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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    The European physical journal 10 (1988), S. 227-232 
    ISSN: 1434-6079
    Keywords: 34.50.L ; 82.40.D
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Experiments performed using a crossed beam apparatus have shown that the reactivity of Na(4D) with HCl and O2 changes substantially as the 4d orbital alignment is varied. This change is found to be different for the two reactions. The favorable alignment for the reaction with HCl has thed orbital aligned along the relative velocity vector of the reactants. This result is consistent with a long range electron transfer initiating the reaction and suggests that the Na-Cl axis dominates over the H-Cl axis in determining the favorable atomic orbital alignment. For the reaction with O2, the NaO formation has a high translational energy threshold, and the favored orbital alignment varies as a function of the NaO laboratory scattering angle. Very restricted conditions are found to be necessary for the reaction: near collinear geometry and thed orbital perpendicular to the molecular axis.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 578 (1989), S. 75-80 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Neue Prophosphatrane: Neuartige Zwischenstufen auf dem Wege zu pentakoordinierten PhosphatranenDie Reaktion von N(CH2CH2NHMe)3 mit P(NMe2)3 oder P(NMe2)2Cl ergibt die Phosphatranvorstufe N(CH2CH2NMe)3P. Dessen Umsetzung mit Oxydationsmitteln ode Elektrophilen führt zu nicht-transannular-stabilisierten, tetrakoordinierten Derivaten N(CH2CH2NMe)3P—X, (X: O, S, Se, N3Ph, NPh, CS2, 1/2 PtCl2). Die Strukturen der beschriebenen Verbindungen werden anhand ihrer 1H-, 13C- und 31P-NMR-Daten diskutiert.
    Notes: The reaction of N(CH2CH2NHMe)3 with P(NMe2)3 or P(NMe2)2Cl yields the phosphatrane precursor N(CH2CH2NMe)2P,4. With oxydizing agents or electrophiles 4 is converted to the untransannulated four-coordinated derivatives N(CH2CH2NMe)3P—X, (X: O, S, Se, N3Ph, NPh, I CS2, 1/2 PtCl2). The structures of the compounds described are discussed by 1H, 13C, and 31P n.m.r. data.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Characterization of Selenium Compounds with the 2,4,6-tris(trifluoromethyl)phenyl SubstituentReaction of 2,4,6-tris(trifluoromethyl)phenyl lithium and red selenium results in a product which by acidic hydrolysis yields bis[2,4,6-tris(trifluoromethyl)phenyl] diselenide 1. With diazomethane this compound reacts to form bis[2,4,6-tris(trifluoromethyl)phenylselenenyl] methane 2, with bis(triphenylphosphine)ethene platinum(0) the corresponding bis(triphenylphosphine)bis-[2,4,6-tris(trifluoromethyl)phenylselenenyl] platinum(II) 3 is formed. Chlorine and bromine cleave the selenium-selenium bond in 1 and 2,4,6-tris(trifluoromethyl)phenylselenenyl chloride 4 and -bromide 5 are formed. The selenenyl halides are starting materials for the preparation of N,N′-bis-[2,4,6-tris(trifluoromethyl)phenylselenenyl] sulfur(IV) diimide 6 and sulfinylimino-2,4,6-tris(trifluoromethyl)phenyl selenide 7. The X-ray structures of 1 and 7 are discussed.
    Notes: Durch Reaktion von 2,4,6-Tris(trifluormethyl)phenyllithium mit rotem Selen und anschließender saurer Hydrolyse des Reaktionsprodukts bildet sich Bis[2,4,6-tris(trifluormethyl)phenyl]diselenid 1. Mit Diazomethan reagiert diese Verbindung zu Bis[2,4,6-tris(trifluormethyl)phenylselenenyl]methan 2, mit Ethen-bis(triphenylphosphan)-platin(0) entsteht Bis[2,4,6-tris(trifluormethyl)phenylselenenyl]bis(triphenylphosphan) platin(II) 3. Chlor und Brom spalten die Selen-Selen Bindung in 1 unter Bildung von 2,4,6-Tris(trifluormethyl)phenylselenenylchlorid 4 und -bromid 5. Die Selenenylhalogenide sind Ausgangsstoffe für N,N′-Bis[2,4,6-tris(trifluormethyl)phenyl-selenenyl]schwefel(IV)-diimid 6 und Sulfinylimino-2,4,6-tris(trifluormethyl)phenyl-selenid 7. Die Einkristall-Röntgenstrukturen von 1 und 7 werden diskutiert.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 535 (1986), S. 47-55 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: C-metalated Aminophosphines. 1. α-lithiated DimethylaminophosphinesThe preparation of dimethylaminophosphines of the general formula Z—CH2—Pdma2 and (Z—CH2)2Pdma, respectively (Z = (CH3)3Si, C6H5), their monometalation and the reactions of these metalated species with chlorosilanes, bis-(dimethylamino)-chlorophosphine and trimethylsilylmethyl-dichlorophosphine are described. The n.m.r. spectra of the prepared compounds are discussed.
