN-222 (Cu, PCN = porous coordination network) as multifunctional heterogeneous catalyst. Compared with homogeneous catalytic system, high TOF value is achieved in the developed method, originating from the synergistic effect of central Cu(II) ions, N atoms of porphyrin rings and terminal –OH groups on Zr-nodes. Notably, density functional theory (DFT) study reveals that five-membered “Cu-N-B-C-C” ring is the key species responsible for the hydroboration process with specific selectivity.