Crystallographic Characterization of Difluoropropargyl Indium Bromide, a Reactive Fluoroorganometallic Reagent

Abstract

Geschnappt: Difluorpropargyl‐Gruppen mit γ‐Substituenten können einen Organoindium(III)‐Komplex stabilisieren. Die daraus resultierende Struktur ist die einzige, in der ein Indiumatom an ein propargylisches Kohlenstoffatom gebunden ist (siehe Bild; F blau, S gelb, C weiß, H grün). Die Umsetzung mit Elektrophilen lieferte je nach Elektrophil ein Difluoralkin oder ein Difluorallen.

Direct Preparation of Trifluoromethylindium Reagents from Trifluoromethyl Iodide: Effective Trifluoromethylation and Perfluoroalkylation Reagents

“…Herein, we report the direct synthesis of trifluoromethylindium reagents prepared from trifluoromethyl iodide by using just one equivalent each of indium, lithium chloride10 or sodium iodide,9,11 and ferrocene, and the carbonyl addition reactions of these reagents were also studied (Scheme ). On the basis of our own DFT calculations on the global minimum configuration of the putative trifluoromethylindium complexes (Scheme ) at the MP2(full)/DGDZVP level in acetonitrile (Supporting Information), we confirmed that essentially no In ··· F interaction in the trifluoromethylindium complexes was present,12 which is in stark contrast to its lithium counterpart (Supporting Information): Kvíčala has already reported that the localized structure of CF 3 Li has a bridged three‐membered C – –F ··· Li + structure that has a highly twisted form that leads to α‐elimination of LiF 12,13…”