Polymeric Tris[trimethyltin(IV)]hexacyanocobaltate(III), a Compound Non-Analogous to “Super Prussian Blue,” and Its Tris[tricyclopentadienyluranium(IV)] Homologue†‡
Dr. Kenan Yünlü
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Search for more papers by this authorDipl.-Chem. Nils Höck
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Search for more papers by this authorCorresponding Author
Prof. Dr. R. Dieter Fischer
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)Search for more papers by this authorDr. Kenan Yünlü
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Search for more papers by this authorDipl.-Chem. Nils Höck
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Search for more papers by this authorCorresponding Author
Prof. Dr. R. Dieter Fischer
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)Search for more papers by this authorChemistry of the Tricyclopentadienyluranium(IV) Cation in Aqueous Solution, Part 4. We thank J. P. Jacobsen for his assistance. This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.—Part 3: [1a].
Dedicated to Professor Helmut Behrens on the occasion of his 70th birthday
Abstract
The coordination polymer 1 with a three-dimensional network of Co atoms is formed as shown below. Distorted octahedral Co(CN)6 structural units are present in 1, which are linked through SnMe3 bridges such that the partial structures …CoCN → SnMe3 ← NCCo… are formed. The Sn atoms are coordinated trigonal-bipyramidally. Since, surprisingly, two-thirds of the chains are nonlinear, no super Prussian blue analogue can form; such an analogue should contain cubic Co8 cages.
References
- 1(a) See: R. D. Fischer, E. Klähne, G. R. Sienel, J. Organomet. Chem. 238 (1982) 99; (b) K. W. Bagnall, M. J. Plews, D. Brown, R. D. Fischer, E. Klähne, G. W. Landgraf, G. R. Sienel, J. Chem. Soc. Dalton Trans. 1982, 1999.
- 2 R. D. Fischer, G. R. Sienel, G. W. Landgraf, H. Wagner in U. Croatto, M. Graziani (Eds.): Proc. 7th ICOMC, Venice (Italy) Sept. 1975, Abstr. No. 1.
- 3 R. D. Fischer, G. R. Sienel, Z. Anorg. Allg. Chem. 419 (1976) 126.
- 4 R. D. Fischer, G. R. Sienel, J. Organomet. Chem. 156 (1978) 383.
- 5 R. D. Fischer, K. Yünlü, Proc. 28th IUPAC Congress, Vancouver (Canada), Aug. 1981, Abstr. No. IN 28.
- 6 K. Yünlü, Dissertation, Universität Hamburg 1983.
- 7 1 : A solution of K3[Co(CN)6] (0.72 g, 2.1 mmol) in 20 mL of H2O was added slowly to a stirred aqueous solution (20mL) of (CH3)3SnCl (1.3 g, 6.5 mmol). The white precipitate was filtered off (G4 sintered glass filter), washed in portions with 100mL of H2O, and dried in a drying cabinet at 100°C for 1h. M. p. = 335°C (decomp.). IR (KBr): v = 3000 (m, br.), 2915 (m), 1198 (w), 790 (vs, br.); Raman: v = 2995 (s, br.), 2920 (vs), 1210 (m, br.). - Correct elemental analyses. Corresponding reactions were carried out successfully with R = C2H5, n-C3H7, n-C4H9, and C6H5, as well as with [Fe(CN)6]3-, instead of [Co(CN)6]3- (R = CH3)[6].
- 8 E. g., H2O, tetrahydrofuran (THF), C6H6, and CCL4, but not dimethylsulfoxide or mineral acids.
- 9 IR: Perkin Elmer Model 325, Nujol mull, v = 2172 (s, CN), 2155 (vs, br., CN), 554 (s, (SnC) as) cm−1. KBr: v = 2175 (unclear, sh), 2157 (s).
- 10 Raman spectrometer Cary (Varian) Model 82; ca.-200°C (very poor scattering power at room temperature). v = 2195 (vs, CN), 2180 (s, CN), 2170 (sh, br., CN), 556 (m, br., (SnC) as), 524 (s, (SnC) sym) cm−1. We thank Prof. H. Schomborg, Kiel, for the measurements.
- 11 JEOL Model JNM-C-60 HL (K3[Co(CN)6]/H2O ext.) δ = −225. We thank Dr. W.-D. Basler, Hamburg, for the measurement.
- 12(a) See also: D. R. Eaton, C. V. Rogerson, A. C. Sandercock, J. Phys. Chem. 86 (1982) 1365; (b) H. Siebert, M. Weise, Z. Naturforsch. B30 (1975) 669.
- 13 Mössabauer spectrometer FHT 400 (Frieseke and Höpfner): γ-source: CaSnO2; standard: SnO2; −150°C; δ = 1.72; ΔE = 3.84 mm s-1. We thank Prof. K. Nagorny, Hamburg, for the measurement.
