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Crystallographic characterization of rare-earth cyano-tri-phenyl-borate complexes and the cyano-borates [NCBPh₃]^1-, [NCBPh₂Me]^1-, and [NCBPh₂(μ-O)BPh₂]¹.

ABSTRACT: 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.

SUBMITTER: Dumas MT

PROVIDER: S-EPMC8340972 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The salt [K(18-crown-6)]2[Ru(CN)2(CO)3] ([K(18-crown-6)]2[1]) was generated by the reaction of Ru(C2H4)(CO)4 with [K(18-crown-6)]CN. An initial thermal reaction gives [Ru(CN)(CO)4]-, which, upon ultraviolet (UV) irradiation, reacts with a second equiv of CN-. Protonation of [1]2- gave [HRu(CN)2(CO)3]- ([H1]-), which was isolated as a single isomer with mutually trans cyanide ligands. The complex cis,cis,cis-[Ru(pdt)(CN)2(CO)2]2- ([2]2-) was prepared by the UV-induced reaction of [1]2- with propanedithiol (pdtH2). The corresponding iron complex cis,cis,cis-[Fe(pdt)(CN)2(CO)2]2- ([3]2-) was prepared similarly. The pdt complexes [2]2- and [3]2- were treated with Fe(benzylideneacetone)(CO)3 to give, respectively, [RuFe (μ-pdt)(CN)2(CO)4]2- ([5]2-) and [Fe2(μ-pdt)(CN)2(CO)4]2- ([4]2-). The pathway from [3]2- to Fe2 complex [4]2- implicates intermetallic migration of CN-. In contrast, the formation of [5]2- leaves the Ru(CN)2(CO) center intact, as confirmed by X-ray crystallography. The structure of [5]2- features a "rotated" square-pyramidal Fe(CO)2(μ-CO) site. NMR measurements indicate that the octahedral Ru site is stereochemically rigid, whereas the Fe site dynamically undergoes turnstile rotation. 57Fe Mössbauer spectral parameters are very similar for rotated [5]2- and unrotated Fe2 complex [4]2-, indicating the insensitivity of that technique to both the geometry and the oxidation state of the Fe site. According to cyclic voltammetry, [5]2- oxidizes at E1/2 ∼ -0.8 V vs Fc+/0. Electron paramagnetic resonance (EPR) measurements show that 1e- oxidation of [5]2- gives an S = 1/2 rhombic species, consistent with the formulation Ru(II)Fe(I), related to the Hox state of the [FeFe] hydrogenases. Density functional theory (DFT) studies reproduce the structure, 1H NMR shifts, and infrared (IR) spectra observed for [5]2-. Related homometallic complexes with both cyanides on a single metal are predicted to not adopt rotated structures. These data suggest that [5]2- is best described as Ru(II)Fe(0). This conclusion raises the possibility that for some reduced states of the [FeFe]-hydrogenases, the [2Fe]H site may be better described as Fe(II)Fe(0) than Fe(I)Fe(I).

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Crystallographic characterization of rare-earth cyano-tri-phenyl-borate complexes and the cyano-borates [NCBPh₃]^1-, [NCBPh₂Me]^1-, and [NCBPh₂(μ-O)BPh₂]¹.

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Crystallographic characterization of rare-earth cyano-tri-phenyl-borate complexes and the cyano-borates [NCBPh3]1-, [NCBPh2Me]1-, and [NCBPh2(μ-O)BPh2]1.

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Crystallographic characterization of rare-earth cyano-tri-phenyl-borate complexes and the cyano-borates [NCBPh₃]^1-, [NCBPh₂Me]^1-, and [NCBPh₂(μ-O)BPh₂]¹.