Abstract: Isolation of six extensively rearranged products (I-VI) from reactions of sulfur tetrafluoride with hexa-fluoroisopropylideniminolithium demonstrates that simple, metathetical reactions do not occur. A possible mechanism is proposed. Similar rearranged products (VII-IX) form from the lithium salt with CF3SF3 and (CF3)* SF2. Long-range coupling of nuclei separated by ten u bonds is observed in the lQF nmr spectrum of 111. ...