Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49Ti Solid-State Nuclear Magnetic Resonance Spectroscopy

29 January 2024, Version 3
This content is a preprint and has not undergone peer review at the time of posting.


Treatment of Ziegler-Natta (ZN) catalysts with BCl3 improves their activity by increasing the number of active sites. Here we show how 47/49Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables to understand the electronic structure of the Ti surface sites present in such ZN pre-catalysts, prior to activation with alkyl aluminium. High-field (21.1 T) and low temperature (~100 K) NMR augmented by DFT modelling on the pre-catalyst and corresponding molecular analogues enables the detection of 47/49Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associate Ti surface sites exhibit 49Ti NMR signatures (δiso, exp = –170 ppm / CQ, exp = 9.3 MHz / κ = 0.05) corresponding to well-defined fully chlorinat-ed hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl2 support, formed upon post-treatment with BCl3 and re-moval of the alkoxo ligands, paralleling with the increased polymerization activity.


Ziegler-Natta catalysts
Solid-State NMR
DFT calculations
High-field 47/49Ti NMR

Supplementary materials

Supporting Information
Synthesis protocols and corresponding solution NMR, single-crystal XRD structures, solid-state NMR measurement parameters and additional spectra, DFT calculation protocol for NMR parameters.


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