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  • Inorganic Chemistry  (688)
  • Chemical Engineering  (651)
  • 1990-1994  (1,339)
  • 1994  (1,339)
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  • 1990-1994  (1,339)
Year
  • 1
    Electronic Resource
    Electronic Resource
    1,1′-Disubstituierte Titanocen-dithiolen-Chelate des Typs (η5-Me3EC5H4)2Ti(S2C2R2) (E = C, Si, Ge) (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1805-1811 
    Details
    ISSN: 0044-2313
    Keywords: Dithiolene chelates ; titanocene complexes ; η5-trimethylelementcyclopentadienyl complexes ; temperature-dependent 1H NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,1′-Disubstituted Titanocene Dithiolene Chelates of Type (η5-Me3EC5H4)2Ti(S2C2R2) (E = C, Si, Ge)Reaction of the titanocene dichlorides (η5-Me3EC5H4)2TiCl2 (E = C, 1a; E = Si, 1b; E = Ge, 1c) with the 1,2-dithiolates (NaS)2C2H2, (NaS)2C2(CN)2 or (LiS)2C6H3Me-4 gave the new titanocene dithiolene chelates (η5-Me3EC5H4)2Ti(S2C2H2) (2a-c), (η5-Me3EC5H4)2Ti[S2C2(CN)2] (3a-c) and (η5-Me3EC5H4)2Ti(S2C6H3Me-4) (4a-c). These have been characterized by 1H NMR, IR, and mass spectroscopy, and have been compared with the unsubstituted η5-C5H5 analogues 2d, 3d and 4d. Activation energies for the chelate ring inversion in solution of 2a-c, 3a-d and 4a-c have been estimated by temperature-dependent 1H NMR spectroscopy.
    Notes: Die Reaktion der Titanocen-dichloride (η5-Me3EC5H4)2TiCl2 (E = C, 1a; E = Si, 1b; E = Ge, 1c) mit den 1,2-Dithiolaten (NaS)2C2H2, (NaS)2C2(CN)2 oder (LiS)2C6H3Me-4 ergab die neuen Titanocen-dithiolen-Chelate (η5Me3EC5H4)2Ti(S2C2H2) (2a-c), (η5-Me3EC5H4)2Ti[S2C2(CN)2] (3a-c) und (η5-Me3EC5H4)2Ti(S2C6H3Me-4) (4a-c). Sie wurden durch 1H-NMR-, IR- und Massen-Spektroskopie charakterisiert und mit den unsubstituierten η5-C5H5-Analoga 2d, 3d und 4d verglichen. Für 2a-c, 3a-d und 4a-c wurden die Aktivierungs-energien der Chelatringinversion in Lösung aus temperatur-abhängig aufgenommenen 1H-NMR-Spektren abgeschätzt.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946201024
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  • 2
    Electronic Resource
    Electronic Resource
    1,1-Dithiooxalsäurederivate als Liganden in Übergangsmetallkomplexen: Struktur von O-Methyl-1,1-dithiooxalato-bis(triphenylphosphin)kupfer(I) und -silber(I) (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 498-504 
    Details
    ISSN: 0044-2313
    Keywords: Thiooxalates ; 1,1-Dithiooxalate ; 1,1-Dithiooxalic ester ; transition metal complex ; Crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,1-Dithiooxalic Acid Derivatives as Ligands in Transition Metal Complexes: Structure of O-Methyl-1,1-dithiooxalato-bis(triphenylphosphine)copper(I) and silver(I)Despite O-Alkyl-1,1-dithiooxalates are also tetradentate thioligands their tendency towards the formation of multi-nuclear bridged chelates as found for the basic 1,1-dithiooxalate does practically not exist because of derivatisation. The reaction with triphenylposphinemetal(I)-halogenides yields defined mono-nuclear mixed ligand complexes: O-Methyl-1,1-dithiooxalato-bis(triphenylphosphine)copper(I) (2) and silver(I) (1). X-ray analysis shows that both complexes (1 and 2) are isostructural and crystallize in the monoclinic space group P21/n: (Ph3P)2Ag(S2C2O2Me) (1) with a = 12.794(1), b = 21.314(4), c = 13.560(1) Å, β = 97.983(6)°, and (Ph3P)2Cu(S2C2O2Me) (2) with a = 12.622(1), b = 21.196(2), c = 13.426(1) Å, β = 96.533(7)°. These complexes are the first authentic examples of exclusively end-on coordinated thiooxalate.
