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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2215-2220 
    ISSN: 1434-1948
    Keywords: Magnesium ; Metalation ; Phosphorus ; Polyhedra ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnesiation of triisopropylsilylphosphane with dibutylmagnesium in toluene yields the octanuclear complex [Mg8(PSiiPr3)6{P(H)SiiPr3}4] (1) which consists of MgPSiiPr3 units forming a hexagonal Mg6P6 prism, with two opposite Mg2P2 moieties capped by additional Mg[P(H)SiiPr3]2 groups. If a small amount of THF is present during the metalation reaction [(THF)4Mg6(PSiiPr3)6] (2) also containing a hexagonal Mg6P6 prism can be isolated. The magnesiation of H2P-SiiPr3 in tetrahydrofuran leads to the formation of the tetrameric complex [(THF)MgPSiiPr3]4(3) with a slightly distorted Mg4P4 cubane-like structure.The structures depend strongly on the steric strain caused by the trialkylsilyl substituents and the neutral coligands at the magnesium center. The highest steric strain, which is induced by coordination to every magnesium atom, leads to the smallest MgnPn polyhedron - the central Mg4P4 heterocubane moiety. In compounds 1 and 2 the hexagonal Mg6P6 prism is formed, however, with reduced steric strain as observed for 2 where the Mg-P bond lengths become more similar.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 505-509 
    ISSN: 1434-1948
    Keywords: Chlorobis(dimethylamino)(3-indenyl)diborane(4) ; Bis(dimethylamino)bis(1-indenyl)diborane(4) ; Bis(dimethylamino)(1-indenyl)(3-indenyl)diborane(4) ; Bis(dimethylamino)bis(3-indenyl)diborane(4) ; Rearrangement ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Indenyllithium reacts with dichlorobis(dimethylamino)diborane(4) with formation of bis(dimethylamino)bis(1-indenyl)diborane(4) which rearranges on heating to the isomer bis(dimethylamino)bis(3-indenyl)diborane(4). The „mixed” bis(dimethylamino)(1-indenyl)(3-indenyl)diborane(4) is obtained from indenyllithium and chlorobis(dimethylamino)(3-indenyl)diborane(4). The main structural differences between the two isomers 3 and 4 are a slightly shorter B-B bond in 4, as well as a stronger twist about the B-B bond (89.9° vs. 67.4°) and, as expected, a shorter B-C bond. There is, however, no significant B-C π bonding.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1519-1527 
    ISSN: 1434-1948
    Keywords: B,B′-Dimesityldiborane(4) dihalides ; B,B′-Diamino-B,B′-dimesityldiboranes(4) ; B,B′-Di-tert-butyloxy-B,B′-dimesityldiborane(4) ; B,B′-Dimesityl-B,B′-di(organylthio)diborane(4) ; NMR spectroscopy ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient route to B,B′-dihalo-B,B′-dimesityldiboranes(4) is reported, as well as the conversion of these and of B,B′-dimesityl-B,B′-dimethoxydiborane(4) into other B,B′-dimesityldiboranes B2mes2X2 (X = OR, SR, NR2, NHR). The substituents X influence the shielding of the 11B nucleus in the expected manner. Hindered rotation about the B-N bond is observed for X = pyrrolyl, while in solution there is free rotation about the B-C bond. However, X-ray structural results reveal that the mesityl group is almost orthogonal to the B(B)CY plane in the solid state. The shortest B-B bond is observed in mes2B2I2, indicating that the iodide is the strongest Lewis acid in the reported series of mes2B2Y2 compounds. This is also reflected in short B-C bonds. Moreover, the two mes(Y)B units also approach orthogonality in these diborane(4) compounds, and thus enforce this as a typical structural feature of diborane(4) derivatives. For this reason, the planar C(N)B-B(N)C unit of B,B′-di(benzylamino)-B,B′-dimesityldiborane(4) is regarded as exceptional for aminodiboranes(4).
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0009-2940
    Keywords: Magnesium tetrahydridoaluminate ; Magnesium halide tetrahydridoaluminate ; (Organyloxo)magnesium tetrahydridoaluminates ; X-ray structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular structures of XMg(A1H4) · 4 THF (1a, 2, 3a) (X = A1H4, Cl, Br) have been determined by X-ray structural analysis. Each compound possesses a hexacoordinated Mg center and AlH4- groups bound to this center via a single hydride bridge bond. Attempts to prepare ROMg(AlH4) compounds were successful only for sterically demanding groups R (R = CMe3, CPh3, naph, mes, smes). The 2-naphthoxy derivative 7, a compound with the composition (naphO)Mg-(AlH4) · 2.5 THF, is a dimer with a central Mg2O2 ring. One of its two AlH4- groups is terminally bound to one Mg atom, the other bridges the two Mg centers. This structure indicates how AlH4- transfer may occur from ROMg(AlH4) compounds to form Mg(OR)2 and Mg(AlH4)2.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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