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  • crystal structures  (5)
  • Gallium compounds  (3)
  • syntheses  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 355-359 
    ISSN: 0009-2940
    Keywords: Aluminium compounds ; Gallium compounds ; Indium compounds ; Trimethylfluoro metalates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cesium-Fluorine Four-Membered Rings as Structural Motive in Cesium Triorganofluoro Metalates of Group 13The reactions of AlMe3, GaMe3, and InMe3 with CsF in acetonitrile furnish the corresponding trimethylfluoro metalates Cs[Me3MF] (1: M = Al, 2: M = Ga, 3: M = In). The salt-like compounds 1 - 3 were characterized by NMR, IR, and MS techniques as well as by X-ray structure analysis. Cs2F2 four-membered rings are the structure-dominating units in all three compounds. Compound 1 consists of puckered layers of weakly associated Cs2F2 rings parallel to (100), while the four-membered rings in 2 form infinite ladder-type chains. The Cs-F rings in 3 build up a heterocubane with a Cs4F4 core by ring stacking.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1579-1585 
    ISSN: 0009-2940
    Keywords: Gallium compounds ; Gallane, tribenzyl- ; Gallane, dibenzyl(benzyloxy)- ; Gallate, dibenzyldifluoro- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzylgallium Compounds. Coordination of Benzyl Ligands in Cs[(PhCH2)2GaF2]Dissolving (PhCH2)3Ga (1) in THF yields the complex [(PhCH2)3Ga · THF] (2). Reaction of 1 with dry oxygen in toluene at -78°C leads to [(PhCH2)2GaOCH2Ph]2 (3), which is also formed from 1 and PhCH2OH. The salts K[(PhCH2)2GaF2] (5) and Cs[(PhCH2)2GaF2] (6) were obtained from (PhCH2)2GaCl (4) and KF or CsF, respectively, in acetonitrile. Crystal structures were determined for 2, 3, 6 and {[(PhCH2)2GaCl]2 · toluene} (7). Gallane 2 is a chiral monomeric complex in the solid state. The benzyl substituents create a propeller-shaped molecule with a counterclock-wise orientation of the ligands. 3 and 7 are crystallizing as centrosymmetrical dimers with Ga2X2 rings (X=O, Cl). 6 consists in infinite chains of {Cs[(PhCH2)2GaF2]}2 units with Cs-F contacts. In addition to the Cs-F interaction, the coordination of each Cs+ ion by two phenyl rings in a η6- fashion is observed.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 67-71 
    ISSN: 0009-2940
    Keywords: Gallium compounds ; Heterocubanes, gallium-phosphorus ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Characterization of Gallium-Phosphorus HeterocubanesThe reaction of iPrGaCl2 with tBuPLi2 in Et2O at -78°C gives the heterocubane [iPrGaP(tBu)]4 (1) by using the “dilution principle”. {(MesGa)3[GaP(H)tBu][P(tBu)]4} (2) was formed, when three equivalents of MesGaCl2 and one equivalent of GaCl3 in THF at -78°C were treated with 5 equivalents of tBuPLi2. Compounds 1 and 2 were characterized by NMR, IR, and MS techniques as well as by X-ray structure determination. The heterocubane molecules of 1 are disordered in the crystal; every atom site of the central cubical frame work is occupied by gallium and phosphorus atoms (occupation factor 0.5). The structure of 2 contains two crystallographically unique molecules, which are not disordered because of the additional P(H)tBu groups.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1897-1904 
    ISSN: 0044-2313
    Keywords: Mesityltrifluoro gallates ; mesitylbromo indates ; syntheses ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mesityltrifluoro Gallates. The Crystal Structures of Cs[MesGaF3] and K[MesInBr3]Mes3Ga reacts with GaBr3 in the ratio 1:2 in a commutation reaction to MesGaBr2 (1). 1 can be reacted with KF and CsF in MeCN to K[MesGaF3] (2) and Cs[MesGaF3] (3), respectively. K[MesInBr3] (4) was isolated when MesInBr2 was treated with KF in MeCN. The use of 15-crown-5 was leading to [K(15-crown-5)2][Mes2InBr2] (5) in a substituent exchange reaction. 1-5 were characterized by NMR-, IR- and MS-techniques. The solid state structures of 3 and 4 could be established by X-ray structure determinations. According to these determinations, a layer-type arrangement of the molecules is both structures in common. In the center of the layers, ionic interactions were formed, while the separation of the layers is caused by the bulky mesityl substituents.
