UC Irvine

The investigation of the coordination chemistry of rare-earth metal complexes with cyanide ligands led to the isolation and crystallographic characterization of the Ln ^III cyano-tri-phenyl-borate complexes di-chlorido-(cyano-tri-phenyl-borato-κN)tetra-kis-(tetra-hydro-furan-κO)lanthanide(III), [LnCl₂(C₁₉H₁₅BN)(C₄H₈O)₄] [lanthanide (Ln) = dysprosium (Dy) and yttrium Y)] from reactions of LnCl₃, KCN, and NaBPh₄. Attempts to independently synthesize the tetra-ethyl-ammonium salt of (NCBPh₃)^- from BPh₃ and [NEt₄][CN] in THF yielded crystals of the phenyl-substituted cyclic borate, tetra-ethyl-aza-nium 2,2,4,6-tetra-phenyl-1,3,5,2λ⁴,4,6-trioxatriborinan-2-ide, C₈H₂₀N⁺·C₂₄H₂₀B₃O₃ ^- or [NEt₄][B₃(μ-O)₃(C₆H₅)₄]. The mechanochemical reaction of BPh₃ and [NEt₄][CN] without solvent produced crystals of tetra-ethyl-aza-nium cyano-diphenyl-λ⁴-boranyl di-phenyl-borinate, C₈H₂₀N⁺·C₂₅H₂₀B₂NO^- or [NEt₄][NCBPh₂(μ-O)BPh₂]. Reaction of BPh₃ and KCN in THF in the presence of 2.2.2-cryptand (crypt) led to a crystal of bis-[(2.2.2-cryptand)potassium] 2,2,4,6-tetra-phenyl-1,3,5,2λ⁴,4,6-trioxatriborinan-2-ide cyano-methyl-diphenyl-borate tetra-hydro-furan disolvate, 2C₁₈H₃₆KN₂O₆ ⁺·C₂₄H₂₀B₃O₃ ^-·C₁₄H₁₃BN^-·2C₄H₈O or [K(crypt)]₂[B₃(μ-O)₃(C₆H₅)₄][NCBPh₂Me]·2THF. The [NCBPh₂(μ-O)BPh₂]^1- and (NCBPh₂Me)^1- anions have not been structurally characterized previously. The structure of 1-Y was refined as a two-component twin with occupancy factors 0.513 (1) and 0.487 (1). In 4, one solvent mol-ecule was disordered and included using multiple components with partial site-occupancy factors.