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Solutions of Gallium Trichloride in Ethers

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Solutions of Gallium Trichloride in Ethers Solutions of Gallium Trichloride in Ethers: A 71 Ga NMR Study and the X-Ray Structure of GaCl3 • Monoglyme Stefan Böck, Heinrich Nöth*, and Astrid Wietelmann Institute oflnorganic Chemistry, University of Munich, Meiserstraße 1, D-8000 München 2 Dedicated to Prof. Dr. G. Fritz on the occasion o f his 70 th birthday Z. Naturforsch. 45b, 979-984 (1990); received January 22, 1990 71Ga NMR Spectra, Gallium Trichloride-Ether, Gallium Trichloride-Tetrahydrofuran, rä-Dichloro-bis(dimethylglycolether)gallium-tetrachlorogallate Solutions of GaCl 3 in various ethers have been studied by 7lGa NMR spectroscopy. <S7lGa data indicate that the predominant species in diethylether and tetrahydrofuran solutions are G aC l3 0 (C 2H 5) 2 and G aC l3 -2 0 C 4Hg, respectively. However, in monoglyme solution disso­ ciation occurs and the product crystallizing from the solution is [c 7's-GaCl2(monoglyme)2]- G aCl4 as demonstrated by an X-ray structure determination of the solvate GaCl 3 • monoglyme. Introduction deduced from spectroscopic studies (IR, Raman, Aluminium trichloride, which crystallizes in an N M R ) [8]. Dissociation of A1C1 3 in diethylether ionic lattice, dissolves in many polar solvents and has been observed not only by the electrical con­ forms a large number of coordination compounds. ductance of its solution but also by : 7A1 N M R spectroscopy [1,9, 10], Dissociation processes are [Al(OH2)6]Cl3 crystallizes from acid aqueous solu­ increasingly favoured in the series diethylether, tions of A1C1 3 [1], The compound A1C1 3-2C H 3CN THF, dimethylglycolether (monoglyme), and di- can be obtained from solutions of A1C1 3 in acetoni- trile, and this compound was shown to be methyldiglycolether [10], Moreover, crown ethers L support ionization, as shown by the complex of [A1C1(NCCH3)5][A1C14]2 • CHjCN by X-ray struc­ 2 A1C1 -4-crown-12 [11] producing the salt ture determination [2]. In addition, a second 3 acetonitrile adduct has been found to be [C12A1L]A1C14. Many additional cations have been detected in [A1(NCCH3)6](A1C14)3 [3]. Pyridine (py) yields sev­ solutions o f A1C1 in highly polar solvents by A1 eral compounds with A1C1 3 depending on the 3 27 mode of preparation, and the structures of NMR spectroscopy. However, the question whether the solid in equilibrium with the solution AlCl3-3py and AlCl 3-2py have been determined reflects the solution state needs still further explo­ to be mer-A1C13 • 3 py and [/ra^ 9-Cl2Al(py) 4][AlCl4], respectively [4], From diethylether the compound ration. From this point of view it was of considera­ ble interest to compare the behaviour of GaCl 3 to ­ A1C13-0 (C 2H5)2, containing a tetracoordinated aluminium atom, has been isolated [5]. Moreover, wards ethers as solvents with that of A1C13. Al­ though 71Ga NMR spectroscopy is not as versatile two different kinds of A1C1 3-2THF compounds (THF = tetrahydrofuran) have been character­ as 27A1 NMR spectroscopy, the method can be ized. The first one results from the action of THF used to get information on solution species. on the adduct (Me 2N)3SiCl- A1C13. It is the molec­ Results ular compound A1C1 3-2THF with a pentacoordi- nated Al-atom in a trigonal-bipyramidal environ­ Gallium trichloride in diethylether ment and the THF molecules in apical positions The low melting adducts GaX 3 O E t2 (X = Cl, [6]. In contrast, if toluene is added to a solution of Br, I) have been isolated and characterized [12], A1C1 in tetrahydrofuran the solid A1C1 -2T H F , 3 3 and it is well known that G aC l 3 dissolves much which separates, is the ionic compound [cis- more readily in organic solvents than does A1C13. C1 A1(THF) ]A1C1 [7] whose existence was first 2 4 4 In contrast to A1C1 3 solutions in diethylether those of G aC l 3 show only very weak electrical conduc­ * Reprint requests to Prof. Dr. H. Nöth. tivity. 0.204 and 0.123 M solutions of GaCl 3 in di­ Verlag der Zeitschrift für Naturforschung, D-7400 Tübingen ethylether are almost non-conducting, while the 0932 - 0776/90/0700 - 0979/$ 01.00/0 specific electrical conductivity of comparable Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung This work has been digitalized and published in 2013 by Verlag Zeitschrift in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der für Naturforschung in cooperation with the Max Planck Society for the Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Advancement of Science under a Creative Commons Attribution Creative Commons Namensnennung 4.0 Lizenz. 4.0 International License. 