    Notes: Mes3Ga reagiert mit GaBr3 im Verhält-nis 1:2 in einer Kommutierungsreaktion zu MesGaBr2 (1). 1 kann mit KF bzw. CsF in MeCN zu K[MesGaF3] (2) bzw. Cs[MesGaF3] (3) umgesetzt werden. Dagegen konnte bei der Reaktion von MesInBr2 mit KF in MeCN nur K[MesInBr3] (4) isoliert werden. Der Einsatz von 15-Krone-5 führt nach einer Substituentenaustauschreaktion zu [K(15-Krone-5)2][Mes2InBr2] (5). 1-5 wurden mittels NMR- und IR-Spektroskopie sowie Massenspektrometrie charakterisiert. Die Festkörperstrukturen von 3 und 4 konnten mit Röntgenstrukturanalysen aufgeklärt werden.Danach ist beiden Verbindungen ein schichtartiger Aufbau gemeinsam, wobei im Zentrum der Schichten die interionischen Wechselwirkungen ausgebildet werden. Die Separation der Schichten folgt aus der abschirmenden Wirkung der Mesitylgruppen an der Oberfläche der Schichten.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 597-606 
    ISSN: 0044-2313
    Keywords: Diorganogallium fluorides ; Diorganoindium fluorides ; reactions ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Diorganogallium(indium) Fluorides. The Crystal Structure of Mes2InFMes2GaF (1) reacts with t-BuNH2 at 20°C to the amine adduct [Mes2Ga(F)(t-BuNH2)] (2). Treatment of 1 with H2S gives after a redox reaction γ-S8-Sulfur (Muthmanns' Sulfur) (3) as the only isolated product. When i-Pr2InF (4) is reacted with [SnCl2(dioxane)] in toluene at 70°C one yields after workup [i-PrInCl2(dioxane)] (5), which is formed after ligand exchange and reaction with dioxane.2 and 5 were investigated by NMR-, IR- and MS-techniques. In addition, 2 · 2,5 THF, 3, 5 and Mes2InF were characterized by an X-ray structure determination. According to that 2 · 2,5 THF contains dimeres, associated by hydrogen brigdes, while 5 possesses a polymeric structure with bridging dioxane molecules. 3 forms eightmembered rings with C2-symmetry. Me2InF is a trimer in the solid state with an In3F3-backbone.
    Notes: Mes2GaF (1) reagiert mit t-BuNH2 bei 20°C zum Aminaddukt [Mes2Ga(F)(t-BuNH2)] (2). Bei Einwirkung von H2S auf 1 tritt eine Redoxreaktion ein, deren einziges isoliertes Produkt der γ-S8-Schwefel (Muthmannsche Schwefel) (3) ist. Wird i-Pr2InF (4) mit [SnCl2(Dioxan)] in Toluol bei 70°C umgesetzt erhält man nach Aufarbeitung das durch Ligandenaustausch und Adduktformierung gebildete [i-PrInCl2(Dioxan)] (5).2 und 5 wurden mittels NMR- und IR-Spektroskopie sowie Massenspektrometrie untersucht. Zusätzlich wurden 2 · 2,5 THF, 3, 5 und Mes2InF durch eine Röntgenstrukturanalyse charakterisiert. 2 · 2,5 THF liegt danach als über Wasserstoffbrückenbindungen assoziiertes Dimer vor, während 5 eine polymere Struktur mit verbrückenden Dioxanmolekülen besitzt. 3 bildet achtgliedrige Ringe mit zweizähliger Lagesymmetrie. Mes2InF formt Trimere mit einem In3F3-Sechsring-Gerüst.
