Interaction of electroneutral benzenecyclopentadienyliron with halogen derivatives

Benchmarking of Gas‐Assisted Atomization Systems for Liquid Disintegration

“…2b 2 is rapidly oxidized to 2b + in chlorobenzene‐ d 5 in air, but shows good air stability in tetrahydrofuran‐ d 8 . All the dimers are readily oxidized in chloroform, consistent with previous reports of the reaction of (cyclopentadienyl)(benzene)iron dimer with alkyl halides 14…”

“…Although the focus of this paper is primarily on dimers incorporating the costly elements ruthenium and rhodium, it should be remembered that dopants are often used at low levels and only in a small portion of a device. Moreover, a few dimeric (cyclopentadienyl)(arene)iron dimers10, 14 are known and we have also shown that one such example, 2c 2 , behaves in a similar fashion to the Rh and Ru species. While we have shown that the dimers can be handled in air prior to device fabrication, solution‐processing of the inevitably air‐sensitive doped films, at least for the example of IIb doped with rhodium or ruthenium dimers, should be carried out in inert atmosphere since significant formation of the sensitive ETM radical anion takes place on the timescale of spin‐coating or drop‐casting.…”

“…Several other related dimeric systems are known; to test the generality and tunability of the approach the known (pentamethylcyclopentadienyl)(1,3,5,‐trimethylbenzene)ruthenium dimer,9 2a 2 , and its new triethyl analogue, 2b 2 , were synthesized (Figure 2). While most of the reported dimers of this type incorporate costly 4d or 5d transition metals, certain (cyclopentadienyl)(arene)iron compounds also form dimers,10, 14 and so 2c 2 was also synthesized. The ruthenium and iron compounds show comparable air stability to 1 2 in both the solid state (stable for weeks) and in benzene‐ d 6 (ca.…”

“…Compared to previously examined approaches to air‐stable precursors to molecular n‐dopants, our approach has the advantages that chemical side reactions are likely to be minimized and that the dopants are highly reducing, n‐doping ETMs with relatively low EAs, such as IIa and IIb . Moreover, a number of different dimers of this type are known,8–10, 14, 20–22 and additional examples can potentially be developed, allowing properties such as solubility, volatility, and monomer and dimer redox potentials to be varied. Although the focus of this paper is primarily on dimers incorporating the costly elements ruthenium and rhodium, it should be remembered that dopants are often used at low levels and only in a small portion of a device.…”

Reductively Induced Dimerization of the Ligated Benzene in [Mn(η6-C6H6)(CO)3]+: Formation of the Initial C−C Bond by Anion/Cation Addition

“…This unprecedented transition metal promoted dimerization is an interesting addition to the known reactions of benzene, and our interest in potential applications has led to a mechanistic study which has now established (Scheme ) that the reaction proceeds through the dimer [{Mn(CO) 3 } 2 {μ(η 5 -C 6 H 6 -η 5 -C 6 H 6 )}] ( 3 ), which is itself formed by addition of [Mn(η 4 -C 6 H 6 )(CO) 3 ] - ( 4 - ) to 1 + to give the key C−C bond. An ionic coupling step is in surprising contrast with the radical coupling mechanism established for reductive dimerization of [Fe(η 5 -C 5 H 5 )(η 6 -C 6 H 6 )] + to [{Fe(η 5 -C 5 H 5 )} 2 {μ(η 5 -C 6 H 6 -η 5 -C 6 H 6 )}] , and raises the intriguing possibility of using the reaction to cross couple arenes since there is a clear distinction between the arenes in 4 - and 1 + prior to coupling.…”