    Notes: Obwohl potentiell auch vierzähnig, ist die Tendenz von O-Alkyl(bzw. Aryl)-1,1-dithio-oxalaten zur Ausbildung von Brücken in Mehrkern-Chelaten durch die Derivatisierung gegenüber dem Stammliganden 1,1-Dithiooxalat praktisch nicht mehr vorhanden. Durch Umsetzung mit Triphenylphosphinmetall(I)-halogeniden sind definierte einkernige Gemischtligandenkomplexe zugänglich. O-Methyl-1,1-dithiooxalato-bis(triphenylphosphin)kupfer(I) und -silber(I) konnten mittels Röntgenkristallstrukturanalyse strukturell gesichert werden. Beide Komplexe sind isostrukturell und kristallisieren in der monoklinen Raumgruppe P21/n: (Ph3P)2Ag(S2C2O2Me) (1), mit a = 12,794(1), b = 21,314(4), c = 13,560(1) Å, β = 97,983(6)° und (Ph3P)2Cu(S2C2O2Me) (2), mit a = 12,622(1), b = 21,196(2), c = 13,426(1) Å, β = 96,533(7)°. Diese beiden Komplexe sind die ersten strukturell gesicherten Vertreter mit ausschließlich end-on koordiniertem Thiooxalat.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946200317
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  • 3
    Electronic Resource
    Electronic Resource
    1,2-Azaborolyl-Komplexe, XXIX. Synthese und Eigenschaften von 1,2-Azaborolylboranen (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 73-80 
    Details
    ISSN: 0009-2940
    Keywords: 1,2-Azaborolylboranes ; Iron complexes ; Sandwich complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Azaborolyl Complexes, XXIX[1].  -  Synthesis and Properties of 1,2-AzaborolylboranesThe Li salts of variously substituted 1,2-azaboroles 1a-1c react with numerous halogenoboranes to give the corresponding mono(1,2-azaborol-3-yl)boranes 2-12. In the case of 11, which is substituted by SiMe3 at C-3, 2,5-dihydro isomers can be observed as intermediates by NMR spectroscopy with a B(Cl)NMe2 group at C-5 and the SiMe3 substituent either at C-4 (11a) or at C-3 (11b). The thermodynamically stable final product 11 is probably formed from 11b via an allylic transition state. The X-ray structure analysis of 11 at ca. 0°C proves the suggested structure. The first and only example of a bis(1,2-azaborol-3-yl)borane 13 was realized by the reaction of (1-tert-butyl-2,3-dihydro-2-methyl-1H-1,2-azaborol-3-yl)-chloro(dimethylamino)borane (3) with 1-tert-butyl-2-methyl-1,2-azaborolyllithium (1a). The X-ray structure analysis of bis(1-tert-butyl-2,3-dihydro-2-methyl-1H-1,2-azaborol-3-yl)-(dimethylamino)borane (13) shows one of the two NMR-spectroscopically observed diastereoisomers with perpendicularly oriented azaborolyl rings. Two iron sandwich complexes were synthesized; 15 is formed via 1-tert-butyl-3-[bis(dimethylamino)boryl]-2-methyl-1,2-azaborolyllithium (14) and FeCl2, whereas the ClB-substituted sandwich complex 16 results from the reaction of 15 with BCl3.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270111
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  • 4
    Electronic Resource
    Electronic Resource
    1,3,5-Cyclohexatrien-1,4-diyl und 2,4-Cyclohexadien-1,4-diyl (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1765-1779 
    Details
    ISSN: 0009-2940
