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  • 1
    Electronic Resource
    Electronic Resource
    Synthesis and structure of a metallophosphenium-borane(3) complex containing a bridging BH3 group (1986)
    s.l. : American Chemical Society
    Organometallics 5 (1986), S. 380-383 
    Details
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/om00133a031
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  • 2
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 164. Über (Benzyl-tert-butylamino)borane und Bis(benzyl-tert-butylamino)bor(1+)-Salze (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 313-324 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contribution to the Chemistry of Boron, 164. (Benzyl-tert-butylamino)boranes and Bis(benzyl-tert-butylamino)boron(1+) SaltsThe introduction of one amino group into BX3 (X = Cl, Br) is readily achieved by reacting benzyl-tert-butylamine, RR′NH, with BX3 to give RR′N—BX2. However, (RR′N)2BX can only be prepared via the metal amide LiNRR′ (5). The corresponding aminoboron fluorides are readily obtained from BF3. O(C2H5)2 and 5. Amination of (RR′N)2BX (X = F, Cl) by 5 was not achieved. (RR′N)2BH results, however, from the reaction of [(RR′N)2B]BBr4 with excess 5. - Bis(amino)boron salts are obtained by halide abstraction from (RR′N)2BHal with AlCl3 or BBr3. The structure of [(RR′N)2B]AlCl4 (10) was determined by X-ray crystallography. The cation possesses an allene type structure with a linear NBN skeleton and rather short BN bonds (1.332 Å). This bond is 0.08 Å shorter than in (RR′N)2BCl (6a), whose structure has also been determined. The barrier to rotation of the BN bonds of the cation has been estimated to be ΔG* = 82 ± 3 kJ mol-1.
    Notes: Während mit Benzyl-tert-butylamin, RR′NH, in BCl3 oder BBr3 eine Aminogruppe leicht zu Aminoboranen RR′N—BX2 (X = Cl, Br) einzuführen ist, erhält man Bis(amino)borane (RR′N)2BX (X = Cl, Br) nur bei Verwendung des Amids LiNRR′ (5). Die entsprechenden Aminoborfluoride entstehen aus BF3. O(C2H5)2 und 5. Eine Aminierung von (RR′N)2BX (X = F, Cl) mit 5 zu B(NRR′)3 gelingt nicht. Die Reaktion von [(RR′N)2B]BBr4 mit überschüssigem 5 führt zu (RR′N)2BH. - Bis(amino)bor-Salze sind durch Halogenid-Abspaltung mit AlCl3 oder BBr3 aus (RR′N)2BHal leicht zugängig. Die Röntgenstrukturanalyse von [(RR′N)2B]AlCl4 (10) zeigt ein Allen-analoges Kation mit linearer NBN-Struktur und kurzer BN-Bindung (1.332 Å). Die BN-Bindung verkürzt sich beim Übergang von (RR′N)2BCl (6a), dessen Struktur ebenfalls rötgenographisch ermittelt wurde, in 10 um 0.08 Å. Die Rotationsbarriere der BN-Bindung im Kation beträgt ΔG* = 82 ± 3 kJ mol-1.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190127
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  • 3
    Electronic Resource
    Electronic Resource
    Contributions to the Chemistry of Boron, 227Part 226: Ref.. The P-centered Chemistry of [(Di-tert-butylphosphanyl)imino]-(2,2,6,6-tetramethylpiperidino)boraneDedicated to Professor Helmut Werner on the occasion of his 60th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 205-212 
    Details
    ISSN: 0009-2940
    Keywords: Borane, [(di-tert-butylphosphanyl)imino](2,2,6,6-tetramethylpiperidino) dimer ; Phosphonium, di-tert-butylmethyl[(2,2,6,6-tetramethylpiperidinoborylene)imino]iodide ; Haloboration ; Hydroboration ; Metal carbonyl complexes of [(di-tert-butylphosphanyl)imino](2,2,6,6-tetramethylpiperidino)borane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The elements oxygen, sulfur, and selenium add to the P atom of the title borane 1. In contrast to the formation of tmp—B≡N—P(X)tBu2 (X = S, Se), the P oxide (X = O) dimerizes to [tmp—B≡N—P(O)tBu2]2 (5) with an eight-membered flat boat-shaped B2N2P2O2 