Reactivity and conformation of a phosphine-substituted dihalocarbene complex. X-ray crystal structures of [(.eta.5-C5H5)Fe(CO)(PPh3)(CF2)][BF4] and [(.eta.5-C5H5)Fe(CO)2(CCl2)][BCl4]

The Trifluoromethyl Group in Transition Metal Chemistry

“…80 %) 112. The fact that the Fe=CF 2 distance (172.4 pm) in the solid‐state structure (X‐ray) is significantly shorter than the Fe=CCl 2 distance (180.8 pm) observed in the related dichlorocarbene complex [CpFe(CO) 2 (=CCl 2 )] + was attributed to the strong π‐acceptor character of the difluorocarbene unit owing to the high electronegativity of the fluorine substituents 115. The compound suffered rapid hydrolysis when exposed to moisture to afford [CpFe(CO) 3 ][BF 4 ].…”

Fluorine as a ligand substituent in organometallic chemistry: A second chance and a second research career

“…Transition metal complexes containing CF 2 ligands were already well known [71,72,76,[91][92][93][94][95][96], but perfluoroalkylidene analogues were not generally accessible. If these reactions are done in the dark they result in clean formation of 37 and 38; [97] it should be noted that the stereochemistry of 37 was incorrectly assigned by us in the original publication [89].…”

Conversion of Carbon–Fluorine Bonds α to Transition Metal Centers to Carbon–Hydrogen, Carbon–Carbon, and Carbon–Heteroatom Bonds

“…(2) Abstraction of fluoride from M-CF 3 groups to give cationic [M=CF 2 ] + compounds was also discovered, along with the realization that these cations were extremely sensitive to attack by water to give HF and a cationic CO complex [Equation (3)]. [138] In the examples shown in Equation (3), the cationic CF 2 complexes could only be observed in solution by NMR spectroscopy, but similar reactions afforded isolable analogues, [MoCp*(CO) 3 [140] which were crystallographically characterized, but which were also extremely reactive towards reaction with water to give cationic CO complexes. BF 3 [138][139][140][141][142][143][144][145] and protic acids [137,[146][147][148] have been shown to act as fluoride acceptors, leading to similar hydrolysis reactions.…”