Nickel(II) Cyanoborates and Cyanoborate-Ligated Nickel(II) Complexes.

Nickel(II) cyanoborates Ni[BH(CN)]·HO (·HO), Ni[BH(CN)]·0.5HO (·0.5HO), and Ni[B(CN)]·0.

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) with triorganyllead halides. Salts of the anions [R PbB(CN) ] (R=Ph, Et) were isolated and found to be stable in air at room temperature. In the case of Me PbHal (Hal=Cl, Br), a mixture of the anions [Me Pb{B(CN) } ] (n=1, 2) was obtained.

Stable and Storable N(CF ) Transfer Reagents.

Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF ) group are rare.

Hydroxytricyanoborate Anion: Synthetic Aspects and Structural, Chemical, and Spectroscopic Properties.

In recent years, salts of the hydridotricyanoborate anion [BH(CN)] () have become readily available. In spite of the unusually high stability of the anion, it can be used as a valuable starting material for the preparation of selected tricyanoborates, for example, the boron-centered nucleophile B(CN). A further unprecedented example is the hydroxytricyanoborate anion [B(OH)(CN)] that is accessible by oxidation of (HO) with elemental bromine in water.

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

High-yield syntheses up to molar scales for salts of [BH(CN) ] (2) and [BH (CN) ] (3) starting from commercially available Na[BH ] (Na5), Na[BH (CN)] (Na4), BCl , (CH ) SiCN, and KCN were developed. Direct conversion of Na5 into K2 was accomplished with (CH ) SiCN and (CH ) SiCl as a catalyst in an autoclave. Alternatively, Na5 is converted into Na[BH{OC(O)R} ] (R=alkyl) that is more reactive towards (CH ) SiCN and thus provides an easy access to salts of 2.

Properties of perhalogenated {closo-B} and {closo-B} multiply charged anions and a critical comparison with {closo-B} in the gas and the condensed phase.

closo-Borate anions [closo-BnXn]2- are part of the most famous textbook examples of polyhedral compounds. Substantial differences in their reactivity and interactions with other compounds depending on the substituent X and cluster size n have been recognized, which favor specific closo-borates for different applications in cancer treatment, chemical synthesis, and materials science. Surprisingly, a fundamental understanding of the molecular properties underlying these differences is lacking.

Lanthanide Coordination Polymers and MOFs based on the Dicyanodihydridoborate Anion.

New lanthanide cyanoborates were synthesized from anhydrous lanthanide chlorides and the acid H[BH (CN) ] in either acetonitrile or pyridine. Reactions in acetonitrile lead to three-dimensional, anionic metal-organic frameworks (MOFs) [Ln {BH (CN) } ]⋅[Ln(CH CN) ] (Ln=Ce, Eu, Tb) which incorporate complex cations [Ln(CH CN) ] in the pores of the framework for charge compensation. In contrast, the reactions in pyridine result in the formation of one-dimensional coordination polymers [H(py) ][LnCl {BH (CN) } (py) ]⋅0.

Stepwise Introduction of Cyano Groups into nido- and closo-Undecaborate Clusters.

Eleven-vertex closo and nido boron clusters with one or two exo-cyano groups were obtained by a series of consecutive cage-opening and cage-closure reactions starting from K [closo-B H ] (K 1). In the first step, K 1 reacts with KCN in water at elevated temperatures to yield [7-NC-nido-B H ] (5 a). Oxidation of 5 a with PbO gives [NC-closo-B H ] (2).

Anhydrous, Homoleptic Lanthanide Frameworks with the Pentafluoroethyltricyanoborate Anion.

Pentafluoroethyltricyanoborate frameworks of rare-earth metal ions of the general formula [Ln{CFB(CN)}(OH)] (Ln = La, Eu, Ho; n = 0, 3; [Ln1(OH)]) were synthesized using the oxonium salt (HO)[CFB(CN)] ((HO)1) and lanthanide chlorides LnCl·nHO as starting compounds. Single-crystals of [La{CFB(CN)}] ([La1]) are obtained from the room temperature ionic liquid (RTIL) [EMIm]1 using either a ionothermal approach or by recrystallization of anhydrous microcrystalline [La1] that is obtained from reactions in aqueous media after drying in a vacuum. Removal of water from [Ln1(OH)] (Ln = Eu, Ho) to give microcrystalline [Ln1] is achieved in a vacuum at elevated temperatures.

Protonation versus Oxonium Salt Formation: Basicity and Stability Tuning of Cyanoborate Anions.

Anhydrous H[BH (CN) ] crystallizes from acidic aqueous solutions of the dicyanodihydridoborate anion. The formation of H[BH (CN) ] is surprising as the protonation of nitriles requires strongly acidic and anhydrous conditions but it can be rationalized based on theoretical data. In contrast, [BX(CN) ] (X=H, F) gives the expected oxonium salts (H O)[BX(CN) ] while (H O)[BF (CN) ]/H[BF (CN) ] is unstable.