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  • 6
    ISSN: 0044-2313
    Keywords: Organoindium compound ; organothallium compound ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Trimesitylthallium. A Comparison of the Trimesitylelement Compounds of Group 13The reaction of T1C13 with MesMgBr (Mes = 2,4,6-Me3C6H2) in THF at 0°C gives trimesitylthallium, TlMes3 (2). 2 has been characterized with NMR, IR and MS techniques as well as by an X-ray structure determination. 2 crystallizes isostructural to InMes3 (1a). The molecules of 2 are coordinated by the three mesityl substituents in a planar fashion. A new modification of InMes3 (1b) could be obtained by recrystallization of InMes3 from toluene/n-pentane in the space group C2/c. The literature known modification 1a and the new metallane 2 crystallize in the space group P21/n. The molecules in 1b possess C2-symmetry. The trimesitylelement compounds EMes3 (E = B, A1, Ga, In, T1) have been compared with each other.
    Notes: Die Reaktion von TlCl3 mit MesMgBr (Mes = 2,4,6-Me3C6H2) in THE bei 0°C liefert Trimesitylthallium, TlMes3 (2). 2 wurde mittels NMR- und IR-Spektroskopie bzw. Massenspektrometrie untersucht. Die Röntgenstrukturanalyse ergab ein isostrukturell zu InMes3 (1 a) kristallisierendes Molekül, dessen Tl-Zentrum planar von den drei Mesitylsubstituenten umgeben ist. Durch Kristallisation aus Toluol/n-Pentan konnte eine neue Modifikation des In-Mes3 (1 b) erhalten werden, die im Gegensatz zu 1 a und 2 (P21/n) in der Raumgruppe C2/c kristallisiert, wobei die Moleküle von 1 b C2-Symmetrie besitzen. Die Trimesitylelement-Verbindungen EMes3 (E = B, Al, Ga, In, Tl) werden miteinander verglichen.
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  • 7
    ISSN: 0044-2313
    Keywords: Mixed polyselenido complexes of zinc/tungsten, Mercury/tungsten ; crystal structures ; FIR spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses and Crystal Structures of the Polyselenido Complexes (PPh4)6[M(Se4)2]2[WSe4] · DMF with M = Zinc and MercuryThe title compounds have been prepared by the reactions of the acetates of zinc and mercury, respectively, with excess (PPh4)2 WSe4 in boiling dimethylformamide, forming black-red single crystals. According to the X-ray structure determinations both compounds crystallize isotypically in the space group 12/a with four formula units per unit cell. (PPh4)6[Zn(Se4)2]2[WSe4] · DMF: a = 2888.1(6), b = 1740.3(2), c = 2893.9(4) pm, β = 90.47(1)°. 3230 observed unique reflections, R = 0.009.(PPh4)6[Hg(Se4)2]2[WSe4] · DMF: a = 2891.8(5), b = 1738.0(4), c = 2920.1(5) pm, β = 90.29(2)°. 2978 observed unique reflections, R = 0.115%.The compounds consist of PPh4+ ions, spirocyclic octaseleno metallates [M(Se4)2]2-, tetrahedral WSe42-ions, and disordered DMF Molecules.
