title: Small molecule activation: SbF3auto-ionization supported by transfer and mesoionic NHC rearrangement.
abstract: The reactivity of antimony trifluoride, SbF3, in non-polar aprotic solvents has been unexplored due to its negligible solubility. The reaction of the [SbF3(tmen)] complex (2) with the N-heterocyclic carbene, 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, (LDipp), probably leads to the formation of a neutral [(LDipp)SbF3] intermediate (3) in non-polar solvents. Mild heat treatment of the reaction mixture unexpectedly activates the SbF3molecules to undergo the auto-ionization reaction. In this process, one of the (LDipp) ligands undergoes rearrangement into the mesoionic carbene (MIC) and further coordinates to the cation to form [(LDipp)2SbF2]+[SbF4]-, product (4). Studies have confirmed that N,N,N',N'-tetramethylethane-1,2-diamine (tmen) present in the solution is not involved in the conversion mechanism and serves solely as an auxiliary ligand to increase the solubility of SbF3. The compound (4) shows a rare pnictogen(iii) halide auto-ionization process with the first mesoionic NHC rearrangement on any metal/metalloid fluoride compound and the first reported reaction system where a N-heterocyclic carbene ligand facilitates the auto-ionization process on a fluorido substrate.
authors.affiliation: Jožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia. gasper.tavcar@ijs.si and Jožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia.
authors.forename: Blaž
authors.identifier: http://orcid.org/0000-0002-8845-4335
authors.initials: B
authors.lastname: Alič
authors.affiliation: Jožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia. gasper.tavcar@ijs.si and Jožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia.
authors.forename: Aleš
authors.initials: A
authors.lastname: Štefančič
authors.affiliation: Jožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia. gasper.tavcar@ijs.si and Jožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia.
authors.forename: Gašper
authors.initials: G
authors.lastname: Tavčar