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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 417-420 
    ISSN: 0009-2940
    Keywords: Gallium ; Low-valent compounds ; Gallium-gallium bond ; Terminal triphenytriazenido ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane (4) 1 reacts with 1,3-diphenyltriazene to yield two compounds, which were both characterized by a crystal structure determination. The gallium-gallium bond is retained in the yellow derivate [(H5C6)2N3](R)Ga-Ga(R)[N3(C6H5)2 2 [R = CH(SiMe3)2], which is formed by a ligand exchange reaction and shows two terminal chelating triazenido ligands besides two bis(trimethylsilyl)methyl groups; the Ga—Ga bond length is 245.79(6) pm. The second product is the orange dialkyl(diphenyltriazenido)gallium derivative R2Ga[N3(C6H5)2] 3, where the triazene has reacted as an oxidant by the cleavage of the Ga—Ga bond and probably by release of elemental hydrogen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1269-1272 
    ISSN: 0009-2940
    Keywords: Indium ; Clusters ; Low-valent compounds ; Trapping reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrahedral cluster compound tetrakis[[Tris(trimethylsilyl)methyl]indium(I)] 91) reacts in boiling n-hexane with benzil derivatives (p-X-C6H4)C(O)(p-X-C6H4) (X = H, OMe, Br), to yield the 1,4-cycloadditon products of the monomeric alkylindium(I), In-C(SiMe3)3, in which the In atoms are coordinated by a chelating enediolato ligand, to form a five-membered InO2C2 heterocycle. As shown by two crystal structure determinations (X = H, OMe), the products are dimeric in the solid state, with a four-membered In2O2 heterocycle in the molecular center and both C(SiMe3)3 groups, as well as both enediolato substitutents in a cis arrangement.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 355-360 
    ISSN: 1434-1948
    Keywords: Gallium ; Indium ; Low-valent compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1) with a Ga-Ga single bond and the corresponding diindane(4) 2 with an In-In single bond were treated with different protic reagents: tert-Butyl alcohol did not react with 1 at all, while phenol gave a mixture of unknown products, which could not be separated. The more acidic pentafluorophenol did not react as an acid, but C-F bonds were cleaved to form almost quantitatively the dimer (R2GaF)2 5, which was characterized by a crystal-structure determination. Water and 1 yielded the dimeric dialkylgallium hydroxide 6. The Ga-Ga bond was also cleaved by the reaction of 1 with durylthiophenol (duryl = 2,3,5,6-tetramethylphenyl), which gave two main products: R2Ga(SDuryl) 7 and RGa(SDuryl)2 8. In contrast, the chelating acid dibenzoylmethane reacted by means of a substituent exchange, with the release of two equiv. of bis(trimethylsilyl)methane for each formula unit of 1, to form 9, in which the Ga-Ga bond is retained and each chelating 1,3-diphenyl-1,3-propanedionato ligand is in a terminal position bonded to only one Ga atom, in more than 80% yield. The Ga-Ga bond is shortened [244.1(1) pm] compared to that in the starting compound tetraalkyldigallane(4) 1. The In-In bond of diindane(4) 2 is, however, cleaved in a similar reaction with dibenzoylmethane, and only the fragmentation product dialkyl(1,3-diphenyl-1,3-propanedionato)indium 10 could be isolated.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 201-207 
    ISSN: 1434-1948
    Keywords: Aluminium ; Gallium ; Low-valent compounds ; Insertion reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 reacted with trimethylsilyldiazomethane and bis(trimethylsilyl)diazomethane at room temperature by the insertion of the terminal nitrogen atoms into its aluminium-aluminium bond. As shown by a crystal structure determination, one of the aluminium atoms of each product enhanced its coordination number to four by the interaction with the central nitrogen atom of the C=N-N group, which results in the formation of a three-membered AlN2 heterocycle bearing an exocyclic N=C double bond. The reactions of the corresponding gallium compound (2) containing a gallium-gallium single bond needed more drastic conditions. Mixtures of many unknown products were formed, and only on treatment with trimethylsilyldiazomethane two compounds could be isolated after repeated recrystallization in yields below 10%, which were characterized by crystal structure determinations. One was identified as the trimeric dialkylgallium cyanide (8) with a nine-membered Ga3C3N3 heterocycle, and the other one (9) has a dialkylgallium fragment coordinated by both terminal nitrogen atoms of the chelating ligand NH2-N=C(SiMe3)-NH-. Due to the NMR spectroscopic characterization, 8 seems to be tetrameric in solution with an asymmetric structure containing four different gallium atoms. With this unusual structure, the IR spectrum of tetrameric dimethylgallium cyanide could now completely be interpreted, which was published more than 20 years ago.
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1661-1665 
    ISSN: 1434-1948
    Keywords: Gallium ; Low-valent compounds ; Macrocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane(4) 1 reacts with dicarboxylic acids like 1,4-benzenedi(methylcarboxylic) acid, 1,4-cyclohexanedicarboxylic acid, 1,6-hexanedicarboxylic acid, and 1,4-butanedicarboxylic acid (adipinic acid) by the release of two equivalents of bis(trimethylsilyl)methane and the retention of the Ga-Ga bond. Products are formed, in which the very short Ga-Ga bonds (237.7 pm on average) are bridged by two carboxylato groups. Two of these moieties are connected in each compound by two spacers (dimethylbenzene, cyclohexane, hexane, or butane) to form macrocyclic compounds with up to 22 atoms in the resultant heteroatomic rings. The dimeric form is also observed in solution. For comparison, the synthesis and structure of the product of the reaction of 1 with 1-adamantanecarboxylic acid is included, which also has the Ga-Ga bond (239.1 pm) bridged by two carboxylato groups.
    Additional Material: 3 Ill.
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