    Notes: Die Titelverbindungen entstehen in Form schwarz-roter Einkristalle beim Erhitzen der Acetate von Zink und Quecksilber mit überschüssigem (PPh4)2 WSe4 in Dimethylformamid-Lösungen. Nach den Röntgenstrukturanalysen kristallisieren die Verbindungen isotyp in der Raumgruppe I2/a mit vier Formeleinheiten pro Elementarzelle. (PPh4)6[Zn(Se4)2]2[WSe4]· DMF: a = 2888,1(6), b = 1740,3(2), c = 2893,9(4) pm, β = 90,47(1)°. 3230 beobachtete unabhängige Reflexe, R = 9,9%.(PPh4)6[Hg(Se4)2]2[WSe4] · DMF: a = 2891,8(5), b = 1738,0(4), c = 2920,1(5) pm, β = 90,29(2)°. 2978 beobachtete unabhängige Reflexe, R = 11,5%.Die Verbindungen bestehen aus PPh4 +-Ionen, spirocyclischen Octaselenometallaten [M(Se4)2]2-, tetraedrischen WSe42- Ionen und eingelagerten, fehlgeordneten DMf-Molekülen.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 847-850 
    ISSN: 0044-2313
    Keywords: Diorganoindium cations ; syntheses ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diorganoindium Cations. The Crystal Structure of [Mes2In][BF4](PhCH3)2In and Mes3In react with BF3 · OEt2 in a ratio of 3:4 at 80°C in toluene to the corresponding salts [R2In][BF4] [R = PhCH2 (1), Mes (2)]. The same results could be obtained, when the diorganoindium fluorides (PhCH2)2InF and Mes2InF were treated with BF3 · OEt2 at 80°C in toluene. 1 und 2 were characterized by NMR-, IR- und MS-techniques. The arrangement of the ions in 2 could be established by an X-ray structure determination. The cations and anions of 2 are forming infinite chains. The metal centers are coordinated by two BF4--ions, so that every In atom possesses a distorted octahedral coordination sphere.
    Notes: (PhCH2)3In und Mes3In reagieren mit BF3 · OEt2 im Verhältnis 3:4 bei 80°C in Toluol zu den entsprechenden Salzen [R2In][BF4] [R = PhCH2 (1), Mes (2)]. Zum selben Ergebnis gelangt man, wenn die Diorganoindiumfluoride (PhCH2)2InF und Mes2InF mit BF3 · OEt2 bei 80°C in Toluol behandelt werden. 1 und 2 wurden mittels NMR- und IR-Spektroskopie sowie Massenspektrometrie charakterisiert. Die Anordnung der Ionen in 2 konnte durch eine Röntgenstrukturanalyse aufgeklärt werden. 2 bildet danach unendliche Ketten aus Kationen und Anionen, wobei durch eine chelatartige Anordnung zweier BF4--Ionen an jedes Metallzentrum eine verzerrt oktaedrische Koordinationssphäre der Indiumatome resultiert.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 718-726 
    ISSN: 0044-2313
    Keywords: Organoindium fluorides ; organoindium fluoride cesium fluoride complexes ; syntheses ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Insertion of Metal Fluorides in Organoindium Fluorides.The reaction of i-Pr2InCl (1) with CsF in acetonitrile at room temperature yields [(i-Pr2InF)5(CsF · 2 MeCN)] ([2 · 2 MeCN]). {[(MesInF2)10MgF2] · 5 toluene} ({3 · 5 toluene}) can be isolated as a by-product in the reaction of Mes3In with BF3 · OEt2 in the presence of MgBrCl. [2 · 2 MeCN] and {3 · 5 toluene} were characterized by NMR spectroscopy as well as by X-ray structure determinations. [2 · 2 MeCN] forms infinite double chains of (i-Pr2InF)5-blocks and CsF-units. The coordination sphere of the cesium atom consists of three fluorine atoms and the nitrogen atoms of three acetonitrile molecules, which wrap the metal atom in a strongly distorted octahedral fashion. One of the acetonitrile molecules in [2 · 2 MeCN] has a μ2-bridging function. This results in the formation of four membered Cs2N2-rings.In {3 · 5 toluene}, ten molecules of MesInF2 are forming a cage in which a linear MgF2-unit is inserted.