ring. Borane 1 reacts readily with Mel to yield a phosphonium salt 8 and with BBr3 to give an adduct 9 with a B—P bond. In contrast, bis(dichloroboryl)-methane not only adds to 1 to generate a coordinate B—P bond but also chloroborates the B≡N triple bond, the final product being a new five-membered heterocycle 10. Similarly, the BH3 component of BH3·SMe2 first adds to the P atom of 1 followed by reaction of a second mol of BH3·SMe2 which hydroborates the B≡N triple bond. Finally, metal carbonyl fragments add only to the P atom of 1, demonstrating also that the chemistry of the molecule 1 is dominated by the basicity of its P center.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280302
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  • 4
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 170. Synthese und Struktur eines 1,3,2,4-Diphosphadiboretans (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2681-2685 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Boron, 170. Synthesis and Structure of a 1,3,2,4-DiphosphadiboretaneDehydrohalogenation of chloro[(1,1-diethylpropyl)phosphino](2,2,6,6-tetramethylpiperidino)borane (1) produces no compound with a PB double bond but its diphosphadiboretane dimer 3, whose crystal structure has been determined. The molecule has a crystallographic center of symmetry. Its BP bond lengths (1.916, 1.933 Å) are comparatively long, suggesting weak BP bonds.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190825
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  • 5
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 180. Zur Kenntnis von [(Trimethylsilyl)amino]borinium-Kationen (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 3849-3855 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 180. Syntheses of [(Trimethylsilyl)amino]borinium CationsFluoro[(trimethylsilyl)amino]boranes react with an excess of boron tribromide to give the (silylamino)borinium tetrabromoborates 3. The thermal stability of these salts decreases as the number of trimethylsilyl groups increases. Already at room temperature [(Me3Si)2- N=B=N(SiMe3)2]BBr4 (3e) decomposes into Me3SiBr besides (Me3SiN — BBr)4 (4).
    Notes: Fluor[(trimethylsilyl)amino]borane reagieren mit einem Überschuß von Bortribromid zu den (Silylamino)borinium-tetrabromoboraten 3. Deren thermische Stabilität nimmt mit der Anzahl der Trimethylsilylgruppen im Kation ab. [(Me3Si)2N=B=N(SiMe3)2]BBr4 (3e) zersetzt sich bereits bei Raumtemperatur zu Me3SiBr und (Me3SiN — BBr)4 (4).
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861191227
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  • 6
    Electronic Resource
    Electronic Resource
    Contributions to the chemistry of boron, 188. Synthesis and Structures of New 1,3,2,4-Diphosphadiboretanes (1988)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 871-879 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Beiträge zur Chemie des Bors, 188.  -  Synthese und Strukturen Neuer 1,3,2,4-DiphosphadiboretaneDrei Methoden wurden zur Darstellung neuer Diphosphadiboretane entwickelt: a) Die baseninduzierte Elimierung von Halogenwasserstoff aus (Amino)phosphinobor-halogeniden, b) Tris-(trimethylsilyl)phosphan-Abspaltung aus R2N—B[P(SiMe3)2]2-Zwischenprodukten und c) Organylphosphan-Eliminierung aus Aminobis(organylphosphino)boranen R2N—B(PHR′)2. Die Molekülstrukturen von drei neuen 1,3,2,4-Diphosphadiboretanen (3, 4a, 4c) wurden mittels Röntgenbeugung bestimmt. Sie sind durch planare B2P2-Ringe charakterisiert. Die P-Substituenten stehen trans zueinander. Experimentelle Ergebnisse werden mit MNDO III Rechnungen verglichen; letztere ergeben eine geringe Aktivierungsbarriere (ΔE = 5 kcal/mol) für die Dimerisierung von H2N—B=PMe zu (H2N—BPMe)2.
