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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 596 (1991), S. 89-92 
    ISSN: 0044-2313
    Keywords: Calcium oxychloride ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Oxychloride of Calcium: Ca4OCl6Ca4OCl6 (hexagonal, P63mc, Z = 2), a = 905.8(3), c = 686.3(4) pm, (R = 0.031) crystallizes as colourless needles from reducing melts (CaCl2, Ca) that contain small amounts of „oxygen“. It contains „isolated“ tetrahedral units [Ca4O] and is isotypic with e.g., Ba4OCl6, Yb4OCl6 and K6HgS4. Ca4OCl6 does not form in the dehydration process of, for example, CaCl2 · 6 H2O.
    Notes: Ca4OCl6 (hexagonal, P63mc, Z = 2, a = 905.8(3)); c = 686.3(4) pm, (R = 0,031) kristallisiert in Form farbloser Nadeln aus „reduzierenden Schmelzen“ (CaCl2, Ca), die wenig „Sauerstoff“ enthalten. Es enthält „isolierte“ tetraedrische [Ca4O]-Einheiten und ist isotyp mit z. B. Ba4OCl6, Yb4OCl6 oder K6HgS4. Ca4OCl6 entsteht nicht beim Entwässern von z. B. CaCl2 · 6 H2O.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2025-2026 
    ISSN: 0009-2940
    Keywords: Aza-nido-decaborane(12) ; (1H-Triazen-1,3-diyl)-aza-arachno-decaborane(13) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Addition of Azides to Azadecaborane: 6-Azadecaborane-4,9-diyltriazenesnido-NB9H12 (1) reacts with azides RN3 to form a coordinative B-N bond between B9 and N1 of RN3, accompanied by the α-addition of the B4-H bond of 1 to the N3 atom of RN3. The products 2a, b (R = H, CH2Ph, respectively) thus contain an azadecaborane skeleton and a five-membered unsaturated B2N3 ring with a common B-B edge. The product 2a crystallizes in the space group Pna21.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1803-1806 
    ISSN: 0009-2940
    Keywords: Singlet carbenes ; [4 + 1] Cycloadditions ; 1,2,4,5-Tetrazines ; SEAr reactions, intramolecular ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wanzlick Carbenes in the [4 + 1] Cycloaddition Reaction with Bis(methylthio)- and Bis(trifluoromethyl)-1,2,4,5-tetrazineThe 3,6-disubstituted 1,2,4,5-tetrazines 3 and 4 have been submitted to a [4 + 1] cycloaddition reaction with the nucleophilic singlet carbenes (Wanzlick carbenes) 2a-d, which are generated from the precursors 1a-d. With 3 as diazadiene the expected spiro compounds 6a-d are formed. In contrast to this presumed two-step reaction sequence of 3, with the tetrazine 4 the cascade cycloaddition/cycloelimination is surprisingly followed by an intramolecular electrophilic aromatic substitution to yield the chiral tetracyclic compounds of type 8 with high diastereoselectivity. The crystal structure of 8d has been determined by X-ray diffraction methods.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 761-766 
    ISSN: 0009-2940
    Keywords: Tellurium compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cleavage of Bulky Diaryl Ditellurides with Bromine and Iodine; Crystal Structure of Et4N+ 2,4,6-(i-C3H7)3C6H2TeI-2Bis(2,4,6-triisopropylphenyl) ditelluride (1a), obtained from 2,4,6-triisopropylphenylmagnesium bromide with tellurium followed by oxidation with oxygen, and bis(2,4,6-tri-tert-butylphenyl) ditelluride (1b) react with equimolar amounts of bromine and iodine to provide new monomeric arenetellurenyl halides 2,4,6-R3C6H2TeX (2a, b, 3a, b: R = i-C3H7, t-C4H9; X = Br, I). Both tellurenyl iodides are thermally more stable than the corresponding bromides. Green 2,4,6-(i-C3H7)3C6H2TeI (3a) reacts with Et4N+I- to give the stable, red adduct Et4N+ 2,4,6-(i-C3H7)3C6H2TeI-2 (4a). An X-ray crystal structure determination of 4a revealed a T-shaped structure of the hypervalent aryldiiodotellurate(II) anion. Iodide-ion transfer between aryldiiodotellurate(II) and arenetellurenyl iodide is a fast process (1H-NMR time scale). 125Te-NMR data of this anion and of tellurenyl halides are compared with those of the ditellurides and of lithium benzenetellurolates (LiTeR·(THF)x).
