Pengfei Ji†, Joseph B. Solomon†, Zekai Lin, Alison Johnson, Richard F. Jordan, and Wenbin Lin*
We report the stepwise and quantitative transformation of the Zr6(μ3-O)4(μ3-OH)4(HCO2)6 nodes in Zr-BTC (MOF-808) to the [Zr6(μ3-O)4(μ3-OH)4Cl12]6– nodes in ZrCl2-BTC, and then to the organometallic [Zr6(μ3-O)4(μ3-OLi)4R12]6– nodes in ZrR2-BTC (R = CH2SiMe3 or Me). Activation of ZrCl2-BTC with MMAO-12 generates ZrMe-BTC, which is an efficient catalyst for ethylene polymerization. ZrMe-BTC displays unusual electronic and steric properties compared to homogeneous Zr catalysts, possesses multimetallic active sites, and produces high-molecular-weight linear polyethylene. Metal–organic framework nodes can thus be directly transformed into novel single-site solid organometallic catalysts without homogeneous analogs for polymerization reactions.