Utilizing the Perfluoronaphthalene Radical Cation as a Selective Deelectronator to Access a Variety of Strongly Oxidizing Reactive Cations.

A selective deelectronation reagent with very high potential of +2.00 (solution) / +2.41 V (solid-state) vs. Fc+/0 and based on a room temperature stable perfluoronaphthalene (naphthaleneF) radical cation salt was developed and applied. The solid-state deelectronation of commercial naph-tha-leneF with [NO]+[F{Al(ORF)3}2]- generates [naphthaleneF]+∙[F{Al(ORF)3}2]- (ORF = OC(CF3)3) in gram scale. Thermo-chemical analysis unravels the solid-state de-electronation potential of the starting [NO]+-reagent to be +2.34 V vs. Fc+/0 with [F{Al(ORF)3}2]- counterion, but only +1.14 V vs. Fc+/0 with the small [SbF6]- ion. Selective reactions demonstrate the selectivity of [naphthaleneF]+∙ for deelectronation of a multitude of organ(ometall)ic molecules and elements in solution: providing the molecular struc-tures of the acene dications [tetracene]2+, [pentacene]2+ or spectroscopic evi-dence for the carbo-nyl complex of the ferrocene dication [Fc(CO)]2+, the [P9]+ cation from white phosphor-us, the solvent-free copper(I) salt starting from copper metal and the dicationic Fe(IV)-scorpionate complex [Fe(sc)2]2+.

Isolation, Structural and Physical Characterization as well as Reactivity of Persistent Acenium Radical Cation Salts.

The unsubstituted acenium radical cations (ARCs) are extremely sensitive and were hitherto only studied in situ, i. e. in the gas phase, as dilute solutions in strong acids or by matrix isolation spectroscopy at about 10 K. In this study, room temperature stable ARC salts with the weakly coordinating anion [F{Al(ORF )3 }2 ]- (ORF =-OC(CF3 )3 ) supported by the weakly coordinating solvent 1,2,3,4-tetrafluorobenzene (TFB) were prepared and structurally, electrochemically and spectroscopically characterized. Reaction of the neutral acenes with Ag+ [F{Al(ORF )3 }2 ]- led, non-innocent,[54] to intermediate [Ag2 (acene)2 ]2+ complexes, which decompose over time to Ag0 and the corresponding (impure) ARC salts. By contrast, direct deelectronation with the recently developed innocent[54] deelectronator radical cation salt [anthraceneHal ]+⋅ [F{Al(ORF )3 }2 ]- led to phase-pure products [acene]+⋅ [F{Al(ORF )3 }2 ]- (anthraceneHal =9,10-dichlorooctafluoroanthracene; acene=anthra-, tetra-, pentacene). For the first time, a homogenous set of spectroscopic data on analytically pure ARC salts was obtained. In addition, cyclovoltammetric measurements of the acenes connected the potentials in solution with those in the gas-phase. Hence, the data complement the existing isolated gas-phase, strong acid or matrix isolation studies. A first entry to follow-up chemistry of the acenium radical cations as ligand forming oxidizers was demonstrated by reaction with 1 / 2 ${{ 1/2 }}$ Co2 (CO)8 giving [Co(anthracene)(CO)2 ]+ .

Coordination versus Insertion: On the Interaction of 5 d-Transition Metal Carbonyl Clusters with Silver(I).

The title silver(I) complex salts [Ag{Re2 (CO)10 }{Re(CO)5 }2 ]+ [Al(ORF )4 ]- (AgRe4 ; ORF =-OC(CF3 )3 ) and [Ag{Ir4 (CO)12 }2 ]+ [Al(ORF )4 ]- (AgIr8 ) form upon reaction of Ag+ [Al(ORF )4 ]- and the transition metal carbonyls (TMCs) Re2 (CO)10 and Ir4 (CO)12 respectively. The solid-state structure of the AgRe4 cluster shows an unexpected asymmetric coordination motif, wherein the silver(I) cation has inserted into the Re-Re bond of one Re2 (CO)10 moiety, while the other dirhenium carbonyl coordinates only over one metal atom towards the silver(I) cation. The AgIr8 cluster is formed by the edge-on coordination of two Ir4 tetrahedra and the silver cation in a D2 symmetric fashion with a torsion angle of 46.5°. QTAIM analysis shows bond paths between the silver atom and the nearby metal atoms in all cases, whereas only the non-inserted Re2 (CO)10 moiety shows additional bond paths between the carbonyl ligands and the silver cation. In addition, the insertion of the Ag+ cation into the Re-Re bond in Re2 (CO)10 removes the bond path between the two rhenium atoms. The EDA-NOCV analysis suggests an increase of the interaction energy between the silver(I) cation and the respective metal carbonyls from the metal centered transition metal carbonyl (TMC) donors W(CO)6