    Notes: Es wird die Darstellung von Dimethylaminophosphinen der allgemeinen Formulierung Z—CH2—Pdma2 bzw. (Z—CH2)2Pdma, deren Monolithiierung zu Z—CH(Li)—Pdma2 bzw. Z—CH(Li)—P(dma)—CH2—Z (Z = (CH3)3Si, C6H5) und die Reaktionen dieser lithiierten Spezies mit Chlorsilanen sowie Bis-(dimethylamino)-chlorphosphin und Trimethylsilylmethyldichlorphosphin beschrieben. Die NMR-Daten der dargestellten Verbindungen werden diskutiert.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 405 (1974), S. 286-298 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: ESR Studies of Radiation Processes in Phosphate GlassesRadiation processes in phosphate glasses are investigated by ESR and optical measurements. ESR shows a hole-centre in the systems K2O/P2O5 and K2O/MGO/P2O5 which depends on manner and concentration of the cations. Its nature is explained in somewhat a different way than given by BEEKENKAMP or by MIURA and HASEGAWA. Another hole-centre which is independent of cations is discussed in agreement with optical investigations. The electrons set free by radiation react with O2 solved in the glass or with cations. The particels Ag0, Ag2+, Ag+2 have been found and Agn+4 may be present too in the system K2O/MgO/Ag2O/P2O5. The system K2O/MgO/Tl2O/P2O5 shows analogous reactions, but full explanation of the lines could not yet be given.
    Notes: Durch ESR-Untersuchungen und Vergleiche mit optischen Messungen werden Aussagen über die durch Bestrahlung in Phosphatgläsern ablaufenden Vorgänge gemacht. In den Systemen K2O/P2O5 und K2O/MgO/P2O5 wird durch ESR-Messungen ein kationenabhängiges Lochzentrum gefunden, dessen Natur in Abweichung von den Modellen nach BEEKENKAMP und nach MIURA u. HASEGAWA erklärt wird. Ein weiteres kationenunabhängiges Lochzentrum wird in Übereinstimmung mit optischen Untersuchungen gedeutet. Die durch Bestrahlung freigesetzten Elektronen lagern sich an im Glas gelösten Sauerstoff (O2) an oder reagieren mit den Kationen. Im System K2O/MgO/Ag2O/P2O5 werden die Teilchen Ag0, Ag2+, Ag+2 gefunden und Agn+4 wahrscheinlich gemacht. Für das System K2O/MgO/Tl2O/P2O5 gelten analoge Verhältnisse. Eine ausführliche Zuordnung konnte aber dabei noch nicht vorgenommen werden.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 459 (1979), S. 131-139 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ylidenmalonitrilphosphines (NC)2C=C(X)PRR′Ylidenmalonitrilphosphines of the general formula (NC)2C=C(X)PRR′ (X = Alkyl, Cl, NH2, PRR′; R = Ph, R′ = Ph, H) are prepared under different conditions from (NC)2C=C(X)Cl (X = Alkyl, Cl, NH2) and prim. or sek. phosphines and their monosubstituted alkali or trimethylsilyl derivatives respectively. The synthesis as well as the behaviour of (NC)2C=C(X)PRR′ are compared with the corresponding oxygen analogues of the type O=C(X)PRR′. The structure of the title compounds are elucidated by investigation of their mass, i.r., and n.m.r. spectra.
    Notes: Ylidenmalonitrilphosphine der allgemeinen Formel (NC)2C=C(X)PRR′ (X = Alkyl, Cl, NH2, PRR′; R = Ph, R′ = H, Ph) lassen sich unter verschiedenen Reaktionsbedingungen aus (NC)2C=CXCl (X = Alkyl, Cl, NH2) und prim. oder sek. Phosphinen bzw. deren monosubstituierten Alkali- sowie Trimethylsilylderivate herstellen. Sowohl Synthese als auch Eigenschaften der Ylidenmalonitrilphosphine werden mit den Sauerstoffanaloga des Typs O=C(X)PRR′ verglichen und IR-, NMR- sowie massenspektroskopisch charakterisiert.
    Additional Material: 1 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 473 (1981), S. 85-90 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Carbosilylated phospha-alkenesLithium-tris-trimethylsilylmethanide, (Me3Si)3C-Li, reacts with various organodichlorophosphines to give tris-(trimethylsilyl)-methyl-organochlorophosphines, the termal treatment of which under elimination of trimethylchlorosilane results in formation of the title compounds of the general formula B.NMR-data as well as the synthesis of compounds A and B will be discussed.
