Molecular and Crystal Structures of Some Fluorocymantrenes

Abstract

The crystal and molecular structures of the fluorocymantrenes [(C5H4F)Mn(CO)3] and [(C5H5−nFn)Mn (CO)2(PPh3)] (n = 1–3) have been studied. The influence of the phosphine for carbonyl substitution on the bond parameters is larger than the influence of the increasing fluorine content. In most cases the Mn → P vector is in a transoid position relative to the fluorine substituents, and therefore the conformational parameters of the PPh3 propeller are in these cases very similar. The crystal structures show many intermolecular C–H⋯O hydrogen bonds and only very few C–H⋯F hydrogen bonds. Graphic Abstract The influence of the phosphine for carbonyl substitution on the bond parameters of the fluorocymantrenes [(C5H4F)Mn(CO)3] and [(C5H5−nFn)Mn (CO)2(PPh3)] (n = 1–3) is larger than the influence of the increasing fluorine content.

From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene

“…32 Although the latter were used to prove the additive effect of fluorines on the ionization energy, 33 most of the studies were focused on the properties of Ru( 5 -C5F5)Cp*. [34][35][36][37] Di-and trifluorocymanthrene derivatives 38 have also been prepared, and isolated in pure form in small amount for crystallographic studies, 39 whilst synthetic routes to 1,2-difluoroferrocene have also been developed. 40 The first polyfluoroferrocene was prepared by Sünkel in 2015 from fluoroferrocene by iterative deprotometalation-NFSI (Nfluorobenzenesulfonimide) electrophilic trapping.…”

Synthesis and Coordination Chemistry of Fluorinated Cyclopentadienyl Ligands

“…10,11 Although less explored, the same strategy can also be used for half-sandwich complexes, e.g., containing manganese instead of iron. 12,13 A database survey in the Cambridge Crystallographic Database (CSD) revealed 49 hits for transition-metal cyclopentadienyl complexes with at least one fluorine substituent. The vast majority (43) of the complexes contained monofluorinated cyclopentadienyl ligands.…”