Abstract: | The facile synthesis of a stable and isolable compound with a fluoroalkynyl group, M?C≡CF, is reported. Reaction of Ru(C≡CH)(η5‐C5Me5)(dppe)] with an electrophilic fluorinating agent (NFSI) results in the formation of the fluorovinylidene complex Ru(=C=CHF)(η5‐C5Me5)(dppe)]N(SO2Ph)2]. Subsequent deprotonation with LiN(SiMe3)2 affords the fluoroalkynyl complex Ru(C≡CF)(η5‐C5Me5)(dppe)]. In marked contrast to the rare and highly reactive examples of fluoroalkynes that have been reported previously, this compound can be readily isolated and structurally characterized. This has allowed the structure and bonding in the CCF motif to be explored. Further electrophilic fluorination of this species yields the difluorovinylidene complex Ru(C=CF2)(η5‐C5Me5)(dppe)]N(SO2Ph)2]. |