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The Taming of Redox‐Labile Phosphidotitanocene Cations
Author(s) -
Normand Adrien T.,
Bonnin Quentin,
Brandès Stéphane,
Richard Philippe,
FleuratLessard Paul,
Devillers Charles H.,
Balan Cédric,
Le Gendre Pierre,
Kehr Gerald,
Erker Gerhard
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805430
Subject(s) - homolysis , chemistry , electron paramagnetic resonance , ligand (biochemistry) , redox , crystallography , diphenylacetylene , oxidation state , photochemistry , lewis acids and bases , radical , stereochemistry , inorganic chemistry , metal , organic chemistry , catalysis , nuclear magnetic resonance , physics , receptor , biochemistry
Tame d 0 phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one‐electron oxidation of d 1 precursors with [Cp 2 Fe][BPh 4 ]. 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 d 0 complexes, whereas dπ–pπ repulsion prevents such interactions in the d 1 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 d 0 complexes were found to be light sensitive, and decompose through Ti−P bond homolysis to give Ti III species. A naked d 0 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.