Transformation of Metal–Organic Framework Secondary Building Units into Hexanuclear Zr-Alkyl Catalysts for Ethylene Polymerization

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-...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2017-08, Vol.139 (33), p.11325-11328
Main Authors: Ji, Pengfei, Solomon, Joseph B, Lin, Zekai, Johnson, Alison, Jordan, Richard F, Lin, Wenbin
Format: Article
Language:English
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Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b05761