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  • 1
    Electronic Resource
    Electronic Resource
    Formation of Calcium-Carbon Bonds From a Lewis Acid-Base Reaction of Calcium Bis[bis(trimethylsilyl)amide] and Tris(trimethylsilylmethyl)alane (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2209-2214 
    Details
    ISSN: 1434-1948
    Keywords: Aluminium ; Amides ; Calcium ; Metallacycles ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of calcium bis[bis(trimethylsilyl)amide] with two equivalents of tris(trimethylsilylmethyl)alane yields (Me3SiCH2)2Al-N(SiMe3)2 (1) and the dimer [(Me3Si)2N-Ca(μ-CH2SiMe3)2Al(CH2SiMe3)2]2 (2). The five-coordinate bridging carbon atoms show Ca-C bond lengths of 264 and 268 pm. A similar reaction with calcium bis[bis(trimethylsilyl)phosphanide] gives the dimer [(Me3SiCH2)2Al-P(SiMe3)2]2 (3) with crystallographic C2 symmetry. A calcium-containing species is not isolable, however, in the presence of DME - ether cleavage reactions and the formation of the centrosymmetric dimer [(Me3SiCH2)2Al-OCH2CH2OMe]2 (4) are observed. The central moiety is an Al2O2 cycle with fivefold coordinated aluminium centers.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Magnesiation of Triisopropylsilylphosphane: Synthesis and Structures of New Mg2nP2m Polyhedra (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2215-2220 
    Details
    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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  • 3
    Electronic Resource
    Electronic Resource
    Synthesis and Homomolecular Metalation of Trialkylsilylphosphanides of Calcium and Barium (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 743-750 
    Details
    ISSN: 1434-1948
    Keywords: Arsenic ; Barium ; Calcium ; Metalations ; NMR spectroscopy ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metalation of triisopropylsilylphosphane with bis(tetrahydrofuran-O)calcium bis[bis(trimethylsilyl)amide] in tetrahydropyran (thp) in a molar ratio of 3:2 yields (Me3Si)2NCa[μ-P(H)SiiPr3]3Ca(thp)3 (1) containing a trigonal-bipyramidal Ca2P3 core, the metal atoms occupying apical positions. Reaction of two equivalents of triisopropylsilylphosphane or -arsane with bis(tetrahydrofuran-O)barium bis[bis(trimethylsilyl)amide] in tetrahydrofuran gives the corresponding bis(phosphanide) 2 and bis(arsanide) 3, compounds of the type (thf)3Ba[μ-E(H)SiiPr3]Ba(thf)2E(H)SiiPr3 with E = P, As. The equimolar reaction of (tri-tert-butylsilyl)phosphane with (thf)2Ba[N(SiMe3)2]2 in toluene yields heteroleptic dimeric (thf)2Ba[N(SiMe3)2][P(H)SitBu3] (4). Addition of a further equivalent of H2PSitBu3 leads to the formation of homoleptic (thf)nBa[P(H)SitBu3]2 (5). Dissolution of the latter in aromatic hydrocarbons leads to the elimination of H2PSitBu3, yielding dimeric (thf)Ba3(PSitBu3)2[P(H)SitBu3]2 (6). The inner core of 6 consists of the tetramer (BaPSitBu3)4 based on a Ba4P4 heterocubane unit, two opposite faces being capped with (thf)Ba[P(H)SitBu3]2 molecules.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Oligomeric Solvent-Free Magnesium Bis(phosphanides) - Molecular Structure of Trimeric Magnesium Bis[bis(trimethylsilyl)phosphanide] (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 517-521 
    Details
    ISSN: 1434-1948
    Keywords: Bis(silyl)phosphanes ; Magnesium ; NMR spectroscopy ; Oligomers ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metathesis reaction of (dme)LiPH2 and chlorodiisopropylsilane yields HP(SiHiPr2)2 (1) and P(SiHiPr2)3 (2). The metalation of 1 by n/sec-dibutylmagnesium in heptane leads to the formation of dimeric magnesium bis[bis(diisopropylsilyl)phosphanide] [(3)2]. A toluene solution of magnesium bis[bis(trimethylsilyl)phosphanide] (4) shows a dimer-trimer equilibrium in the 31P{1H}-NMR spectrum at -40°C with an increasing amount of the dimer with increasing temperature. A molecular mass determination by freezing-point depression in benzene yields a value of 516 g·mol-1, which lies between a monomeric and a dimeric molecule. Cooling of the toluene solution to -30°C leads to the precipitation of single crystals of monoclinic {(Me3Si)2P-Mg[μ-P(SiMe3)2]2}2Mg [(4)3].
