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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selective oxidations of bis(tricarbonyliron) complexes of methyl (3,7,8-trimethylidenebicyclo[2.2.2]oct-5-en-2-ylidene)methyl ketones 15-17 afforded selectively the tricarbonyl {(1RS,4SR,7SR,8RS)-C,7,8,C-η-[methyl (3,7,8-trimethylidenebicyclo[2.2.2]oct-5-en-(2Z)-2-ylidene)methyl ketone]}iron (12), the corresponding (2E)-derivative 13 and the tricarbonyl{(1RS,2RS,3SR,4SR)-C,2,3,C-η-[methyl (3,7,8-trimethylidenebicyclo[2.2.2]oct-5-en-(2Z)-2-ylidene)methyl ketone]}iron (18). The stereoselectivity of the Diels-Alder reactions of the uncomplexed (Z)- and (E)-hexadienone 12 and 13, respectively, was established. The face of the diene syn with respect to the C(5), C(6) etheno bridge was preferred for the cycloadditions of N-phenyltriazolinedione (NPTAD). In contrast, the reactions of dimethyl acetylenedicarboxylate (DMAD) and methyl propynoate showed a slight preference for addtion to the face of the hexadienones anti with respect to the etheno bridges of 12 and 13. The crystal structure of the adduct 25 resulting from the cycloaddition of NPTAD to 12 is reported.
    Additional Material: 4 Tab.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 2201-2208 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Elektronenübertragungen und Konformationsänderungen in 1,n-Diphenylpolyenen1,4-Diphenylbutadien (1), 1,6-Diphenylhexatrien (2) und 1,8-Diphenyloctatetraen (3) werden mit Alkalimetallen reduziert, und die resultierenden paramagnetischen Monoanionen sowie diamagnetischen Dianionen werden durch ESR- bzw. (1H-, 13C-)-NMR-Spektroskopie charakterisiert. Das stereodynamische Verhalten der Ionen wird als Funktion der Kettenlänge, der Ladung und des Gegenions untersucht. Die Reduktion von 1, 2 und 3 dient als Modellexperiment für die Beladung von ausgedehnten linearen Polyenen (Polyacetylenen).
    Notes: 1,4-Diphenylbutadiene (1), 1,6-diphenylhexatriene (2), and 1,8-diphenylocatatetraene (3) are reduced with alkali metals and the resulting paramagnetic monoanions and diamagnetic dianions characterized by ESR and (1H-, 13C-)NMR spectroscopy, respectively. The stereodynamic behavior of the ions is studied as a function of chain length, charge, and counterion. The reduction of 1, 2, and 3 serves as a model experiment for the doping of extended linear polyenes (polyacetylenes).
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1623-1627 
    ISSN: 0009-2940
    Keywords: Binuclear complexes ; Molybdenum complexes ; Rhodium complexes ; Sulfur dioxide bridges ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sulfur(IV) Compounds as Ligands, IX.  -  Binuclear Molybdenum-Rhodium Complexes with Sulfur Dioxide as a Bridging LigandThe hetero-binuclear complexes [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) and [MoRh(CN)(CO)3(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) are the first compounds which contain sulfur dioxide as a bridging ligand connected to two metal atoms from different groups of the periodic table. The synthesis starts from Mo(CO)3(NCMe)3 (7), which reacts with the chelating ligands Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm), and Ph2AsCH2AsPh2 (daam) to give the mononuclear precursors Mo(CO)3-(η2-Ph2E1CH2E3 Ph2)(η1-Ph2E2CH2E4 Ph2) (9-12). With [Rh2Cl2(CO)4] these are converted to the binuclear complexes [MoRhCl(CO)4(μ-Ph2E1CH2E3 Ph2)(μ-Ph2E2CH2E4Ph 2)] (15-18). Reversible CO/SO2 exchange finally gives 1-4 and the analogous bromide 5, the cyanide complex 6 is obtained from 1 and NaCN in liquid ammonia.
    Notes: Die heteronuklearen Zweikernkomplexe [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) und [MoRh(CN)(CO)3-(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) sind die ersten Verbindungen, in denen Schwefeldioxid als Brückenligand an zwei Metallatome aus verschiedenen Gruppen des Periodensystems gebunden ist. Die Synthese geht von Mo(CO)3(NCMe)3 (7) aus, das mit den Chelatliganden Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm) und Ph2AsCH2AsPh2 (daam) zu den einkernigen Vorstufen Mo(CO)3(η2-Ph2E1CH2E3 Ph2) (η1-Ph2E2CH2E4 Ph2) (9-12) umgesetzt wird. Daraus entstehen mit [Rh2Cl2(CC)4] die Zweikernkomplexe [MoRhCl(CO)4(μ-Ph2E1CH2E3Ph 2)(μ-Ph2E2CH2E4Ph2)] (15-18). Reversibler CO/SO2-Austausch ergibt schließlich 1-4 und das analoge Bromid 5, der Cyanokomplexe 6 wird aus 1 und NaCN in flüssigem Ammoniak erhalten.
    Additional Material: 1 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 19 (1936), S. 625-639 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1. Die Lösungen der Sulfate des drei- und vierwertigen Titans reagieren miteinander unter Bildung einer braunviolett gefärbten, Komplexverbindung mit dem Verhältnis von TiIII: TiIV = 4:3, welcher das Oxyd Ti7O12 beziehungsweise 3 TiO2 · 2 Ti2O3 zu Grunde liegt.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 19 (1936), S. 639-645 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die optische Drehung der Titan(IV)tartrate hängt von der Wasserstoffionenkonzentration der Lösung ab; nur Titan- bzw. Titanyl-ionen bewirken eine starke Vergrösserung der Drehung der Weinsäure, komplexe Ionen haben keinen Einfluss. Sowohl in saurer als auch in neutraler Lösung besteht je ein Maximum und dazwischen ein starkes Minimum mit Umkehrung des Drehsinns (auf Weinsäure bezogen).
