[Tc(NO)Cl(PPh)(CHCN)] and Its Reactions with 2,2'-Dipyridyl Dichalcogenides.

The sparingly soluble technetium(I) complex [Tc(NO)Cl(PPh)(CHCN)] () slowly dissolves during reactions with 2,2'-dipyridyl ditelluride, (2-pyTe), 2,2'-dipyridyl diselenide, (2-pySe), or 2,2'-dipyridyl disulfide, (2-pyS), under formation of deeply colored solutions. Blue (Te compound) or red solids (Se compound) of the composition [{Tc(NO)Cl(PPh)}{µ-(2-pyE)}], E = Te (), Se (), precipitate from the reaction solutions upon addition of toluene. They represent the first technetium complexes with dichalcogenides.

On pyridine chloronium cations.

We present the first solid-state structural evidence of mono- and bis(pyridine)chloronium cations. The latter was synthesized from a mixture of pyridine, elemental chlorine and sodium tetrafluoroborate in propionitrile at low temperatures. The mono(pyridine) chloronium cation was realized with the less reactive pentafluoropyridine, using ClF, AsF, and CFN in anhydrous HF.

A decacationic ferrocene-based metallostar.

Decacationic metallostars have been prepared by the reaction of permercurated ferrocene FeC(HgOCCF) with superacidic (CFNH)(SbF) (p = -11 estimated in HO) in multigram scale. In the resulting compound, [FeCHg(NCF) ][SbF], the labile pentafluoropyridine ligands are readily displaced by acetonitrile (MeCN) or tetrahydrothiophene (THT). In the X-ray structure of [FeCHg(THT)][SbF]·24 MeCN no cation-anion contacts between mercury and fluorine were observed.

Increasing the oxidation power of TCNQ by coordination of B(CF).

The oxidation power of the cyanocarbon TCNQ (tetracyano-quinodimethane) can be significantly increased to approximately = +0.9 V CpFe by coordination of up to four equivalents of the strong fluorinated Lewis acid B(CF), resulting in a highly reactive but easy-to-use oxidation system. Thianthrene and tris(4-bromophenyl)amine were oxidized to the corresponding radical cations.

Eightfold Electrophilic Methylation of Octacyanotungstate [W(CN)]: Preparation of Homoleptic, Eight-Coordinate Methyl Isocyanide Complexes [W(CNMe)].

Homoleptic eightfold coordinated methyl isocyanide complexes of W(IV) and W(V) have been prepared for the first time. The reaction of [NBu][W(CN)] with methyl triflate (MeOTf) gives [W(CNMe)][OTf]. The even stronger methylating mixture of methyl fluoride (MeF) and arsenic pentafluoride (AsF) in liquid sulfur dioxide (SO) is able to fully alkylate both [NBu][W(CN)] and [NBu][W(CN)].

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC (HgX).

The permercuration of ferrocene was achieved by reacting ferrocene with 10 equivalents of mercury(II) butyrate Hg(O CC H ) in a facile one-pot reaction in multi-gram scale and high yields. The butyrate groups in FeC (HgX) (X=O CC H ) can be exchanged by treatment with trifluoro- or trichloroacetic acid (X=O CCF , O CCCl ). Substitution of the trifluoroacetate groups by halides (X=Cl, F) proceeds easily in aqueous THF.

The [2+2] cycloaddition product of perhalogenated cyclopentadienyl cations: structural characterization of salts of the [CCl] and [CBr] dications.

Instead of monomeric cyclopentadienyl cations, the low-temperature reaction of hexachloro- and hexabromocyclo-pentadiene (C5Cl6 and C5Br6) with powerful Lewis acids SbF5 and AsF5 in SO2ClF yields salts of perhalogenated dications [C10Cl10][Sb3F16]2 and [C10Br10][As2F11]2 which are characterized via single crystal X-ray diffraction and NMR spectroscopy. Additionally, this reactivity is rationalized by quantum-chemical calculations.