Synthesis and characterization of perhalogenated triphenylphosphine-cymantrenes [(C5X5)Mn(CO)2(PPh3)] (X = F, Cl, Br) and [(C5HI4)Mn(CO)2(PPh3)]

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.…”

Molecular and Crystal Structures of Some Fluorocymantrenes

“…The synthesis and characterization of all compounds was published elsewhere recently [17]. Although the spectroscopic data have already been reported, the NMR data are collected here once again: The pre-purified compounds obtained after column chromatography were dissolved at r.t. in the minimum amount of an 85:15 mixture of petroleum ether/diethyl ether and transferred in an open vial to a refrigerator operating at + 5 °C.…”

“…In both molecules the fluorine atom is disordered over two positions at C3/C6 and C33/C35, with one orientation clearly dominating (87% in A, 97% in B). An alternative interpretation (and quite possible regarding the contamination of 2 with 3 even after chromatography, [17] of the disorder would be co-crystallization of 2 and 3. Refinement of such a situation gave slightly worse R-values.…”

“…Most of the experimental work on fluorometallocenes after 2011 was done with the ferrocene system, mainly by the group of Erb at the University of Rennes [8,15,16]. Although fluorocymantrene was the very first fluorometallocene prepared [10], there were no other reports on it until very recently [17]. This seems astonishing, considering the still active research on cymantrene derivatives in cancer research on one hand [18,19], and the importance of 18 F-labeled arenes in Positron Emission Tomography (PET) [4].…”

Crystal and molecular structures of some phosphane-substituted cymantrenes [(C5H4 X)Mn(CO)LL′] (X = H or Cl, L = CO, L′ = PPh3 or PCy3, and LL' = Ph2PCH2CH2PPh2)

“…Synthesis of 1b. Compound 1b was prepared according to the method reported by Klein-Hessling et al (2021). Recrystallization from petroleum ether (with some added Et 2 O) by slow evaporation in a refrigerator at 5 C yielded crystals.…”