Dismutation of Tricyanoboryllead Compounds: The Homoleptic Tetrakis(tricyanoboryl)plumbate Tetraanion.

A series of unprecedently air-stable (tricyanoboryl)plumbate anions was obtained by the reaction of the boron-centered nucleophile B(CN)3 2- with triorganyllead halides. Salts of the anions [R3 PbB(CN)3 ]- (R=Ph, Et) were isolated and found to be stable in air at room temperature. In the case of Me3 PbHal (Hal=Cl, Br), a mixture of the anions [Me4-n Pb{B(CN)3 }n ]n- (n=1, 2) was obtained. The [Et3 PbB(CN)3 ]- ion undergoes stepwise dismutation in aqueous solution to yield the plumbate anions [Et4-n Pb{B(CN)3 }n ]n- (n=1-4) and PbEt4 as by-product. The reaction rate increases with decreasing pH value of the aqueous solution or by bubbling O2 through the reaction mixture. Adjustment of the conditions allowed the selective formation and isolation of salts of all anions of the series [Et4-n Pb{B(CN)3 }n ]n- (n=2-4) including the homoleptic tetraanion [Pb{B(CN)3 }4 ]4- .

Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination.

Different types of high-yield, easily scalable syntheses for cyano(fluoro)borates Kt[BFn (CN)4-n ] (n=0-2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal-free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)2 {OC(O)Et}]- to result in [BF(CN)2 {OC(O)Et}]- is described.

Carba-closo-dodecaboranylethynyl ligands facilitating luminescent reversed charge-transfer excited states in gold/silver complexes.

A set of mono- and dinuclear AuI and AgI alkynyl complexes bearing the carba-closo-dodecaboranylethynyl ligand show intense room temperature phosphorescence. The {closo-1-CB11} cage participates in an unprecedented way as an electron donating moiety, changing the direction of the charge-transfer excited state.

Cyanohydridoborate Anions: Synthesis, Salts, and Low-Viscosity Ionic Liquids.

High-yield syntheses up to molar scales for salts of [BH(CN)3 ]- (2) and [BH2 (CN)2 ]- (3) starting from commercially available Na[BH4 ] (Na5), Na[BH3 (CN)] (Na4), BCl3 , (CH3 )3 SiCN, and KCN were developed. Direct conversion of Na5 into K2 was accomplished with (CH3 )3 SiCN and (CH3 )3 SiCl as a catalyst in an autoclave. Alternatively, Na5 is converted into Na[BH{OC(O)R}3 ] (R=alkyl) that is more reactive towards (CH3 )3 SiCN and thus provides an easy access to salts of 2. Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et}2 ] (Na7 b) and Na[BH(CN)2 {OC(O)Et}] (Na8 b). A third entry to 2 and 3 uses ether adducts of BHCl2 or BH2 Cl such as the commercial 1,4-dioxane adducts that react with KCN and (CH3 )3 SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm]3 has the lowest viscosity and highest conductivity with 10.2 mPa s and 32.6 mS cm-1 at 20 °C known for non-protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye-sensitized solar cells (Grätzel cells).

Perfluoroalkyltricyanoborate and Perfluoroalkylcyanofluoroborate Anions: Building Blocks for Low-Viscosity Ionic Liquids.

The potassium perfluoroalkyltricyanoborates K[Cn F2 n+1 B(CN)3 ] [n=1 (1 d), 2 (2 d)] and the potassium mono(perfluoroalkyl)cyanofluoroborates K[Cn F2 n+1 BF(CN)2 ] [n=1 (1 c), 2 (2 c)] and [Cn F2 n+1 BF2 (CN)]- [n=1 (1 b), 2 (2 b), 3 (3 b), 4 (4 b)] are accessible with perfect selectivities on multi-gram scales starting from K[Cn F2 n+1 BF3 ] and Me3 SiCN. The K+ salts are starting materials for the preparation of salts with organic cations, for example, [EMIm]+ (EMIm=1-ethyl-3-methylimidazolium). These [EMIm]+ salts are hydrophobic room-temperature ionic liquids (RTILs) that are thermally, chemically and electrochemically very robust, offering electrochemical windows up to 5.8 V. The RTILs described herein, exhibit very low viscosities with a minimum of 14.0 mPa s at 20 °C for [EMIm]1 c, low melting points down to -57 °C for [EMIm]2 b and extraordinary high conductivities up to 17.6 mS cm-1 at 20 °C for [EMIm]1 c. The combination of these properties makes these ILs promising materials for electrochemical devices as exemplified by the application of selected RTILs as component of electrolytes in dye-sensitised solar cells (DSSCs, Grätzel cells). The efficiency of the DSSCs was found to increase with a decreasing viscosity of the neat ionic liquid. In addition to the spectroscopic characterisation, single crystals of the potassium salts of the anions 1 b-d, 2 d, 3 b and 4 c as well as of [nBu4 N]2 c have been studied by X-ray diffraction.

Borylation of fluorinated arenes using the boron-centred nucleophile B(CN)32- - a unique entry to aryltricyanoborates.

The potassium salt of the boron-centred nucleophile B(CN)32- (1) readily reacts with perfluorinated arenes, such as hexafluorobenzene, decafluorobiphenyl, octafluoronaphthalene and pentafluoropyridine, which results in KF and the K+ salts of the respective borate anions with one {B(CN)3} unit bonded to the (hetero)arene. An excess of K21 leads to the successive reaction of two or, in the case of perfluoropyridine, even three C-F moieties and the formation of di- and trianions, respectively. Moreover, all of the 11 partially fluorinated benzene derivatives, C6F6-n H n (n = 1-5), generally react with K21 to give new tricyano(phenyl)borate anions with high chemo- and regioselectivity. A decreasing number of fluorine substituents on benzene results in a decrease in the reaction rate. In the cases of partially fluorinated benzenes, the addition of LiCl is advantageous or even necessary to facilitate the reaction. Also, pentafluorobenzenes R-C6F5 (R = -CN, -OMe, -Me, or -CF3) react via C-F/C-B exchange that mostly occurs in the para position and to a lesser extent in the meta or ortho positions. Most of the reactions proceed via an SNAr mechanism. The reaction of 1,4-F2C6H4 with K21 shows that an aryne mechanism has to be considered in some cases as well. In summary, a wealth of new stable tricyano(aryl)borates have been synthesised and fully characterized using multi-NMR spectroscopy and most of them were characterised using single-crystal X-ray diffraction.