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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 205-209 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reaction between Mono- or Dichloroalkylphosphites and Hexa- or Heptamethyldisilazane The Preparation of Silylated Amidophosphites and N-Methylimido-bridged DiphosphitesDialkylmonochlorophosphites react with hexa- or heptamethyldisilazane with replacement of a trimethysilyl group to give dialkyl (trimethylsilyamido)- or -[methyl(trimethylsilyl)-amido]phosphites, (RO)2PNHSi(CH3)3 (4) or (RO)2PN(CH3)3 (8). Compounds such as 4 exist in a temperatur-dependent tautomeric equilibrium with the imide form, (RO)2P)H)=NSi(CH3)3 (5). it is also possible to split off two trimethylsilyl groups from heptamethyldisilazane to obtain the previously unknown methylimido-bis (dialkylphosphites), CH3N[P(OR)2]2 (9). The reaction between alkyldichlorophosphites and heptamethyldisilazene leads to alkyl bis[methyl(trimethylsily)amido]phosphites, [CH3)3SiNCH3]2POR (10). - )31-n.m.r. spectra are reported.
    Notes: Dialkymonochlorophosphite reagieren mit Hexa- bzw. Heptamethyldisilazan unter substitution einer Trimethylsilygruppe zu Dialkyl-(trimethylsilyamido)- bzw. -[methyl(trimethylsily)-amido]phosphiten, (RO)2PNHSi(Ch3)3 (4) bzw. (RO)2PN(CH3)3 (8). Verbindungen vom Typ 4 stehen in einem Temperaturabhängigen tautomeren Gleichgewicht mit der Imid-form, (RO)2P(H)—NSi(CH3)3 (5). Durch Abspaltung beider Trimethylsilygruppen vom Heptamethyldisilazan erhält man die bisher unbekannte Methylimido-bis(dialkyphosphite), CH3N[P(OR)2]2 (9). Die Reaktion von alkyldichlorophosphiten mit Heptamethyldisilazan liefert Alkyl-bis[methyl(trimethylsly)amido]phosphite, ([CH3)3SiNH3]2POR (10). - Die 31P-NMR-spektren werden Diskutiert.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1049-1056 
    ISSN: 0009-2940
    Keywords: Triborane(7) derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The First Monosubstituted Derivatives of triborane(7). - Crystal and Molecular Structure of Benzoyloxytriborane(7)B6H14 generated in situ has been shown to react with carboxylic acids, monothiocarboxylic acids, dialkoxydithiophosphorus acids, and diaryldithiophosphinic acids by splitting off H2 to form the chelate-stabilized compounds of the type B3H6X, where X = RCO2, RCOS, (RO)2PS2 und R2PS2. Reactions of carboxylic acids with some triborane(7) adducts or B4H10 produce the same type of compounds. The X-ray structure determination of Ph—CO2B3H6 is reported. All compounds show fluxional behaviour on the 11B-NMR time scale.
    Notes: Generiert man B6H14 in situ in Gegenwart von Carbonsäuren, Monothiocarbonsäuren, Dialkoxydithiophosphorsäuren oder Diaryldithiophosphinsäuren, so entstehen unter H2-Abspaltung die Chelat-stabilisierten Verbindungen des Typs B3H6X, wobei X = RCO2, RCOS, (RO)2PS2 und R2PS2 sein kann. Zum gleichen Verbindungstyp gelangt man bei der Reaktion zwischen bestimmten Triboran(7)-Addukten bzw. B4H10 mit Carbonsäuren. Von Ph—CO2B3H6 wurde eine Röntgenstrukturanalyse durchgeführt. Sämtliche Verbindungen zeigen im 11B-NMR-Spektrum dynamisches Verhalten.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 427-432 
    ISSN: 0009-2940
    Keywords: Chalcogenoboron hydride structure ; Adamantane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [(BH6)2]S4]2-, [(BH2)Se4]2-: New Chalcogenoboron Hydride Anions with Adamantane StructureThe reaction of THF·BH3/NaBH4 (2: 1) with H2S produces Na[H3B-μ2-S(B2H5)] (5) with hydrogen evolution. 5 reacts with an excess of H2S to give Na2[(BH2)6S4] (3a), which is also formed in the reaction of THF·BH3 with NaSH or anhydrous Na2S. These reactions proceed via 5 and the intermediates 7 or 8 by loss of BH-4 and cyclization. The analogous compound Na2[(BH2)6Se4] (4a) is obtained by the reaction of elemental selenium with NaBH4 (1:1) in triglyme. The primary product is Na2[H3B-Se-Se-BH3] (9). Treatment of 9 at 100 - 110°C yields 4a and polymers, 3a and 4a react with CsBr to form the crystalline compounds Cs2[(BH2)6Se4]·CsBr (3b) and Cs2-[(BH2)6Se4]·CsBr (4b), characterized by X-ray structure determinations. The anions of 3b and 4b consist of an adamantane skeleton. The Br- ion is octahedrally coordinated by Cs+ ions. The Cs6Br octahedra share faces to form columns along the hexagonal c axis. The crystal structures of the isotypic compounds 3b and 4b are closely related to the structure of CsNiCl3.