- 14See also: K. C. Molloy, M. B. Hossain, D. van der Helm, D. Cunningham, J. J. Zuckerman, Inorg. Chem. 20 (1981) 2402, and references cited therein.
- 15 Debye-Scherrer procedure; Philips PW 1050 powder diffractometer (Cukα, Ni filter); we thank Dr. W. Metz, Hamburg, for the measurement.
- 16 (a) Colorless, transparent crystals of 1 were grown from an initially clear THF/H2O solution (ca. 80 mL THF, 10–15 mL H2O) containing (CH3)3SnCl (1.75 g, 9 mmol) and K3[Co(CN)6] (0.96 g, 3 mmol) after approximately 7 d at 4°C; (b) structure determination: Hilger and Watts (Y290) four - circle diffractometer, MOκα (λ = 0.71069 Å), 18°C, ρexp. = 1.50 g. cm−1, ρcalcd = 1.58 g. cm−1; space group P2; due to unsatisfactory standard deviations, alternative refinement also for C2/c (75 reflections with 4σ ≤I≤ 15σ were not accounted for). The results of the two calculations differ only in the positions of the methyl groups on the linear [-CoCNSnNC-]∞ chains; a = 16.857 (6), b = 12.941(7), c = 14.664(5) Å, β = 106.99(3)°, V = 3083(4)Å3, Z = 4, θ/2θ-scan (4° <2θ <50°); from 5940 mostly symmetry-related reflections, 1123 independent reflections with |I|3 σ were obtained (in C2/c); R = 0.0780. -We thank Dr. J. Kopf, Hamburg, for valuable discussions. -Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2, by quoting the depository number CSD 51436, the names of the authors, and the journalcitation.
- 17(a) Nonlinear MNC linkages have also been identified in, e. g., coordination polymers of the [Fe(CN)6]4- ion. K2Zn3[Fe(CN)6]2. x H2O; Zn-N-C 155–158°; P. Gravereau, E. Garnier, A. Hardy, Acta Crystallogr. B 35 (1979) 2843; (b) KCe(H2O)3Fe(CN)6. H2O, Ce-N-C 155.9°; D. F. Mullica, W. O. Milligan, J. D. Oliver, Inorg. Nucl. Chem. Lett. 15 (1979) 1; (c) the tbp cation [(CH3CN)2Sn(c-C6H11)3]+ is nearly linear (C2NSnNC2) but lacks a mirror plane (Ψ-D3h): Sn-N-C 168–173°, Sn-N 2.37–2.47 Å; W. A. Nugent, R. J. McKenney, R. L. Harlow, Organometallics 3 (1984) 1315.
- 18 Two likewise nonequivalent Me3SnO2 (tbp) units are present in onedimensionally polymeric trimethyltin (IV) α-Phenylphosphonate [14].
- 19 2: Cp3UC1 (1.92 g, 4.1 mmol) was dissolved in ca. 150 mL of O2-free H2O on a G-4 Schlenk fritted glass filter and filtered. A solution of K3[Co(CN)6] (0.46 g, 1.4 mmol) in 30 mL of H2O, was rapidly added to the green filtrate. The finely dispersed, light-green precipitate was collected, washed with a small amount of H2O, and dried for ca. 2 h in high vacuum (ca. 30°C). Yield: 1.1 g (61.8%). Correct elemental analysis. Paramagnetism: μeff(293K) = 2.30 B. M. [25]. An X-ray powder diffraction pattern could not be obtained [15].
- 20 In contrast to the tbp systems [Cp3U(NCS)(NCCH3)] and [Cp3UCN]∞ [1], 2 did not afford a recognizable mass spectrum below 200°C.
- 21 M.p. ≥310°C (decomp.). For comparison, [Cp3UNCS]: m. p. = 180°C (decomp.), [Cp3UCN]∞: m.p. = 200°C (decomp.); see [1b].
- 22 For example, H2O, C2H5OH, CH3CN, (CH3)2CO, THF, C6H6.
- 23 NIR/VIS4 Cary 17 spectrometer; Teflon pellet in transmission; v = 16470 (s), 9700 (w), 7735 (s), 6486 (vs) cm−1 [1, 4, 6]. IR (KBr; Nujol) v = 2145 cm−1; Δv relative to K3[Co(CN)6]: +20 cm−1.
- 24 Compare also the space-filling model (a) of the anionic tbp system [Cp3U(NbW5O19)2]5−: V. W. Day, W. G. Klemperer, D. J. Maltbie, Organometallics 4 (1985) 104.
- 25 We thank Prof. B. Kanellakopulos, Karlsruhe, for susceptibility measurements in the range 4.2–320 K.