980 St. Böck et al. ■ Solutions of Gallium Trichloride in Ethers AICI3 solutions in diethylether is 1.2-10 ~2 cm2 ß“ 1 exhibits two 71Ga NM R signals, a broad and rela­ [13]. Thus, G aC l3 in diethylether appears to form tively weak signal at Ö = 329 ppm and a strong and almost no ionic products. fairly sharp one at 3 = 261 ppm. On dilution, the In consonance with these findings is the broad broad resonance vanishes while the other becomes 7lGa NMR signal at S = 260 ppm which we ob­ increasingly sharper (260 versus 160 Hz at half serve at much lower field than reported by Akitt height). These results clearly indicate dissociation et al. (<S71Ga = 137 ppm) [14]. This signal corre­ of GaCl3, presumably according to sponds to the formation of Cl3Ga • OEt2. Exchange 2G aC l3 L G aC l2L2+ + G aC l4“ (1) of this etherate with solvent ether is slow as two sets of 13C NM R signals are observed. or 2 G aC l 3 • L G aC l2L+ + G a C lf + L (2) The 71Ga NMR chemical shift (S = -329 ppm) Gallium trichloride in tetrahydrofuran and dioxane corresponds best with tetracoordination: both a pentacoordinated as well as hexacoordinated gal­ Tetrahydrofuran dissolves GaCl 3 quite readily. lium center should show a resonance at much Solutions in the concentration range 0.12-0.97 higher field [17]. We therefore assign this signal to m ol /1 show negligible electrical conductivity in a tetracoordinated GaCl3 L adduct. Whether dis­ contrast to A1C1 3 solutions in this solvent [15]. sociation occurs according to eq. ( 1 ) or ( 2) cannot These solutions produced a detectable 7,Ga NMR be decided on the basis of the 71Ga NMR spectra signal neither at ambient temperature nor at lower alone. temperature (-20 °C). Also, the isolated G aC l3 • THF, dissolved in C 6D6, gave no 7lGa reso­ The structure of [GaCl2(monoglyme)2]GaCl4 nance. Obviously, quadrupolar relaxation is very The adduct GaCl3 • monoglyme separating from fast for this compound. As expected, two l3C monoglyme solutions forms well shaped crystals NMR signals are observed for GaCl 3 TH F. The from dichloromethane solutions suitable for an carbon atoms bonded to the oxygen atom are X-ray crystallographic study. The crystals are shifted to lower field compared with the free ligand orthorhombic, and 8 GaCl3- monoglyme units are while the carbon atoms of the other CH 2 groups found in the unit cell. However, as depicted in are slightly better shielded. Broad resonances are Fig. 1 the compound is not a molecular adduct but observed for the two sets of CH 2 groups. rather the salt [Cl2Ga(monoglyme) 2]GaCl4. Bond­ A 71Ga NM R spectrum may allow to distinguish ing parameters are summarized in Table I. between tetra- or pentacoordination in solution. The tetrachlorogallate anion deviates only No 7,Ga NMR signal could be recorded for satu­ slightly from a regular tetrahedron, the C l-G a- rated solutions of GaCl 3 in dioxane. This definitely also excludes the formation of the readily detecta­ ble GaCl4_ anion. This is ascertained by the very low electrical conductivity of the GaCl 3 solution in dioxane. In this respect, GaCl 3 behaves like A1C13 in dioxane, where a 27Al NMR signal at ö = 66 ppm points to the presence of pentacoordinated Al [17]. N o signal at Ö = 105 ppm, typical for the presence of A1C14~ [17] was found. This excludes dissociation of A1C1 3 in dioxane into solvated A1C12+ and A1C14“. Gallium trichloride in monoglyme and diglvme Compared to solutions of GaCl 3 in diethylether or tetrahydrofuran the solubility of this halide in monoglyme is low (< 0.1 M). This is one of the rea­ ^>C I3 sons why no 71Ga NMR signal was recorded. In Fig. 1. ORTEP plot of [Cl 2Ga(monoglyme):]GaCl4. contrast, a 0.34 M solution of GaCl 3 in diglyme Thermal ellipsoids represent a 30% probability. St. Böck et al. ■ Solutions of Gallium Trichloride in Ethers 981 Table I. Selected bond distances (in A) and bond angles neat liquid fits, with tetracoordination [14], The (in degrees) of [GaCl 2(monoglyme) 2]GaCl4. Estimated 71Ga NMR signal for solutions of GaCl 3 in di- standard deviations in parenthesis. ethylether is found at lower field (Ö = 260 ppm); Bond distances this chemical shift value would correspond with Ga 1 - Cl 2 2.187(2) Ga2-08 2.064(8) the form ation of G aC l4~ [17]. The line width G a l- C l 2 2.177(2) G a 2 - 0 11 2.081(6) (—7500 Hz), however, excludes such an assign­ G a l- C l 3 2.171(2) 02-C 1 1.365(18) ment, as does the low electrical conductivity. G a 1-C 14 2.170(2) 02-C3 1.540(9) G a2 -C 1 5 2.204(5) 05-C6 1.435(12) Therefore, we have to conclude that the principal G a2 -C 1 6 2.223(4) 0 5 - C 4 1.437(15) species in solution is GaCl 3 • OE t2.
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