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 naphthaleneF with [NO]+[F{Al(ORF)3}2]- generates [naphthaleneF]+⋅[F{Al(ORF)3}2]- (ORF=OC(CF3)3) in gram scale. Thermochemical analysis unravels the solid-state deelectronation 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 structures of the acene dications [tetracene]2+, [pentacene]2+ or spectroscopic evidence for the carbonyl complex of the ferrocene dication [Fc(CO)]2+, the [P9]+ cation from white phosphorus, the solvent-free copper(I) salt starting from copper metal and the dicationic Fe(IV)-scorpionate complex [Fe(sc)2]2+.

[Ni(CO)4 ]+ as NiI Synthon: Synthesis and Characterization of NiI Half-Sandwich and Sandwich Cations.

The stable, easily accessible salt [Ni(CO)4 ]+ [F{Al(ORF )3 }2 ]- (RF =C(CF3 )3 ) was used as a NiI synthon to generate the novel half-sandwich complexes [Ni(arene)(CO)2 ]+ (arene=C6 H6 , o-dfb=1,2-F2 C6 H4 ). By irreversible removal of CO from the equilibrium, even the rather endergonic reaction to a [Ni(o-dfb)2 ]+ salt was successful (Δr G°(solv) =+78 kJ mol-1 ). The latter displays an unprecedented slipped η3 ,η3 -sandwich structure and is the ultimate synthon to NiI -chemistry.

The Unified Redox Scale for All Solvents: Consistency and Gibbs Transfer Energies of Electrolytes from their Constituent Single Ions.

We have devised the unified redox scale Eabs H2O , which is valid for all solvents. The necessary single ion Gibbs transfer energy between two different solvents, which only can be determined with extra-thermodynamic assumptions so far, must clearly satisfy two essential conditions: First, the sum of the independent cation and anion values must give the Gibbs transfer energy of the salt they form. The latter is an observable and measurable without extra-thermodynamic assumptions. Second, the values must be consistent for different solvent combinations. With this work, potentiometric measurements on silver ions and on chloride ions show that both conditions are fulfilled using a salt bridge filled with the ionic liquid [N2225 ][NTf2 ]: if compared to the values resulting from known pKL values, the silver and chloride single ion magnitudes combine within a uncertainty of 1.5 kJ mol-1 to the directly measurable transfer magnitudes of the salt AgCl from water to the solvents acetonitrile, propylene carbonate, dimethylformamide, ethanol, and methanol. The resulting values are used to further develop the consistent unified redox potential scale Eabs H2O that now allows to assess and compare redox potentials in and over six different solvents. We elaborate on its implications.

Measurements and Utilization of Consistent Gibbs Energies of Transfer of Single Ions: Towards a Unified Redox Potential Scale for All Solvents.

Utilizing the "ideal" ionic liquid salt bridge to measure Gibbs energies of transfer of silver ions between the solvents water, acetonitrile, propylene carbonate and dimethylformamide results in a consistent data set with a precision of 0.6 kJ mol-1 over 87 measurements in 10 half-cells. This forms the basis for a coherent experimental thermodynamic framework of ion solvation chemistry. In addition, we define the solvent independent pe abs H 2 O - and the E abs H 2 O values that account for the electronating potential of any redox system similar to the pH abs H 2 O value of a medium that accounts for its protonating potential. This E abs H 2 O scale is thermodynamically well-defined enabling a straightforward comparison of the redox potentials (reducities) of all media with respect to the aqueous redox potential scale, hence unifying all conventional solvents' redox potential scales. Thus, using the Gibbs energy of transfer of the silver ion published herein, one can convert and unify all hitherto published redox potentials measured, for example, against ferrocene, to the E abs H 2 O scale.

Influence of the cofactor structure on the photophysical processes initiating signal transduction in a phototropin-derived LOV domain.

Due to their biological importance, the photochemistry of blue-light photoreceptor proteins has been studied extensively over the last few decades. Most blue-light photoreceptors, such as cryptochromes and phototropins, utilize flavin chromophores as their cofactors. After irradiation with light, the chromophore undergoes electron transfer with nearby redox-active amino-acid residues within the protein, whereby this first step of signal transduction may be initiated either from the flavin's excited singlet or triplet state. Despite the collective effort of theoreticians and experimentalists to characterize and understand the photochemistry of flavoproteins, the mechanistic details of the excited state processes initiating signal transduction are yet to be revealed. Here, we use a light-oxygen-voltage-sensing domain from Avena sativa phototropin to get additional insight into the excited state photochemistry of flavoproteins. The influence of structural variations of the cofactor flavin mononucleotide (FMN) is explored by varying the methyl substitution pattern in positions 7 and 8 of the flavin core. The photophysical properties of the FMN derivatives, in the absence and presence of the protein environment, are investigated by UV-vis absorption, fluorescence, and electron paramagnetic resonance spectroscopies as well as cyclic voltammetry. The comparison of the properties of the modified flavin cofactors with those of FMN shows that the rates of the different excited state reactions, and therefore also the singlet/triplet yields, can be modulated substantially by only minor structural modifications of the flavin core.