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Synthese von substituierten Calcium-bis(disilylamiden) mittels der Transmetallierung von Zinn(II)- und Zinn(IV)-amidenProfessor Max Herberhold zum 60. Geburtstag gewidmet (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 1295-1305 
    Details
    ISSN: 0044-2313
    Keywords: Transmetalation ; Calcium, Stannylene ; Tin ; Amide ; NMR Spectroscopy, X-Ray Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Substituted Calcium-bis(disilylamides) by Transmetalation of Tin(II) and Tin(IV) AmidesStannylenes as well as stannanes with substituted disilylamino groups are valuable synthons for the synthesis of alkaline earth metal bis(disilylamides) via the transmetallation reaction. Whereas bis[2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentyl]stannylene 1 is a suitable reagent for this type of reaction, bis[trimethylsilyl-tris(trimethylsilyl)silylamino]stannylene 2 (monoclinic, P21/c, a = 1492.6(2), b = 1705.2(2), c = 1865.3(3) pm, β = 109.03(2)º, Z = 4) is not only attacked at the Sn—N-bond but also the N—Si-bond is cleaved by calcium metal. Similar light sensitivity as for 2 is observed for the mercury bis[trimethylsilyl-tris(trimethylsilyl)silylamide] 3, the homolytic M—N-bond cleavage leads to the formation of the trimethylsilyl-tris(trimethylsilyl)silylamino radical (g = 2.00485; a(N) = 16.2 G). The calcium tin exchange reaction of 1 in THF yields tris(tetrahydrofuran-O)calcium-bis[2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentanide] 4 (monoclinic, P21/n, a = 1060.9(2), b = 1919.3(5), c = 1686.0(3) pm, β = 90.30(2)º, Z = 4). The stannanes Men-4Sn[N(SiMe3)2]n with n = 1 or 2 are also valuable materials for the synthesis of bis(tetrahydrofuran-O)calcium-bis[bis(trimethylsilyl)amide].
    Notes: Stannylene und Stannane mit substituierten Disilylamino-Substituenten eignen sich als Edukte für die Transmetallierungsreaktion zur Synthese von Calcium-bis(disilylamiden). Anwendung fanden Bis[2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentyl]stannylen 1 und Bis[trimethylsilyl-tris(trimethylsilyl)silylamino]stannylen 2 (monoklin, P21/c, a = 1492,6(2), b = 1705,2(2), c = 1865,3(3) pm, β = 109,03(2)º, Z = 4). Bei der Verwendung von 2 greift das destillierte Calcium allerdings nicht nur die Sn - N-, sondern auch die N—Si-Bindung an. Ähnlich wie bei dem Quecksilber-bis[trimethylsilyl-tris(trimethylsilyl)silylamid] 3 beobachtet man bereits bei Tageslicht die homolytische Spaltung der Sn—N- bzw. Hg—N-Bindung und die Bildung des Trimethylsilyl-tris(trimethylsilyl)silylamino-Radikals 5 (g = 2,00485; a(N) = 16,2G). Der heterogen geführte Zinn-Calcium-Austausch bei Verbindung 1 in THF führt in guten Ausbeuten zum Tris(tetrahydrofuran-O)calcium-bis[2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentanid] 4 (monoklin, P21/n, a = 1060,9(2), b = 1919,3(5), c = 1686,0(3) pm, β = 90,30(2)º, Z = 4). Auch die Stannane Men-4Sn[N(SiMe3)2]n mit n = 1 oder 2 eignen sich als Synthone zur Synthese von Bis(tetrahydrofuran-O)calcium-bis[bis(trimethylsilyl)amid].
