Acceptor-Substituted Cyclopentadienyl Compounds

Efficient methodologies for the synthesis of acceptor-substituted perfunctionalized cyclopentadienyl (Cp) compounds were investigated. A facile multigram, one-pot synthesis of [FeC10(HgO2CC3H7)10] from ferrocene and Hg(O2CC3H7)2 is reported. In the corresponding compound, the Hg-C bonds are inert towards oxygen, moisture and even strong Brønsted acids like trifluoroacetic acid and [C5F5NH][SbF6]. Instead, protonation of the carboxylic groups is observed yielding [FeC10(HgO2CCF3)10] and [FeC10Hg10(C5F5N)n][SbF6]10. In the compound [FeC10Hg10(C5F5N)n][SbF6]10, the labile C5F5N ligands are readily displaced by MeCN or tetrahydrothiophene (THT) to afford rare examples of organometallic decacations [FeC10(HgL)10][SbF6]10 (L = MeCN, THT). Electrochemical investigations on the (soluble) permercurated compounds reveal increasing redox potentials of the corresponding Fe(II)/Fe(III) redox couples with increasing Lewis acidity of the Hg-sites. The isolation of the oxidized forms was realized by reaction with [NO]+ or [NO2]+ salts or MoF6. Furthermore, the first crystallographic characterization of permetalated aromatic compounds [FeC10(HgX)10] (X = Cl, O2CCF3, O2CCCl3), [FeC10(HgTHT)10][SbF6]10 and [FeC10(HgMeCN)10][SbF6]10[MoF6] is presented. Complete halodemercuration is observed in the reaction of [FeC10(HgO2CC3H7)10] with K[Br3] followed by halogenation with FeBr3 and elemental Br2. An oxidation potential of E1/2 = 1.1V renders the corresponding ferrocenium cation as potent oxidizing agent. The isolation is realized by reaction of [FeC10Br10] with AsF5. Further functionalization of [FeC10Br10] is achieved by metalation with elemental Mg or by lithium-halogen-exchange with tBuLi. Quenching experiments with dimethylsilylchloride (DMSCl) yielded polysilylated compounds. Full functionalization was achieved after multiple metalation-silylation sequences. The resulting product [FeC10DMS10] displays the first example of a persilylated metallocene. A series of polysilylated derivatives [FeC10DMSnH10-n] (n = 7, 8, 9, 10) is analyzed by CV, single-crystal XRD, NMR and UV/VIS spectroscopy to evaluate the effect of silylation on the electronic properties of metallocenes. The obtained data are supported by quantum-chemical calculations. In the context of perhalogenated Cp compounds, the reaction of C5X6 (X = Cl, Br) with AsF5 and SbF5 is investigated. Here, the formation of unprecedented [2+2]-cycloaddition products of two Cp cations [C5X5]+ is observed. The obtained dications [C10X10]2+ are analyzed by XRD and NMR spectroscopy. DFT calculations reveal that the dimerzation to [2+2]- instead of [2+4]-products is thermodynamically preferred due to the formation of two allylic p-electron systems. Furthermore, in cooperation with the group of Prof. Dr. Schulz the electrochemical properties of [C5(C6F5)5]+ are presented

Tenfold Metalation of Ferrocene: Synthesis, Structures and Metallophilic Interactions in FeC10(HgX)10

The permercuration of ferrocene was achieved by reacting ferrocene with 10 equivalents of mercury(II) butyrate Hg(O2CC3H7)2 in a facile one‐pot reaction in multi‐gram scale and high yields. The butyrate groups in FeC10(HgX)10 (X=O2CC3H7) can be exchanged by treatment with trifluoro‐ or trichloroacetic acid (X=O2CCF3, O2CCCl3). Substitution of the trifluoroacetate groups by halides (X=Cl, F) proceeds easily in aqueous THF. The completeness of metalation was confirmed by NMR and vibrational spectroscopy, mass spectrometry, as well as elemental analysis. Additionally, the first crystal structures of permetallated metallocenes are presented: FeC10(HgX)10 (X=Cl, O2CCF3, O2CCCl3)

Increasing the oxidation power of TCNQ by coordination of B(C6F5)3

The oxidation power of the cyanocarbon TCNQ (tetracyano-quinodimethane) can be significantly increased to approximately E = +0.9 V vs. Cp2Fe by coordination of up to four equivalents of the strong fluorinated Lewis acid B(C6F5)3, resulting in a highly reactive but easy-to-use oxidation system. Thianthrene and tris(4-bromophenyl)amine were oxidized to the corresponding radical cations. Dianionic [TCNQ·4 B(C6F5)3]2− was formed upon reduction with two equivalents of ferrocene or decamethylcobaltocene. [TCNQ·4 B(C6F5)3]− and [TCNQ·4 B(C6F5)3]2− are rare cases of redox-active weakly-coordinating anions

A Decacationic Ferrocene-Based Metallostar

Decacationic metallostars have been prepared by the reaction of permercurated ferrocene FeC10(HgO2CCF3)10 with superacidic (C5F5NH)(SbF6) (pKa = −11 estimated in H2O) in multigram scale. In the resulting compound, [FeC10Hg10(NC5F5)n][SbF6]10, the labile pentafluoropyridine ligands are readily displaced by acetonitrile (MeCN) or tetrahydrothiophene (THT). In the X-ray structure of [FeC10Hg10(THT)10][SbF6]10 ‧ 24 MeCN no cation-anion contacts between mercury and fluorine were observed. Moreover, cyclic voltammetry measurements of [FeC10(Hg(MeCN))10]10+ and [FeC10(Hg(THT))10]10+ revealed a (quasi)reversible one-electron oxidation of Fe(II) to Fe(III). From the reaction of [FeC10(Hg(MeCN))10]10+ with MoF6 as oxidant the ferrocenium cation [FeC10(Hg(MeCN))10]11+ was obtained and characterized via single crystal XRD. These electrophilic metallostars are promising potential building blocks for the synthesis of dendritic architectures containing a robust, tenfold functionalized ferrocene core