Synthesis, Characterisation and Reactions of Truly Cationic NiI -Phosphine Complexes.

The recently published purely metallo-organic NiI salt [Ni(cod)2 ][Al(ORF )4 ] (1, cod=1,5-cyclooctadiene, RF =C(CF3 )3 ) provides a starting point for a new synthesis strategy leading to NiI phosphine complexes, replacing cod ligands by phosphines. Clearly visible colour changes indicate reactions within minutes, while quantum chemical calculations (PBE0-D3(BJ)/def2-TZVPP) approve exergonic reaction enthalpies in all performed ligand exchange reactions. Hence, [Ni(dppp)2 ][Al(ORF )4 ] (2, dppp=1,3-bis(diphenylphosphino)propane), [Ni(dppe)2 ][Al(ORF )4 ] (3, dppe=1,3-bis(diphenyl-phosphino)ethane), three-coordinate [Ni(PPh3 )3 ][Al(ORF )4 ] (4) and a remarkable two-coordinate NiI phosphine complex [Ni(PtBu3 )2 ][Al(ORF )4 ] (5) were characterised by single crystal X-ray structure analysis. EPR studies were performed, confirming a nickel d9 -configuration in complexes 2, 4 and 5. This result is supported by additional magnetization measurements of 4 and 5. Further investigations by cyclic voltammetry indicate relatively high oxidation potentials for these NiI compounds between 0.7 and 1.7 V versus Fc/Fc+ . Screening reactions with O2 and CO gave first insights on the reaction behaviour of the NiI phosphine complexes towards small molecules with formation of mixed phosphine-CO-NiI complexes and oxidation processes yielding new NiI and/or NiII derivatives. Moreover, 4 reacted with CH2 Cl2 at RT to give a dimeric NiII ylide complex (4 c). As CH2 Cl2 is a rather stable alkyl halide with relatively high C-Cl bond energies, 4 appears to be a suitable reagent for more general C-Cl bond activation reactions.

Basic Remarks on Acidity.

This Review provides a unified view on Brønsted acidity. For this purpose, a brief overview of the concepts acidity, acid strengths, and pH value is given, including problems, proposed solutions, and the use of the pHabs /pHabsH2O scale as a unifying concept. Thereafter, some examples of the accessibility and application of unified pHabs values are given. The Review is rounded off with the analogy of acid-base chemistry to redox chemistry with the introduction of the unified redox scale peabs . The combination of pHabs and peabs values in the protoelectric potential map (PPM), as elaborated in ongoing studies on the thermochemistry of single ions, provides a means to classify and to compare all possible acid-base/redox reactions in a medium-independent and, thus, unified fashion.

The Ideal Ionic Liquid Salt Bridge for the Direct Determination of Gibbs Energies of Transfer of Single Ions, Part I: The Concept.

Described is a procedure for the thermodynamically rigorous, experimental determination of the Gibbs energy of transfer of single ions between solvents. The method is based on potential difference measurements between two electrochemical half cells with different solvents connected by an ideal ionic liquid salt bridge (ILSB). Discussed are the specific requirements for the IL with regard to the procedure, thus ensuring that the liquid junction potentials (LJP) at both ends of the ILSB are mostly canceled. The remaining parts of the LJPs can be determined by separate electromotive force measurements. No extra-thermodynamic assumptions are necessary for this procedure. The accuracy of the measurements depends, amongst others, on the ideality of the IL used, as shown in our companion paper Part II.

The Ideal Ionic Liquid Salt Bridge for Direct Determination of Gibbs Energies of Transfer of Single Ions, Part II: Evaluation of the Role of Ion Solvation and Ion Mobilities.

An important intermediate goal to evaluate our concept for the assumption-free determination of single-ion Gibbs transfer energies Δtr G°(i, S1 →S2 ) is presented. We executed the crucial steps a) and b) of the methodology, described in Part I of this treatise, exemplarily for Ag+ and Cl- with S1 being water and S2 being acetonitrile. The experiments showed that virtually all parts of the liquid junction potentials (LJPs) at both ends of a salt bridge cancel, if the bridge electrolyte is an "ideal" ionic liquid, that is, one with nearly identical diffusion of anion and cation. This ideality holds for [N2225 ]+ [NTf2 ]- in the pure IL, but also in water and acetonitrile solution. Electromotive force measurements of solvation cells between S1 and S2 demonstrated Nernstian behavior for Ag+ concentration cells and constant like cell potentials for solutions with five tested Ag+ counterions.

Absolute Brønsted Acidities and pH Scales in Ionic Liquids.