    Additional Material: 3 Ill.
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  • 4
    ISSN: 0009-2940
    Keywords: Chalcogeno boron hydride ; Noradamantane structure ; Calculations, SCF ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [(BH2)5S4]-: A New Chalcogeno Boron Hydride Anion with Noradamantane Structure - Theoretical Investigation of the Structure[1]The reaction of NaBH4/THF · BH3 with elemental sulfur produces Na[(BH2)5S4] (4a) with hydrogen evolution. These nucleophilic degradation reactions proceed via [H3B -μ2-S(B2H5)]- (1) and the intermediate 3 by loss of BH4- and cyclization. 4 can also be obtained by addition of 1 to 1,2,4,3,5-trithiadiborolane (5). 4 builds up a noradamantane-like skeleton B5S4. An X-ray structure determination of [(C6H5)4P] · 4 failed because of disordering of the anion. 1H-, 11B-NMR shifts and 1J(11B1H) coupling constants convey further structural information. Structural data have been calculated by SCF methods.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: μ4-S(B2H5)2, (H2BSH)2, 1,2-(HS)2B2H4: New Thiaboranes from the Reaction of Diborane with Hydrogen Sulfide. - Theoretical Investigation of the StructuresThe new and unstable compounds 1λ3,3λ3,2λ4,4λ4-dithiadiboretane (H2BSH)2 (1), the isomer 1,2-dimercaptodiborane 1,2-(HS)2B2H4 (2), μ4-thiabis(diborane) μ4-S(B2H5)2 (3), μ2-mercaptodiborane μ2-HS(B2H5) (4), dimercaptoborane HB(SH)2 (5), and polymers are formed in the reaction of B2H6 and H2S, with or without toluene, in a pressure tube at -15 to -10°C. 11B-NMR shifts and 1J(11B1Ht,b) coupling constants convey structural information. Structure data of 1, 3, and 4 have been determined by SCF calculations. According to these results, 1 exists as a mixture of planar Z and E isomers, 3 has a pyramidal structure; the BSB unit in 3 and 4 has some central or open three-center character.
    Notes: B2H6 und H2S reagieren im Einschlußrohr (mit oder ohne Toluol als Lösungsmittel) bei -15 bis -10°C unter H2-Entwicklung zu den neuen, instabilen Verbindungen 1λ3,3λ3,2λ4,4λ4-Dithiadiboretan (H2BSH)2 (1) sowie dem dazu isomeren 1,2-Dimercaptodiboran 1,2-(HS)2B2H4 (2), μ4-Thiabis(diboran) μ4-S(B2H5)2 (3), μ2-Mercaptodiboran μ2-HS(B2H5) (4), Dimercaptoboran HB(SH)2 (5) und Polymeren. Die Strukturen dieser Verbindungen werden durch die 11B-NMR-Parameter belegt. Aus SCF-Rechnungen erhielten wir die Strukturparameter für 1, 3 und 4. 1 besteht danach aus einer Mischung planarer Z- und E-Isomeren, 3 besitzt pyramidale Struktur; in 3 und 4 liegen zentrale bzw. offene 2-Elektronen-3-Zentren-BSB-Bindungen vor.
    Additional Material: 8 Ill.
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  • 6
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The equilibria resulting from ligand exchange reactions in OP(NCS)3/OPCl3 and SP(NCS)3/SPBr3 mixtures, respectively, were studied. Procedures for the preparation of OP(NCS)3 and SP (NCS)3 are described. The chemical shifts of the components of both systems OP(NCS)3/OPCl3 and SP(NCS)3/SPBr3 are tabulated.
    Notes: Die sich in Mischungen von OP(NCS)3 und OPCl3 bzw. von SP(NCS)3 und SPBr3 durch Ligandenaustausch einstellenden Gleichgewichte wurden untersucht. Es wird die Darstellung von OP(NCS)3 und SP(NCS)3 beschrieben. Die chemischen Verschiebungen der einzelnen Komponenten der beiden Systeme OP(NCS)3/OPCl3 und SP(NCS)3/SPBr3 sind tabelliert.
    Additional Material: 2 Ill.
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