    Keywords: Diradicals ; NO and O2 trapping ; Heat of formation ; Energy well ; Rearrangments ; Bergman cyclisation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Energy Well of Diradicals, V[1].  -  1,3,5-Cyclohexatriene-1,4-diyl and 2,4-Cyclohexadiene-1,4-diylThe energy profile of the Bergman rearrangement of (Z)-3-hexene-1,5-diyne (4) has been established from the NO and oxygen dependance of the trapping rate of the intermediate diradical 1 which leads to a heat of formation for 1,4-didehy-drobenzene (1) of δHOf= 138.0 ± 1.0 kcal . morl-1. By the same technique the heat of formation of 1,2,4-cyclohexatriene (2), generated by thermolysis of (Z)-1,3-hexadien-5-yne (10), gives δHOf = 105.1 ± 1.0 kcal . mol-1 which indicates a high diradical character for 2.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270929
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  • 5
    Electronic Resource
    Electronic Resource
    1,3,5-Triphenyl-2,4,6-trimesityl-1,3,5,2,4,6-triphosphatriborinane: A 6π-Electron Heteroaromatic LigandDedicated to Professor Dr. Dr. h. c. mult. E. 0. Fischer on the occasion of his 75th birthday. (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 825-827 
    Details
    ISSN: 0009-2940
    Keywords: Chromium tricarbonyl(η6-1,3,5-triphenyl-2,4,6-trimesityl-1,3,5,2,4,6-triphosphatrnane)- ; 1,3,5,2,4,6-Triphosphatriborinane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of tricarbonyl(η6-1,3,5-triphenyl-2,4,6-trimesityl-1,3,5,2,4,6-triphosphatriane)chromium (4) is reported. Its X-ray structure reveals an orientation of the Cr(CO)3 moiety with respect to the almost planar B3P3 ring typical of an arene metal tricarbonyl complex.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270506
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  • 6
    Electronic Resource
    Electronic Resource
    1,3-Diaza-2λ2-phosphonia-4λ4-gallatacyclobutane (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 2397-2401 
    Details
    ISSN: 0009-2940
    Keywords: [Amino(imino)phosphane]gallium trichloride adduct ; 1,3-Diaza-2λ2-phosphonia-4λ4-gallatacyclobutanes ; Nickel tricarbonyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Diaza-2λ2-phosphonia-4λ4-gallatacyclobutanesReaction of amino(imino)phosphanes 1a-c with gallium trichloride results in the formation of 1,3-diaza-2λ2-phosphonia-4λ4-gallatacyclobutanes 3a, b with elimination of chlorotrimethylsilane (1a) or tert-butyl chloride (1b, c). The intermediately formed amino(imino)phosphane/Lewis acid adducts R(Me3Si)NPN(GaCl3)R′ (2, R,R′ = tBu, Me3Si) can be isolated in the case of compound 2a (R = R′ = SiMe3). A diazaphosphasilacyclobutane - gallium trichloride adduct 4 is formed in a side reaction by isomerization of 2a. Reaction of compound 3b with Ni(CO)4 gives the corresponding transition metal complex 5. The NMR data and X-ray structures of compounds 2a, 4, and 5 are reported.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941271210
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  • 7
    Electronic Resource
    Electronic Resource
    1,4-Diazabuta-1,3-dien-N-Sulfinylamin-Nickel(0)-Komplexe (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 926-930 
    Details
    ISSN: 0044-2313
    Keywords: Nickel(0) complexes ; 1,4-diazabuta-1,3-diene ; N-sulfinylamine ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,4-Diazabuta-1,3-Diene-N-Sulfinylamin Nickel(0) ComplexesSynthesis, properties, and reactions of 1,4-diazabuta-1,3-diene-N-sulfinylamine nickel(0) complexes are described. The highly coloured and extremely air and moisture sensitive nickel(0) complexes have been characterized by means of i.r. and 1H n.m.r.spectroscopy. The N-sulfinylamine ligands are η2-(S,N)-side on coordinated.