Although receiving large interest over the last years, some fundamental aspects of Brønsted acidity in ionic liquids (ILs) have up to now been insufficiently highlighted. In this work, standard states, activity, and activity coefficient definitions for IL solvent systems were developed from general thermodynamic considerations and then extended to a general mixed solvent standard state. By using the bromide/bromoaluminate systems as representative ILs, formulae for thermodynamically consistent pH scales for ILs with simple (Br(-) ) and complex ([Aln Br3n+1 ](-) ) anions were derived on the basis of the chemical potential of the proton. Supported by quantum chemical [ccsd(t)/MP2/DFT/COSMO-RS] calculations, Gibbs solvation energies of the proton were calculated, which allowed the ILs to be ranked in absolute acidity, that is, pHabs or µabs (H(+) , IL), and additionally allowed their acidity to be compared with molecular Brønsted acid systems. It was shown that bromoaluminate ILs are suited for reaching superacidic conditions. The complexity of autoprotolysis processes in C6 MIM(+) [AlBr4 ](-) (C6 MIM=1-hexyl-3-methylimidazolium) with or without the addition of basic (i.e. Br(-) ) or acidic (AlBr3 and/or HBr) solutes was examined in detail by model calculations, and they indicated a large thermodynamic influence of small deviations from the exact stoichiometric composition.

[Ni(cod)2][Al(OR(F))4], a Source for Naked Nickel(I) Chemistry.

The straightforward synthesis of the cationic, purely organometallic Ni(I) salt [Ni(cod)2](+)[Al(OR(F))4](-) was realized through a reaction between [Ni(cod)2] and Ag[Al(OR(F))4] (cod = 1,5-cyclooctadiene). Crystal-structure analysis and EPR, XANES, and cyclic voltammetry studies confirmed the presence of a homoleptic Ni(I) olefin complex. Weak interactions between the metal center, the ligands, and the anion provide a good starting material for further cationic Ni(I) complexes.

The protoelectric potential map (PPM): an absolute two-dimensional chemical potential scale for a global understanding of chemistry.

We introduce the protoelectric potential map (PPM) as a novel, two-dimensional plot of the absolute reduction potential (peabs scale) combined with the absolute protochemical potential (Brønsted acidity: pHabs scale). The validity of this thermodynamically derived PPM is solvent-independent due to the scale zero points, which were chosen as the ideal electron gas and the ideal proton gas at standard conditions. To tie a chemical environment to these reference states, the standard Gibbs energies for the transfer of the gaseous electrons/protons to the medium are needed as anchor points. Thereby, the thermodynamics of any redox, acid-base or combined system in any medium can be related to any other, resulting in a predictability of reactions even over different media or phase boundaries. Instruction is given on how to construct the PPM from the anchor points derived and tabulated with this work. Since efforts to establish "absolute" reduction potential scales and also "absolute" pH scales already exist, a short review in this field is given and brought into relation to the PPM. Some comments on the electrochemical validation and realization conclude this concept article.

Gold carbonyl cations and beyond: homoleptic gold(I) complexes with P4 and P4S3 and the half-sandwich cation [Au(C6H6)(CO)].

Oxidation of Au0 with the synergistic Ag+/0.5 I2 system in the commercial organic solvent 1,2,3,4-tetrafluorobenzene led to the perfluoroalkoxyaluminate salt of the [Au(CO)2]+ cation known from superacid chemistry. This [Au(CO)2]+ salt proved to be an excellent 'naked' Au+-synthon yielding complex salts with [Au(η2-P4)2]+, [Au(η1-P4S3)2]+ and half-sandwich [Au(η2-C6H6)(CO)]+ cation.

Pushing redox potentials to highly positive values using inert fluorobenzenes and weakly coordinating anions.

While the development of weakly coordinating anions (WCAs) received much attention, the progress on weakly coordinating and inert solvents almost stagnated. Here we study the effect of strategic F-substitution on the solvent properties of fluorobenzenes C6FxH6-x (xFB, x = 1-5). Asymmetric fluorination leads to dielectric constants as high as 22.1 for 3FB that exceeds acetone (20.7). Combined with the WCAs [Al(ORF)4]- or [(FRO)3Al-F-Al(ORF)3]- (RF = C(CF3)3), the xFB solvents push the potentials of Ag+ and NO+ ions to +1.50/+1.52 V vs. Fc+/Fc. The xFB/WCA-system has electrochemical xFB stability windows that exceed 5 V for all xFBs with positive upper limits between +1.82 V (1FB) and +2.67 V (5FB) vs. Fc+/Fc. High-level ab initio calculations with inclusion of solvation energies show that these high potentials result from weak interactions of the ions with solvent and counterion. To access the available positive xFB potential range with stable reagents, the innocent deelectronator salts [anthraceneF]+∙[WCA]- and [phenanthreneF]+∙[WCA]- with potentials of +1.47 and +1.89 V vs. Fc+/Fc are introduced.

Isolation of a stable pyridine radical anion.

Reduction of 2,6-bis(diazaboryl)pyridine with KC8 gives a room-temperature-stable yellow colored solution containing the corresponding radical anion. The radical was characterized by single crystal XRD, EPR spectroscopy, UV-vis absorption spectroscopy and electrochemically, supported by theoretical calculations. The negative charge and spin density are mainly distributed over the atoms of the pyridine ring, making this the first isolated pyridine radical anion as its potassium salt.