The Taming of Redox-Labile Phosphidotitanocene Cations.
Adrien T NormandQuentin BonninStéphane BrandèsPhilippe RichardPaul Fleurat-LessardCharles H DevillersCédric BalanPierre Le GendreGerald KehrGerhard ErkerPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2019)
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 [Cp2 Fe][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.
Keyphrases
- solid state
- electron transfer
- ionic liquid
- electron microscopy
- density functional theory
- high resolution
- crystal structure
- hydrogen peroxide
- molecular dynamics simulations
- nitric oxide
- magnetic resonance imaging
- molecular docking
- magnetic resonance
- mouse model
- room temperature
- metal organic framework
- contrast enhanced