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

Pengfei Ji; Joseph B Solomon; Zekai Lin; Alison M. Wilders; Richard F Jordan; Wenbin Lin

doi:10.1021/jacs.7b05761

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

J Am Chem Soc. 2017 Aug 23;139(33):11325-11328. doi: 10.1021/jacs.7b05761. Epub 2017 Aug 15.

Authors

Pengfei Ji¹, Joseph B Solomon¹, Zekai Lin¹, Alison M. Wilders¹, Richard F Jordan¹, Wenbin Lin¹

Affiliation

¹ Department of Chemistry, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.

PMID: 28797163
DOI: 10.1021/jacs.7b05761

Abstract

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.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.