No abstract

Persulfurateda renes are af ascinating class of functional molecules with aw ider ange of potentiala pplications. Ferrocenes are also am ultifaceted class of aromatic compounds that can easily be finetuned for an enormous variety of desired properties. Ac ombinationo f both substancec lasses might yield an even wider field of applications. Herein, we describe the synthesis of two ferrocenesw ith one persulfurated cyclopentadienyl ring [C 5 (SR) 5 ], with R = Me or Ph, together with their crystal structures, optical, and electrochemical properties. Both crystal structures show significant intramolecular sulfuriron interactions as well as weak intermoleculars ulfurcontacts. Cyclovoltammetry of the [C 5 (SPh) 5 ]c ompound shows ah igho xidationp otentialo f6 51 mV vs. FcH/FcH + .Persulfurated arenes still remain an underexploited field of chemistry,d espite their highly interesting physical organic properties and their numerous possible applications, ranging from ion-selectivem embranes over organic conductors and ferromagnets to cation sensors andl iquid crystals. [1] This statement made by M. Gingras in af ascinatingr eview article in this journal more than 10 years ago is still valid. There have been, however,s everali nteresting additions to this field, particularly with extended aromatic systems. Per(arylthio)corannulenes and -coronenes have found potential applicationa sp hotovoltaic devices [2] and for molecular electronics. [3] Substituted hexakis(phenylthio)benzenes showeds trong phosphorescence in the solid state with the potential of OLED applications. [4] Dendrimersw ith a[ C 6 (SAr) 6 ]c ore, so-called" molecular asterisks" have been used as multifunctional ligandsf or the preparation of luminescents ensors and asymmetric metal catalysis. [5] The interesting electronic properties sharedb yt his compound class are mainly due to the fact that "phenylthio substituents attached to aromatic cores result in ar eduction of the HOMO-LUMOg ap", [1, 2a] "primarily due to LUMO stabilization". [6] Upon addition of SPh groups ab athochromic shift of the longest wavelength absorption by 10-15 nm is observed together with an increaseofthereductionpotential by 0.1 V. [2b] Metallocenes are another very important group of aromatics with very interestinge lectronic properties. However,w hile quite af ew metal-freep ersulfurated arenes have been studied, there seem to be no reports of persulfuratedferrocenes. The fivefolds ymmetry of metallocenes would create as tructural motifr arely found with thioether-based "moleculara sterisks" (Scheme 1). [7] While the syntheses of persulfurated cyclopentadienyl anions[ C 5 (SR) 5 ] À (R = Me, Ph) was already reported in the 1980s, [8] attempts to prepare metallocenes from them via reactions with metal halidesm et with failure. However,t he complexes[ C 5 (SMe) 5 ]ML n (ML n = Mn(CO) 3 ,R uCp*) could be obtainedv ia post-functionalization of an already coordinated cyclopentadienyl ring. [9,10] Transfer of this syntheticp rotocol using perhalogenatedo rp ermercurated ferroce...

The pentachloroferrocenes [C5Cl5]Fe[C5H4X] (X = H, Br, SMe) react with LiTMP and MeSSMe to form mixtures of compounds, that contain besides the expected products of deprotonation also one or more complexes with a [C5Cl4(SMe)] ligand. This latter observation makes the otherwise rarely observed occurrence of “halogen dance reactions” in chloroaromatics very probable. 1,2,3‐Trichloroferrocene yields with BuLi and MeSSMe products of both halogen‐metal‐exchange and of deprotonation. Additionally, in all examined systems, the observation of some highly‐substituted complexes with eight or more substituents hints to the involvement of cyclopentadienyl exchange reactions, which has also rarely been observed under such mild conditions. The molecular structures of [C5Cl4(SMe)]Fe[C5H3BrX] (X = SMe or SOMe), [C5Cl4(SMe)]Fe[C5H2Cl(SMe)2], [C5Cl2(SMe)3]2Fe, and [C5HCl3(SMe)]2Fe have been determined by X‐ray diffraction.

Crystals of the aminotetracyanocyclopentadienyl radical were obtained from the reaction of CaCl2 with Ag[C5(CN)4(NH2)] and recrystallization in MeOH was performed in sunlight.

The reaction of Tl(C 5 H 5 ) with Ag[C 5 (CN) 5 ] gives unexpectedly the title compound. Its crystal structure shows a dimeric [Tl 2 [C 5 (CN) 2 ] 2 ] forming the asymmetric unit. These units are connected to "layers" perpendicular to the a axis with formation of numerous 4-, 9-and 14 membered rings, with the Tl ions using three nitrile functions from three different ligands. These layers are connected in a direction with each Tl ion coordinating to three more nitrile functions and additional weak delocalized η 5 or η 3 interactions with a cyclopentadienyl ring.