    Notes: Three methods have been devised to prepare new diphosphadiboretanes: a) Base-induced hydrogen halide elimination from (amino)phosphinoboron halides precursors, b) tris(trimethylsilyl)-phosphane elimination from R2N—B[P(SiMe3)2]2 intermediates prepared in situ from combinations of R2N—B(Cl)—P(SiMe3)2 and LiP(SiMe3)2, and c) organylphosphane elimination from aminobis(organylphosphino)boranes R2N—-B(PHR′)2. The molecular structures of three new 1,3,2,4-diphosphadiboretanes (3, 4a, 4c) were determined by X-ray diffractometry. These are characterized by a planar four-membered B2P2 ring with the phosphorus substituents in trans positions. Their BP bonds represent single bond distances. Experimental results are compared with MNDO III calculations which reveal a low barrier (ΔE = 5 kcal/mol) for the dimerization of the boraphosphene H2N—B=PMe to the diphosphadiboretane (H2N—BPMe)2.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19881210510
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  • 7
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 196. Darstellung und Reaktionen eines 3-Amino-1,2,3-azaphosphaboriridins (1989)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 423-426 
    Details
    ISSN: 0009-2940
    Keywords: 1,2,3-Azaphosphaboriridine, 3-amino- ; Chromium complex, (3-amino-1,2,3-azaphosphaboriridine-P)- ; 1,3,2,4-Thiazaphosphaboretidine-2-sulfide derivative ; Tungsten complex, (3-amino-1,2,3-azaphosphaboriridine-P)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 196. - Preparation and Reaction of a 3-Amino-1,2,3-azaphosphaboriridineThe 1,2,3-azaphosphaboriridine 7, obtained by dehalogenation of the boryl(phosphino)amine precursor 6, reacts with sulfur or selenium not only with ring expansion but also with oxidation of its λ3-P atom to form the new heterocycles 8. The M(CO)5 fragments generated photolytically from Cr(CO)6 and W(CO)6, respectively, add to the P atom of 7. In contrast, MeI does not produce the phosphonium salt derived from 7. Rather the RP fragment is removed as iPr(Me)PI with formation of the iminoborane tmp-iPr.
    Notes: Das 1,2,3-Azaphosphaboriridin 7, dargestellt durch Enthalogenieren der Boryl(phosphino)amin-Vorstufe 6, reagiert mit Schwefel und Selen nicht nur unter Ringerweiterung, sondern zugleich unter Oxidation des λ3-Phosphors zu den neuen Heterocyclen 8. Während sich die aus Cr(CO)6 und W(CO)6 unter Photolyse erzeugten Pentacarbonylfragmente M(CO)5 an das P-Atom von 7 addieren, erhält man mit MeI kein Phosphoniumsalz. Vielmehr wird das RP-Fragment von 7 unter Bildung des Iminoborans tmp-tBu als iPr(Me)PI abgespalten.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19891220305
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  • 8
    Electronic Resource
    Electronic Resource
    Beiträge zur Chemie des Bors, 193. Reaktionen von Amino-imino-boranen mit Organyl-, Methoxy- und Dimethylamino-Verbindungen des Phosphors, Arsens und Antimons (1989)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 419-422 
    Details
    ISSN: 0009-2940
    Keywords: Amino-imino-boranes ; Diaminoboranes, P-, As-, and Sb-substituted ; Insertion reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 193. - Reactions of Amino-imino-boranes with Organyl, Methoxy, and Dimethyl-amino Compounds of Phosphorus, Arsenic, and AntimonyThe insertion of the EO or EN bond of phosphane, arsane, and stibane derivatives of type E(OMe)3 and E(NMe2)3 into the B≡N bond of the amino-imino-boranes 5a, b is determined by the Lewis acidity of the EX3 compounds which increases for this series according to E = P 〈 As 〈 Sb. In addition, steric effects play also a decisive role as demonstrated by a decrease in reactivity for the series PhPCl2 〉 MePCl2 〉 iPrPCl2 ≫ tBuPCl2. Chlorophosphorylation occurs specifically to yield products 7. Aminochlorophosphanes do not react specifically with 5a, but (MeO)2PCl yields the methoxyphosphorylation products 12 and 13.
    Notes: Die Einschiebung der EO- bzw. EN-Bindung von Phosphan-, Arsan- und Stiban-Derivaten E(OMe)3 bzw. E(NMe2)3 in die B≡N-Bindung der Amino-imino-borane 5a, b wird vom Lewis-Säure-Charakter der EX3-Verbindungen bestimmt, der in der Reihe E = P 〈 As 〈 Sb zunimmt. Darüber hinaus spielen sterische Effekte eine Rolle, wie an der Abnahme der Reaktivität in der Reihe PhPCl2 〉 MePCl2 〉 iPrPCl2 ≫ tBuPCl2, die ausschließlich zur Chlorophosphorylierung der Amino-imino-borane führt, gezeigt wird. Aminodichlorphosphane reagieren mit 5a uneinheitlich. (MeO)2PCl liefert die Methoxyphosphorylierungsprodukte 12 und 13.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19891220304
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