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 762-765 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of 1,2-Dimethyl-3,5-diphenylpyrazolium-4-olate and 3,5-Diphenyl-1,2-dithiolylium-4-olate with Singlet OxygenThe pyrazolium-4-olate 1a and 1,2-dithiolylium-4-olate 1b react with singlet oxygen to produce carbon monoxide and 1,2-dibenzoyl-1,2-dimethylhydrazine (5a) or dibenzoyl disulfide (5b), respectively.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1489-1490 
    ISSN: 0009-2940
    Keywords: Binuclear complexes ; Zirconium ; Group VI metals ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heterometallic Binuclear Complexes, I.  -  Reactive Zr(IV)-M(0) Compounds (M = Cr, Mo, W) with Bridging Diphenylphosphinocyclopentadienide LigandsReaction of ZrCl2(C5H4PPh2)2 (1) with labile complexes M(CO)3L3 (M = Cr, L = acetonitrile, M = Mo, W, L3 = cycloheptatriene) gives the binuclear compounds ZrCl(μ-Cl)(μ-C5H4PPh2)2M(CO)3 [M = Cr (2), Mo (3), W (4)]. The Cl bridge is readily cleaved by ligands such as CO, MeCN, or P(OMe)3.
    Additional Material: 1 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 18 (1935), S. 1008-1008 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 4567-4577 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: First 1,4-Dipolar Cycloaddition Reactions of 3,6-Dihydro-6-oxo-1-pyrimidinium-4-olates to 1,2,4-Triazoline-3,5-dionesThe synthesis of some novel representatives of the pyrimidinium-4-olates of type 3 and 7, prepared from amidines 2 or 6 and bis(2,4,6-trichlorophenyl) malonates 1, is described. The representatives 3 or 7, which are substituted at the 5-position, react with the 1,2,4-triazoline-3,5-diones 4 even at room temperature to produce high yields of stable primary adducts 5 or 8, respectively, as a result of a 1,4-dipolar cycloaddition reaction, whereas the betaines 3i,j, which are unsubstituted at the 5-position, react with 4 to give the new betaines 9a,b.
    Notes: Die Synthese einiger neuer Vertreter der Pyrimidinium-4-olate vom Typ 3 und 7 aus den Amidinen 2 bzw. 6 und Malonsäure-bis(2,4,6-trichlorphenylestern) 1 wird beschrieben. Mit den 1,2,4-Triazolin-3,5-dionen 4 reagieren die in 5-Stellung substituierten Vertreter 3 oder 7 bereits bei Raumtemperatur in hohen Ausbeuten zu den stabilen Primäraddukten 5 bzw. 8 als Ergebnis einer 1,4-Dipolaren Cycloaddition, während die in 5-Position unsubstituierten Betaine 3i,j mit 4 die neuen Betaine 9a,b liefern.
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  • 10
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 2,6-Diazabicyclo[2.2.2]oct-7-ene-3,5-diones and 2(1H)-Pyridinones. - A Contribution to the Mechanism and to the Regiochemistry of 1,4-Dipolar Cycloaddition Reactions of New and Known 3,6-Dihydro-6-oxo-1-pyrimidinium-4-olates to Electron-rich and Electron-poor AlkynesThe synthesis of some new representatives of the 3,6-dihydro-6-oxo-1-pyrimidinium-4-olates 3a-f is described. As masked 1,4-dipoles, the betaines 3a-d,g-i combine with bis(diethylamino)ethyne (4a), 1-(diethylamino)-1-propyne (4b), dimethyl acetylenedicarboxylate (4c), or methyl propiolate (4d) to produce the stable heterobicycles 5a-m, whereas the reactions of 3e, f with 4c or 3e with 4d proceed with elimination of phenyl isocyanate to give the 2(1H)-pyridiones 6g, i or 6h, respectively. At higher temperatures, the bicyclic primary adducts 5b-e,k,m also release phenyl isocyanate to form 2(1H)-pyridinone derivatives 6a-f in high yields. In the case of the cycloaddition of 3 to the unsymmetrical alkynes 4b,d the observed regioselectivities are in agreement with the results of MNDO calculations and the FMO and PMO theory.
    Notes: Die Synthese einiger Vertreter der 3,6-Dihydro-6-oxo-1-pyrimidinium -4-olate 3a-f wird beschrieben. Als maskierte 1,4-Dipole vereinigen sich die Betaine 3a-d,g-i mit Bis(diethylamino)ethin (4a), 1-(Diethylamino)-1-propin (4b), Acetylendicarbonsäure-dimethylester (4c) oder Propiolsäure-methylester (4d) zu den stabilen Heterobicyclen 5a-m, während die Reaktionen von 3e, f mit 4c oder 3e mit 4d unter Phenylisocyanat-Eliminierung die 2(1H)-Pyridinone 6g, i bzw. 6h ergeben. Bei höheren Temperaturen spalten auch die bicyclischen Primäraddukte 5b-e,k,m Phenylisocyanat ab und liefern in hohen Ausbeuten 2(1H)-Pyridinon-Derivate 6a-f. Im Falle der Cycloadditionen von 3 an die unsymmetrischen Alkine 4b,d sind die beobachteten Regioselektivitäten mit den Ergebnissen aus MNDO-Rechnungen und der FMO- und PMO-Theorie in Einklang.
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