    Notes: Synthese, Eigenschaften und Reaktionen von 1,4-Diazabuta-1,3-dien-N-sulfinylamin-nickel(0)-Komplexen des Typs Ni(DAB)(RNSO) (R = Ph, p-Tol, Cy) werden beschrieben. Die Charakterisierung der diamagnetischen, intensiv farbigen und extrem oxidations- und feuchtigkeitsempfindlichen Nickel(0)-Komplexe erfolgte mit Hilfe der IR- und 1H-NMR-Spektroskopie. Die N-Sulfinylamin-Liganden sind η2-(S,N)-side on koordiniert.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946200528
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  • 8
    Electronic Resource
    Electronic Resource
    (1α,2α, 7α,8α,12α,17α,18α,19α)-Heptacyclo[17.3.1.18,12.05,23.06,18.07,17.016,24]-tetracosa-5(23),16(24)-dien, ein hyperstabiles Alken (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 219-221 
    Details
    ISSN: 0009-2940
    Keywords: Alkenes ; hyperstable ; Hydrogenation ; catalytic ; Hydrocarbons ; concave ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (1α,6α,7α,8α,12α,17α,18α,19α)-Heptacyclo[17.3.1.18,12.05,23.06,18.07,17.016,24]tetracosa-5(23),16(24)-diene, a Hyperstable AlkeneHydrogenation of the cis-photodimer 1 of acenaphthylene yields the title compound 2, which, though still containing two double bonds, undergoes no further hydrogenation or reaction with bromine for steric reasons. The cyclobutane ring of 2 shows strong steric distortions as revealed by X-ray analysis as well as by force-field and semiempirical MO calculations.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270131
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  • 9
    Electronic Resource
    Electronic Resource
    [2,3]-Thia-Wittig Rearrangements of α-Lithiated Sulfides Via De-aromatized Cyclohexadiene Intermediates Proceed with Inversion of Configuration at the Carbanionic Center (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1949-1957 
    Details
    ISSN: 0009-2940
    Keywords: Stannanes, α-(alkylthio) ; Wittig rearrangement ; Configurational stability ; α-Lithio sulfides ; [2,3] Rearrangement ; Stereoselectivity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nBuLi-induced tin/lithium exchange reactions of the di-astereomeric γ-[(methoxyethoxy)methoxy]-]α-(tributylstannyl) sulfides anti- and syn-8 delivered the α-(lithioalkyl) benzyl sulfides anti- and syn-11, respectively. Within 1 h at -78°C, these species underwent [2,3]-thia-Wittig rearrangements in THF via the de-aromatized cyclohexadiene intermediates syn- and anti-12. Tautomerization and protonation yielded 81:19 (85%) and 19:81 mixtures (96%) of the ortho-functionalized toluenes syn- and anti-13. Probably, both Wittig rearrangements proceeded with 100% inversion of configuration at the carbanionic stereocenter, and the overall loss of stereoselectivity is due to an epimerization anti-11 ⇌ syn-11 of the lithio sulfide intermediates at a rate which is 3.3 times slower than the rearrangement.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941271019
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  • 10
    Electronic Resource
    Electronic Resource
    (2,4,6-iPr3C6H2)(tBu)Si(AsH2)2: Das erste Diarsanylsilan und seine Umwandlung in ein 1,3-Diarsa-2-sila-4-germacyclobutan und ein 1,3-Diarsa-2-sila-4-germabicyclo[1.1.O]butan-DerivatHerrn Prof. Dr. Otto J. Scherer zum 60. Geburtstag gewidmet. (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 477-480 
    Details
    ISSN: 0009-2940
    Keywords: Diarsinosilane ; 1,3-Diarsa-2-sila-4-germacyclobutane ; 1,3-Diarsa-2-sila-4-germabicyclo[1.1.0]butane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (2,4,6-iPr3C6H2)(tBu)Si(AsH2)2: The First Diarsanylsilane and Its Transformation into a 1,3-Diarsa-2-sila-4-germabicyclobutane and a 1,3-Diarsa-2-sila-4-germabicyclo[1.1.0]butane Derivative*The crowded diarsanylsilane (2,4,6-iPr3C6H2)(tBu)Si(AsH2)2 (1) is synthesized by the reaction of (2,4,6-iPr3C6H2)(tBu)-SiCl2 with two equivalents of [LiAsH2(dme)] in 80% yield. Treatment of 1 with two equivalents of nBuLi yields the dilithio compound 7, which reacts with Mes(tBu)GeF2 to give the corresponding 1,3-diarsa-2-sila-4-germacyclobutane 8. The X-ray crystal structures of 1 and 8 were determined. The bond angles at silicon of 1 lie between 113.0(4) and 96.1(4)° indicating a distorted tetrahedral geometry. The four-membered SiGeAs2 ring in 8 is puckered (As1-Si1-As2/As1-Ge1-As2 23.5°) with the two tBu groups being transoriented. Dilithiation of the AsH positions in 8 with nBuLi and subsequent reaction with tBuHgCl leads to the 1,3-bis-(tert-butylmercurio) compound 9. The light-induced elimination of the tBu groups in 9 gives the tBu/tBu-exo,endo-SiGeAs2-bicyclo[1.1.0]butane 10 in 91% yield. 10 does not rearrange to the exo,exo isomer 11.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270305
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