A decacationic ferrocene-based metallostar

Decacationic metallostars have been prepared by the reaction of permercurated ferrocene FeC10(HgO2CCF3)10 with superacidic (C5F5NH)(SbF6) (pKa = −11 estimated in H2O) in multigram scale. In the resulting compound, [FeC10Hg10(NC5F5)n][SbF6]10, the labile pentafluoropyridine ligands are readily displaced by acetonitrile (MeCN) or tetrahydrothiophene (THT). In the X-ray structure of [FeC10Hg10(THT)10][SbF6]10·24 MeCN no cation–anion contacts between mercury and fluorine were observed. Moreover, cyclic voltammetry measurements of [FeC10(Hg(MeCN))10]10+ and [FeC10(Hg(THT))10]10+ revealed a (quasi)reversible one-electron oxidation of Fe(II) to Fe(III). From the reaction of [FeC10(Hg(MeCN))10]10+ with MoF6 as oxidant the ferrocenium cation [FeC10(Hg(MeCN))10]11+ was obtained and characterized via single crystal XRD. These electrophilic metallostars are promising potential building blocks for the synthesis of dendritic architectures containing a robust, tenfold functionalized ferrocene core

Eightfold Electrophilic Methylation of Octacyanotungstate [W(CN)8]4−/3−: Preparation of Homoleptic, Eight-coordinate Methylisocyanide Complexes [W(CNMe)8]4+/5+

Homoleptic eight-fold coordinated methylisocyanide complexes of W(IV) and W(V) have been prepared for the first time. The reaction of [NBu4]4[W(CN)8] with methyl triflate MeOTf gives [W(CNMe)8][OTf]4. The even stronger methylating mixture of methyl fluoride MeF and arsenic pentafluoride AsF5 in liquid sulfur dioxide SO2 is able to fully alkylate both [NBu4]4[W(CN)8] and [NBu4]3[W(CN)8]. The paramagnetic octakis(methylisocyanide)- tungsten(V) [W(CNMe)8][AsF6]5 is thermally highly unstable above −30 °C. All compounds have been characterized via single-crystal X-ray diffraction, IR and Raman, as well as NMR or EPR spectroscopy<br /

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, AsF5, and C5F5N in anhydrous HF. During the course of this study, we also investigated pyridine dichlorine adducts and found a surprising disproportionation reaction of chlorine that depended on the substitutional pattern of the pyridine. Electron richer dimethylpyridine (lutidine) derivatives favor full disproportionation into a positively and a negatively charged chlorine atom which forms a trichloride monoanion, while unsubstituted pyridine forms a 1 : 1 py·Cl2 adduct

Structural Characterization and Bonding Analysis of [Hg{Fe(CO)5}2]2+ [SbF6]-2

The non-classical carbonyl complex [Hg{Fe(CO)5}2]2+ [SbF6]-2 is prepared by reaction of Hg(SbF6)2 and excess Fe(CO)5 in anhydrous HF. The single-crystal X-ray structure reveals a linear Fe-Hg-Fe moiety as well as an eclipsed conformation of the eight basal CO ligands. Interestingly, the Hg-Fe bond length of 2.5745(7) Angstrom is relatively similar to the corresponding Hg-Fe bonds in literature-known [Hg{Fe(CO)4}2]2- dianions (2.52-2.55 Angstrom) which intrigued us to analyze the bonding situation in both the dications and dianions with the EDA-NOCV method. Both species are best described as Hg(0) compounds which are also confirmed by the shape of the HOMO-4 and HOMO-5 of the dication and dianion, respectively, in which the electron pair is located mainly at the Hg. Furthermore, for the dication and the dianion the sigma-backdonation from Hg into the [Fe(CO)5]22+ or the [Fe(CO)4]22- fragment is the most dominant orbital interaction and surprisingly these interaction energies are also very similar even in absolute values. The fact that both iron-based fragments are missing two electrons explains their prominent sigma-acceptor properties

Increasing the oxidation power of TCNQ by coordination of the fluorinated Lewis acid B(C6F5)3

The oxidation power of the cyanocarbon TCNQ (tetracyano-quinodimethane) can be significantly increased to approximately E = +0.9 V vs. Cp2Fe by coordination of up to four equivalents of the strong fluorinated Lewis acid B(C6F5)3. Thianthrene and tris(4-bromophenyl)amine were oxidized to the corresponding radical cations. Dianionic [TCNQ∙4 B(C6F5)3]2ꟷ was formed upon reduction with two equivalents of ferrocene or decamethylcobaltocene

Persilylation of Ferrocene: The Ultimate Discipline in Sterically Overcrowded Metal Complexes

We report the preparation and structural characterization of the first persilylated metallocene via metalation of decabromoferrocene. Whereas Grignard conditions turned to be insufficient due to steric and electronic effects of the silyl groups causing a decreased nucleophilicity of the metalated intermediates, stepwise lithium-halogen exchange yields complex mixtures of polysilylated compounds FeC10DMSnH10−n (n = 10, 9, 8) including the targeted decasilylated ferrocene. Those mixtures were successfully separated allowing a systematic study on silylation effects on ferrocene by XRD, CV, NMR and UV/vis spectroscopy supported by DFT calculations. The findings were used to develop a high-yielding and preparative simple way to generate a perfunctionalized and overcrowded ferrocene, FeC10DMS8Me2