Low-Coordinated Titanium(III) Alkyl-Molecular and Surface-Complexes: Detailed Structure from Advanced EPR Spectroscopy

Florian Allouche; Daniel Klose; Christopher P Gordon; Anton Ashuiev; Michael Wörle; Vidmantas Kalendra; Victor Mougel; Christophe Copéret; Gunnar Jeschke

doi:10.1002/anie.201806497

Low-Coordinated Titanium(III) Alkyl-Molecular and Surface-Complexes: Detailed Structure from Advanced EPR Spectroscopy

Angew Chem Int Ed Engl. 2018 Oct 26;57(44):14533-14537. doi: 10.1002/anie.201806497. Epub 2018 Jul 18.

Authors

Affiliations

¹ Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 1-5, 8093, Zürich, Switzerland.
² Faculty of Physics, Vilnius University, Sauletekio 3, 10257, Vilnius, Lithuania.
³ Current address: Department of Chemistry and Chemical Biology and The Baruch "60 Center for Biochemical Solar Energy, Rensselaer Polytechnic Institute, Troy, NY, 12180, USA.
⁴ Current address: Laboratoire de Chimie des Processus Biologiques, CNRS UMR 8229, Collège de France, Université Pierre et Marie Curie, 11 Place Marcelin Berthelot, 75231, Paris Cedex 05, France.

PMID: 29949230
DOI: 10.1002/anie.201806497

Abstract

The structure of paramagnetic surface species is notoriously difficult to determine. For Ti^III centers related to Ziegler-Natta catalysis, we demonstrate here that detailed structural information can be obtained by advanced EPR spectroscopy and DFT computations, benchmarked on molecular analogs. The hyperfine sublevel correlation (HYSCORE) spectra obtained after reaction with ¹³ C-labeled ethylene provides information about the coupling with a proton in the first coordination sphere of Ti^III as well as significant ¹³ C hyperfine coupling and thereby allows structural assignment of the surface species.

Keywords: EPR spectroscopy; catalysis; coordination chemistry; molecular models; surface chemistry.

Publication types

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

Abstract

Publication types

Grants and funding