Hochreine Metalle durch Elektroraffination in metallorganischen Komplexsalzschmelzen

Dötzer, R.

doi:10.1002/cite.330360606

Cited by 38 publications

(4 citation statements)

References 27 publications

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“…Triorganofluoroalanates were first synthesized by Ziegler et al. in 1960. − The derivatives of the higher homologs gallium and indium, K[Me 3 GaF], K[Et 3 GaF], − [NMe 4 ][Et 3 GaF], [Me 3 NCH 2 Ph][Et 3 GaF], , [Et 3 NCH 2 Ph][Et 3 GaF], and [Me 3 NCH 2 Ph][Me 3 InF], were reported in the following years. However, very little is known about the structures of these substances.…”

Section: Introductionmentioning

confidence: 99%

Cesium Trialkylfluorometalates of Gallium and Indium: Compounds with Heterocubane Structure

1996

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The cesium triorganofluorometalates [Cs{R3MF}]4 (1, M = Ga, R = Et; 2, M = Ga, R = i-Pr; 3, M = In, R = Et; 4, M = In, R = i-Pr) have been prepared by the reaction of the corresponding group 13 metallanes GaEt3, Ga(i-Pr)3, InEt3, and In(i-Pr)3 with CsF in acetonitrile. 1−4 have been fully characterized by elemental analysis, and IR, NMR, and MS techniques. The crystal structures of 2 and 4 have been determined. 2 and 4 are isostructural and crystallize in the cubic space group I23, with a = 1396.3(1) pm, V = 2722.3(5) × 106 pm3, Z = 2, and R 1 = 0.0168 (wR 2 = 0.0343) for 2 and a = 1417.1(2) pm, V = 2845.8(6) × 106 pm3, Z = 2, and R 1 = 0.0166 (wR 2 = 0.0354) for 4. The structures of 2 and 4 display strongly distorted cubes with alternating cesium and fluorine atoms and can be described as (CsF)4 subunits of the CsF structure stabilized by M(i-Pr)3 groups. According to the analytical and spectroscopic data, 1 and 3 also possess Cs−F heterocubane structure.

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Section: Introductionmentioning

confidence: 99%

Cesium Trialkylfluorometalates of Gallium and Indium: Compounds with Heterocubane Structure

1996

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“…Although triorganofluorometalates have been known for 35 years, reports about their structures in the solid state are sparse. The aluminum derivatives − as well as the later published derivatives of the higher homologes gallium and indium, K[Me 3 GaF], K[Et 3 GaF], − [NMe 4 ][Et 3 GaF], [Me 3 NCH 2 Ph][Et 3 GaF], , [Et 3 NCH 2 Ph][Et 3 GaF], and [Me 3 NCH 2 Ph][Me 3 InF], supposedly consist of linear polymer chains of [R 3 MF] - units with a distorted trigonal-bipyramidal coordination sphere. In this case the cations should not be included into strong interionic interactions as it has been found for the salts K[Et 3 AlFAlEt 3 ] and K[Me 3 AlFAlMe 3 ]·C 6 H 6 …”

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confidence: 99%

π-Electron−Cesium Interactions in Cesium Triorganofluorometalates

1996

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The reaction of MMes3 (M = Ga, In; Mes = 2,4,6-Me3C6H2) with CsF in acetonitrile yields the trimesitylfluorometalates [{Cs(MeCN)2}{Mes3MF}]2·2MeCN ([1]2·6MeCN, M = Ga; [2]2· 6MeCN, M = In). Ga(CH2Ph)3 gives with CsF under the same conditions the salt [Cs{(PhCH2)3GaF}]2·2MeCN ([3]2·2MeCN). The treatment of 1 equiv CsF with 2 equiv of GaMes3 does not lead to Cs[Mes3GaFGaMes3] but to [1]2·6MeCN and the adduct [Mes3Ga(MeCN)] (4). [1]2·6MeCN−4 have been characterized by NMR, IR, and MS techniques as well as by X-ray analyses. [1]2·6MeCN and [2]2·6MeCN are solvated ion pairs in acetonitrile, while [3]2·2MeCN shows a monomer−dimer equilibrium. According to the X-ray structure determinations, [1]2·6MeCN and [2]2·6MeCN are isostructural and contain Cs−F four-membered rings. The fluorine centers at the rings are bound to the metallane groups. Each cesium cation is coordinated by two molecules of acetonitrile and by one mesityl group in a η3-fashion. The basic structural feature of [3]2·2MeCN is also a Cs−F four-membered ring; however, the cations in [3]2·2MeCN are surrounded by three phenyl groups of the benzyl substituents. The three η6-bound phenyl rings are contributed from two different metallane units. 4 possesses a distorted tetrahedral coordination sphere with a low pyramidalization of the Ga center (angular sum: 355°).

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“…By themselves symmetrical organometallic compounds of the RMR type and their solutions in polar solvents possess insignificant electrical conductivity [52,53] and cannot therefore be subjected to electrolysis. However, a mixture of such compounds with certain salts of the MX type, alkyl halides RX, metal hydrides MH, and finally other organometallic compounds sometimes gives electrically conducting solutions.…”

Section: Anodic Processesmentioning

confidence: 99%