The Taming of Redox-Labile Phosphidotitanocene Cations |
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Authors: | Dr. Adrien T. Normand Dr. Quentin Bonnin Dr. Stéphane Brandès Dr. Philippe Richard Prof. Paul Fleurat-Lessard Dr. Charles H. Devillers Cédric Balan Prof. Pierre Le Gendre Dr. Gerald Kehr Prof. Gerhard Erker |
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Affiliation: | 1. ICMUB, UMR CNRS 6302, Université de Bourgogne, UFR sciences et techniques, 9 rue Alain Savary-BP 47870, 21078 Dijon Cedex, France;2. Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149 Münster, Germany |
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Abstract: | Tame d0 phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d1 precursors with [Cp2Fe][BPh4]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π-interactions between the phosphido ligand and Ti in the d0 complexes, whereas dπ–pπ repulsion prevents such interactions in the d1 complexes. In addition, CH–π interactions were observed in several complexes, both in solution and in the solid state, between the phosphido ligand and the phosphane arm. The d0 complexes were found to be light sensitive, and decompose through Ti−P bond homolysis to give TiIII species. A naked d0 phosphidotitanocene cation has been trapped by reaction with diphenylacetylene, yielding a Ti/P frustrated Lewis pair (FLP), which was found to be less reactive than a previously reported Zr analog. |
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Keywords: | density functional theory (DFT) frustrated Lewis pair (FLP) phosphorus ligands titanium transition metal phosphides |
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