    Notes: Lithium-tris-trimethylsilylmethanid, (Me3Si)3C-Li, reagiert mit verschieden substituierten Organyldichlorphosphinen zur Tris-Trimethylsilylmethyl-organylchlorphosphinen A, deren thermische Beanspruchung unter Abspaltung von Trimethylchlorsilan zu den Titelverbindungen der allgemeinen Formel B führt.Die NMR-spektroskopischen Daten der Verbindungen des Typs A und B sowie deren Synthese wer-den diskntiert.
    Additional Material: 2 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 488 (1982), S. 75-79 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2,4,6-Tris(tert.butyl)phenyl Substituted PhosphinesTris(tert.butyl)phenyl-lithium reacts with PCl3 to give 2,4,6-tris(tert.butyl)phenyldihalogenophosphine which is reduced by LiAlH4 yielding 2,4,6-tris(tert.butyl)phenylphosphine. The same reaction by using (CH3)3Si—CH2—PCl2 leads to 2,4,6-tris(tert.butyl)phenyl-trimethylsilylmethylhalogenophosphine. Thermal treatment of this compound results under elimination of HCl and (CH3)3SiCl in the formation of . The nmr data of the compounds synthesized are discussed.
    Notes: Tris(tert.butyl)phenyl-lithium reagiert mit PCl3 oder (CH3)3Si—CH2—PCl2 zum 2,4,6-Tris(tert.butyl)phenyl-dihalogenphosphin bzw. entsprechenden -trimethylsilylmethylhalogenphosphin. Während sich ersteres mit LiAlH4 in das 2,4,6-Tris(tert.butyl)phenylphosphin überführen läßt, liefert letzteres durch thermische Beanspruchung nach Abspalten von HCl bzw. (CH3)3SiCl die Phosphine mit zweifach koordiniertem Phosphor. Die 1H- sowie 31P-NMR-Daten der dargestellten Verbindungen werden diskutiert.
    Additional Material: 1 Tab.
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  • 9
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloaddition of Dithiocyanogen and Trithiocyanogen with Hexafluoroacetone and Products of the Cleavage of the Sulfur-Sulfur Bond in Dithiocyan-Hexafluoroacetone Adduct by Elemental ChlorineThe reaction of dithiocyanogen and trithiocyanogen with hexafluoroacetone (HFA) leads to the cycloaddition products (SCN)2 · 4 HFA 1 and S(SCN)2 · 4 HFA 2. These are the first reactions of (SCN)2 and S(SCN)2 without cleavage of the S - S bonds. Elemental chlorine cleaves in 1 the S—S bond and 3 is formed. In 3 the chlorine atom can be replaced by the rests  - CN 4, (C6H11)2N -  5, and n-C4H9- 6. 6 eliminates one molecule of HFA by warming up and the four-membered ring 7 is formed. The compounds were characterized on the basis of mass and nmr spectra.
    Notes: Die Reaktion von Dithiocyan und Trithiocyan mit Hexafluoraceton (HFA) führt zu den Cycloadditionsprodukten (SCN)2 · 4 HFA 1 und S(SCN)2 · 4 HFA 2. Es sind die ersten Reaktionen des (SCN)2 und S(SCN)2, die nicht unter Spaltung der S—S-Bindungen verlaufen. Durch elementares Chlor wird 1 an der S—S-Bindung gespalten und es entsteht 3. In 3 kann das Chloratom durch die Reste  - CN 4, (C6H11)2N -  5 und n-C4H9- 6 ersetzt werden. Beim Erwärmen verliert 6 ein Molekül HFA und es entsteht der viergliedrige Ring 7. Die Verbindungen wurden anhand ihrer Massen- und NMR-Spektren eindeutig charakterisiert.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 495 (1982), S. 115-119 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkali Phosphorus Compounds and their Reactivity. 79. NMR Investigations of Alkali Organophosphides. IThe 31C and 31P NMR spectra display a further separation of ion-pairs of alkali-organophosphides in THF solution after addition of cryptandes . An exception presents LiP(Ph)2, T1—13C-NMR measurements suggest a tetrameric structure in THF.
    Notes: Anhand der 13C- und 31P-NMR-Daten läßt sich zeigen, daß sich die Ionenpaare der Alkali-organophosphide in THF durch Zugabe von Kryptanden entsprechend weiter trennen lassen. Eine Ausnahme bildet LiP(Ph)2, das aufgrund von T1—13C-NMR-Messungen eine tetramere Struktur in THF aufweist.
    Additional Material: 2 Tab.
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