    Notes: Die Reaktion von i-Pr2InCl (1) mit CsF in Acetonitril bei Raumtemperatur führt zu [(i-Pr2InF)5(CsF · 2 MeCN)] ([2 · 2 MeCN]).{[(MesInF2)10MgF2] · 5 Toluol} ({3 · 5 Toluol}) kann als Nebenprodukt bei der Umsetzung von Mes3In mit BF3 · OEt2 in der Gegenwart von MgBrCl erhalten werden. [2 · 2 MeCN] und {3 · 5 Toluol} wurden mittels NMR-Methoden sowie durch Röntgenstrukturanalysen charakterisiert. [2 · 2 MeCN] bildet unendliche Doppelstränge aus (i-Pr2InF)5-Blöcken und CsF-Einheiten. Die Koordinationssphäre des Cs-Atoms besteht aus drei F-Atomen und den N-Atomen von drei Acetonitril-Molekülen, was zu einer stark verzerrt oktaedrischen Umgebung des Metallatoms führt. Eines der Acetonitril-Moleküle in [2 · 2 MeCN] hat eine μ2-verbrückende Funktion, woraus sich die Ausbildung von Cs2N2-Vierringen ergibt.In {3 · 5 Toluol} wird ein Käfig aus zehn MesInF2-Einheiten geformt, in welchem eine lineare MgF2-Einheit eingelagert ist.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 346-358 
    ISSN: 0044-2313
    Keywords: Organoindium bromides ; solvate complexes ; trimagnesiumpentahalogen cation ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Organoindium Bromidesi-Pr3In gives with InBr3 (molar ratio 2:1, toluene, 50°C) i-Pr2InBr (1) and (molar ratio 1:2, toluene, 80°C) i-PrInBr2 (2). The corresponding reaction of (PhCH2)3In and InBr3 (2:1) gives (PhCH2)2InBr (3), while PhCH2InBr2 could be isolated only as ether adduct [PhCH2InBr2(OEt2)n] (4). With DME/MeCN and 2 and 4 with THF, respectively, yields the solvate complexes [InBr3(DME)(MeCN)] (5), [i-PrInBr2(THF)2] (6) and [PhCH2InBr2(THF)2] (7). The compounds 1-7 were investigated with NMR-, IR- and MS-techniques. Pyrolysis of the raw material of i-Pr3In, which contains “MgBrCl” and additional treatment with Et2O yields the salt [Mg3Cl4,65Br0,35(Et2O)6][i-PrInBr2,7Cl0,3] (8). The cation, a trinuclear magnesium complex, possesses local D3h-symmetric of the Mg3X5 backbone (X = Cl, Br).
    Notes: i-Pr3In ergibt mit InBr3 (Molverhältnis 2:1, Toluol, 50°C) i-Pr2InBr (1) und (Molverhältnis 1:2, Toluol, 80°C) i-PrInBr2 (2). (PhCH2)3In und InBr3 (2:1) ergeben entsprechend (PhCH2)2InBr (3), während PhCH2InBr2 nur als Etherat [PhCH2InBr2(OEt2)n] (4) erhalten wurde. Mit DME/MeCN bzw. 2 und 4 mit THF werden die Solvatkomplexe [InBr3(DME)(MeCN)] (5) bzw. [i-PrInBr2(THF)2] (6) und [PhCH2InBr2(THF)2] (7) erhalten. 1-7 wurden mittels NMR-und IR-Spektroskopie bzw. Massenspektrometrie untersucht. Pyrolyse des „MgBrCl“-enthaltenden Rohproduktes von i-Pr3In und nachträgliches Behandeln mit Et2O liefert das Salz [Mg3Cl4,65Br0,35(Et2O)6][i-PrInBr2,7Cl0,3] (8), welches ein dreikerniges, Magnesium-haltiges Kation mit lokaler D3h-Symmetrie des Mg3X5-Gerüstes (X = Cl, Br) enthält.
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