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Crystal structure of [K(18-crown-6)]⁺ ₂[Pt(CN)₄]².

ABSTRACT: In the title compound, di-μ-cyanato-1:2κ² N:C;2:3κ² C:N-di-cyanato-2κ² C-bis-(1,4,7,10,13,16-hexa-oxa-cyclo-octa-deca-ne)-1κ⁶ O;3κ⁶ O-1,3-dipotassium(I)-2-platinum(II), [K₂Pt(CN)₄(C₁₂H₂₄O₆)₂] or [K(18-crown-6)]₂·[Pt(CN)₄], two trans-orientated cyano groups of the square-planar [Pt(CN)₄]^2- dianion (Pt site symmetry ) bind to one potassium ion each, which are additionally coordinated by the six O atoms of 18-crown-6. No Pt⋯Pt inter-actions occur in the crystal, but very weak Pt⋯H contacts (2.79 Å) are observed.

SUBMITTER: Sellin M

PROVIDER: S-EPMC6895955 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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Publications

Crystal structure of [K(18-crown-6)]+ 2[Pt(CN)4]2.

Sellin Malte M Malischewski Moritz M

Acta crystallographica. Section E, Crystallographic communications 20191115 Pt 12

In the title compound, di-μ-cyanato-1:2κ2 N:C;2:3κ2 C:N-di-cyanato-2κ2 C-bis-(1,4,7,10,13,16-hexa-oxa-cyclo-octa-deca-ne)-1κ6 O;3κ6 O-1,3-dipotassium(I)-2-platinum(II), [K2Pt(CN)4(C12H24O6)2] or [K(18-crown-6)]2·[Pt(CN)4], two trans-orientated cyano groups of the square-planar [Pt(CN)4]<su ...[more]

PMID: 31871748

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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).

Dataset Information

Crystal structure of [K(18-crown-6)]⁺ ₂[Pt(CN)₄]².

Publications

Crystal structure of [K(18-crown-6)]<sup>+</sup> <sub>2</sub>[Pt(CN)<sub>4</sub>]<sup>2</sup>.

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