Redox reactions of metallocenes with tungsten and molybdenum hexafluoride

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

“…[306] Interestingly,e ach second-row transition-metal hexafluoride is as tronger oxidant than the heavier third-row congener in the same group.T he calculated oxidation potentials indicate the same general increase from left to right across the period, although the oxidation potential of RuF 6 (7.01 eV) is higher than that of RhF 6 (6.80 eV) on account of the stable electronic configuration of [RuF 6 ] À . [303] is the use of MoF 6 and WF 6 [308] Ar ecent example of the use of ReF 6 as an oxidant, as well as other more common oxidants (EF 5 ,w here E = As or Sb) and [XeF][Sb 2 F 11 ]inHF/SbF 5 ), is the formation of the decamethylferrocenium dication [(Cp*) 2 Fe][ReF 6 ] 2 ,w hich was formed by oxidation of (Cp*) 2 Fe in SO 2 .I nterestingly, the solid-state structure is influenced by the WCAss upporting the [(Cp*) 2 Fe] 2+ dication. Thef ormation of the corresponding metal anion or dianion then generates the supporting WCA.D espite the attractive tunability of MF 6 oxidants,their high reactivity and specialist handling requirements make them relatively underused as general oxidants.…”

“…[303] is the use of MoF 6 and WF 6 for the oxidation of ferrocene and cobaltocene to form [Cp 2 Fe][MF 6 ](where M = Mo or W) and [Cp 2 Co(NCMe) 2 ] n [MF 6 ]( where n = 1, M = W; n = 2, M = Mo). [308] Ar ecent example of the use of ReF 6 as an oxidant, as well as other more common oxidants (EF 5 ,w here E = As or Sb) and [XeF][Sb 2 F 11 ]inHF/SbF 5 ), is the formation of the decamethylferrocenium dication [(Cp*) 2 Fe][ReF 6 ] 2 ,w hich was formed by oxidation of (Cp*) 2 Fe in SO 2 .I nterestingly, the solid-state structure is influenced by the WCAss upporting the [(Cp*) 2 Fe] 2+ dication. Thet ilt observed in the Cp* rings is greater with the smaller [EF 6 ] À (where E = Re,Sb, or As) WCAs, through closer approach of one of the fluoride ligands towards the iron center, than with the larger [E 2 F 11 ] À (where E = Sb or As) WCAs.…”

Electrochemical evidence for the existence of three stable oxidation states for heterocycles of the type XC6H4CN2E2 (E = S, Se). X‐ray crystal structure of the dimer with X = Cl, E = S

“…Electrochemical experiments were performed on a platinum three-electrode system with the platinum working electrode either a Pt-wire or a 0.5 mm diameter Pt-micro-tip. The vacuum-tight all glass cell has been described in detail elsewhere [22]. The cell was charged with electrolyte (NBu4PF6), and the solvent, dry degassed CH3CN or CH,Cl, transferred on a vacuum line.…”

Electrochemistry of methylidyne and 1,2,3,5-dithiadiazole complexes of iron and nickel and a reinterpretation of the composition of "PhCN2S2Fe2(CO)6"

“…A positive feedback circuitry was employed to minimize iR drop losses. The vacuum-tight all-glass electrochemical cell has been described in detail elsewhere (1). The cell was charged with the supporting electrolyte (NBu,PF6) at a concentration of 0.05 mol L-'.…”

“…The enhanced chemical reactivity of many low-valent organometallic compounds, compared to classical coordination compounds, requires the use of special handling techniques, including specialized electrochemical cells and the use of nonaqueous solvents. In this work we use cyclic voltammetry to study several organometallic cluster compounds using an original cell design that is equally capable of operating under a vacuum or a carbon monoxide atmosphere (1). The methylidyne complexes [Fe,(CO),(p-CX),], 1, (X = F, C1, Br, H) (2) and the so-called dithiadiazole complexes [Fe,(CO),-(S,N,CPh)], 2a, and [Ni,Cp,(S,N,CPh)] 3 (3) were investigated.…”