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220804
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  • 6
    Electronic Resource
    Electronic Resource
    Synthese und Charakterisierung heterobimetallischer Bis(trimethylsilyl)phosphanide von Barium und Zinn (1995)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 877-888 
    Details
    ISSN: 0044-2313
    Keywords: Barium ; Bis(trimethylsilyl)phosphanide ; Phosphanide ; Tin ; NMR ; X-ray Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Characterization of Hetero-bimetallic Bis(trimethylsilyl)phosphanides of Barium and TinThe reaction of barium bis[bis(trimethylsilyl)amide] with one equivalent of bis(trimethylsilyl)phosphane in 1,2-dimethoxyethane (dme) yields the heteroleptic dimeric (dme)barium bis(trimethylsilyl)amide bis(trimethylsilyl)phosphanide. This colorless compound crystallizes in the monoclinic space group P21/n with a = 1 259.1(3), b = 1 822.7(4), c = 1 516.1(3) pm, β = 110.54(3)° and Z = 4. The central moiety of the centrosymmetric molecule is the planar Ba2P2-cycle with Ba—P-bond lengths of 329 and 334 pm. In the presence of bis[bis(trimethylsilyl)amino]stannylene hetero-bimetallic bis(trimethylsilyl)phosphanides of tin(II) and barium are isolated. If the reaction of Ba[N(SiMe3)2]2 and Sn[N(SiMe3)2]2 in the molar ratio of 1:2 with six equivalents of HP(SiMe3)2 is performed in toluene, barium bis{tin(II)-tris[bis(trimethylsilyl)phosphanide]} can be isolated. This compound crystallizes in the orthorhombic space group P212121 with a = 1 265.1(1), b = 2 290.1(3), c = 2 731.9(3) pm and Z = 4. The anions {Sn[P(SiMe3)2]3}- bind as two-dentate ligands to the barium atom which shows the extraordinary low coordination number of four. The addition of tetrahydrofuran (thf) to the above mentioned reaction solution leads to the elimination of tris(trimethylsilyl)phosphane and the formation of thf complexes of barium bis{tin(II)-bis(trimethylsilyl)phosphanide-trimethylsilylphosphandiide}. The derivative crystallizes from toluene in the monoclinic space group P21/c with a = 1 301.9(2), b = 2 316.3(3), c = 3 968.7(5) pm, β = 99.29(1)° and Z = 8.
    Notes: Bei der Reaktion von Barium-bis[bis(trimethylsilyl)amid] mit einem Äquivalent Bis(trimethylsilyl)phosphan in 1,2-Dimethoxyethan (DME) wird heteroleptisches, dimeres (1,2-Dimethoxyethan-O,O′)barium-bis(trimethylsilyl)-amid-bis(trimethylsilyl)phosphanid isoliert. Diese farblose Verbindung kristallisiert in der monoklinen Raumgruppe P21/n mit a = 1 259,1(3), b = 1 822,7(4), c = 1 516,1(3) pm, β = 110,54(3)° und Z = 4. Das zentrale Strukturelement des zentrosymmetrischen Moleküls ist der planare Ba2P2-Cyclus mit Ba—P-Bindungslängen von 329 und 334 pm. In Gegenwart des Bis[bis(trimethylsilyl)amino]stannylens erhält man heterobimetallische Bis(trimethylsilyl phosphanide von Zinn(II) und Barium. Wird die Umsetzung von Ba[N(SiMe32]2 and Sn[N(SiMe3)2]2 im molaren Verhältnis 1:2 mit sechs Äquivalenten HP(SiMe3)2 durchgeführt, kann Barium-bis{zinn(II)-tris-[bis(trimethylsilyl)phosphanid]} isoliert werden. Diese Verbindung kristallisiert in der orthorhombischen Raumgruppe P212121 mit a = 1 265,1(1), b = 2 290,1(3), c = 2 731,9(3) pm und Z = 4. Die Anionen {Sn[P(SiMe3)2])3}- binden als zweizähnige Liganden an das Bariumatom, das dadurch die ungewöhnlich niedrige Koordinationszahl vier aufweist. Die Zugabe von THF zu der oben beschriebenen Reaktionslösung führt zur Eliminierung von Tris(trimethylsilyl)phosphan und der Bildung von Barium-bis{zinn(II)-bis(trimethylsilyl)phosphanid-trimethylsilylphosphandiid). Das Derivat kristallisiert aus Toluol in der monoklinen Raumgruppe P21/c mit a = 1 301,9(2), b = 2 316,3(3), c = 3 968,7(5) pm, β = 99,29(1)° und Z = 8.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19956210529
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