Pseudohalogen Chemistry in Ionic Liquids with Non-innocent Cations and Anions.

Within the second funding period of the SPP 1708 "Material Synthesis near Room Temperature",which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non-innocent methyl carbonate anion [CO Me] , served as starting material and enabled facile access to pseudohalide salts by reaction with Me Si-X (X=CN, N , OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT-IL) [nBu MeN][B(OMe) (CN)], we were able to crystallize the double salt [nBu MeN] [B(OMe) (CN)](CN).

Salts of HCN-Cyanide Aggregates: [CN(HCN) ] and [CN(HCN) ].

Although pure hydrogen cyanide can spontaneously polymerize or even explode, when initiated by small amounts of bases (e.g. CN ), the reaction of liquid HCN with [WCC]CN (WCC=weakly coordinating cation=Ph P, Ph PNPPh =PNP) was investigated.

Heavy Neutral and Anionic Pnictogen Thiocyanates.

When [PPN]SCN (1; PPN = [PhP-N-PPh]) is treated with MeSi-SCN in methanol, [PPN][H(NCS)] (2), a hydrogen diisothiocyanate salt bearing the [H(NCS)] anion, was generated, isolated, and fully characterized. Pure heavy E(NCS) [E = Sb (3), Bi (4)] species were obtained from the reaction of EF and an excess of MeSi-SCN, while the tetrahydrofuran (THF) solvates E(NCS)·THF were isolated when the product was recrystallized from THF. When 2 equiv of 1 was combined with MeSi-SCN and SbF, [PPN][Sb(NCS)] (5) could be isolated.

Arsenic-Mediated C-C Coupling of Cyanides Leading to Cyanido Arsazolide [AsC N ].

The chemistry of arsenic cyanides has been investigated and is found to be completely different to the chemistry of the heavier analogs antimony and bismuth as well as phosphorus. The reaction of As(CN) with cyanide salts resulted in the formation of an unknown cyanido arsazolide heterocycle, which represents a structure isomer of the desired [As(CN) ] . The structure, bonding, and formation of this unusual heterocycle is discussed featuring an arsenic mediated C-C coupling of cyanides.

Cyanido Antimonate(III) and Bismuthate(III) Anions.

The reaction of in situ generated E(CN) (E = Sb, Bi) with different amounts of [PhP]CN and [PPN]CN ([PPN] = [PhP-N-PPh]) was studied, affording salts bearing the novel ions [E(CN)], [Bi(CN)], and [Bi(CN)]. The valence lone pair of electrons on the central atom of antimony and bismuth(III) compounds can be either sterically active in an unsymmetric fashion (three shorter bonds + x longer bonds) or symmetric (with rather long averaged bonds). In the presence of weakly coordinating cations (e.

Molecular E(CN) (E=Sb, Bi) Species Synthesized from Ionic Liquids as Solvates.

The heavy pnictogen tricyanides, E(CN) (E=Sb, Bi), were synthesized from EF and Me SiCN in ionic liquids, for example, 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIm][OTf]), which prevents the oligomerization of the molecular E(CN) species by formation of [BMIm][E(CN) (OTf)] salts in solution. Recrystallization of [BMIm][E(CN) (OTf)] from THF led to the isolation and full characterization of the molecular species E(CN) ⋅2 THF.

Tetracyanido(difluorido)phosphates M(+) [PF2 (CN)4 ](.).

The systematic study of the reaction of M[PF6 ] salts and Me3 SiCN led to a synthetic method for the synthesis and isolation of a series of salts containing the unprecedented [PF2 (CN)4 ](-) ion in good yields. The reaction temperature, pressure, and stoichiometry were optimized. The crystal structures of M[PF2 (CN)4 ] (M=[nBu4 N](+) , Ag(+) , K(+) , Li(+) , H5 O2 (+) ) were determined.