Step‐Growth Coordination Polymerization of 5‐Hydroxymethyl Furfural with Dihydrosilanes: Synergistic Catalysis Using Heteroscopionate Zinc Hydride and B(C6F5)3

The utilization of 5‐hydroxymethyl furfural (HMF) as a renewable feedstock for polymer synthesis has not yet been achieved as it is structurally asymmetric and contains three active functional groups. Reported here is the unprecedented step‐growth copolymerization of HMF and dihydrosilanes, through a coordination mechanism, to afford linear poly(silyl ether)s in the presence of B(C₆F₅)₃ and the heteroscorpionate zinc hydride complex LZnH L=(^MePz)₂CP(Ph)₂NPh, ^MePz=3,5‐dimethylpyrazolyl]. The adduct B(C₆F₅)₃???H???Zn, confirmed by NMR spectroscopy and DFT calculations, plays a key role in the synergistic catalysis, where B(C₆F₅)₃ activates ZnH and stabilizes the Zn⁺ active species, and the sterically bulky ZnH effectively inhibits (C₆F₅)₃B from reacting with dihydrosilane to form (C₆F₅)₃B‐H‐Si, which facilely initiates ring opening of furan. The mechanism was studied by DFT simulations.