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 2505-2509 
    ISSN: 0009-2940
    Keywords: Cyclopentadienes, bicyclic ; Face selectivity ; endo selectivity ; Chiral discrimination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general synthetic route to the enantiopure bicyclic cyclopentadienes (S)-3 and (R)-3 of the hydrindane series, starting from the Hajos-Wiechert ketone 4 or its enantiomer is described. Reasons for the excellent face and endo selectivity of cycloadditions and the resulting consequences for chiral recognition are discussed.
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  • 6
    ISSN: 0009-2940
    Keywords: Gold complex, dinuclear / Silyl complex / Gold - gold interaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition-Metal Silyl Complexes, 34. - A Dinuclear Gold Silyl Complex with Gold- Gold Interaction Between an (R3P)2Au and an (R′3,Si)ClAu UnitPh2MeP-Au-Cl reacts with Ph2MeP-Au-SiPh3 to form the dinuclear complex (Ph2MeP)2Au2(Cl)SiPh3, which is in equilibrium with its starting compounds. An X-ray structure analysis reveals that it consists of a (Ph2MeP)2Au and a (Ph3Si)ClAu unit, which are held together by Au-Au interaction [298.07(4) Pm]. The approximately linear AuL2 units are orthogonal to each other.
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 93-95 
    ISSN: 0009-2940
    Keywords: Decaborane ; 1-Phosphabutin, 3,3-dimethyl ; Bis(decaboranyl)methane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of Decaborane with the Phosphaalkyne PC tBuThe borane B10H12(SMe2)2 (1) reacts with the phosphaalkyne P°CtBu to form the product [B10H11(SMe2)][C(tBu)-PH](B10H12) (2), in which two B10 units are linked by a HP-CtBu bridge. The B10 unit B is simply bound to the bridge C atom, whereas the B10 unit A is bound to both bridging atoms, P and C, by atom B6 and, moreover, to the P atom by atom B5. The solvate complex 2 · CH2Cl2 crystallizes in the space group P¯.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 853-855 
    ISSN: 0009-2940
    Keywords: Diethylamine - arachno-nonaborane ; Diethylamine - octadecaborane ; conjuncto-Bis[6′5′:5,6]decaborane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Thermolysis of Amine-arachno-NonaboraneTwo molecules of diethylamine-arachno-nonaborane, B9H13-(NHEt2), undergo a condensation at 140°C to give diethylamine-conjuncto-bis[6′,5′:5,6]decaborane, B18H20(NHEt2) (4). The deprotonation of 4 yields the anion [B18H19(NHEt2)]-which can be crystallized with the cation [NEt3(CH2Ph)]+ (space group P1).
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 697-702 
    ISSN: 0009-2940
    Keywords: Osmium complexes/Oximato ligands, bidentate/Ruthenium complexes/Ring opening, ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Reactions of Hydrido(oxime), Hydrido(oximato) and Alkenyl(oximato) Complexes of Ruthenium and OsmiumThe carbonyl(hydrido) complexes MHCl(CO)[PMe(tBu)2]2 (4: M = Ru; 5: M = Os) react with aldoximes and ketoximes to give the octahedral hydrido(oxime)ruthenium and -osmium compounds MHCl(CO)[N(OH)=CRR′](PMe(tBu)2]2 (8-13) in high yields. Using MHCl(CO)(PiPr3)2 (6, 7) as starting materials, the complexes MHCl(CO)[N(OH)=CRR′](PiPr3)2 (14-16) are obtained. Reactions of 9 (M = Os; R = R′ = CH3) illustrate that the oxime ligand in the hydrido(oxime) compounds is easily displaced by Lewis bases. Either from 4, 5 and Na[N(O) = CRR′] in methanol or from 8-13 and NaH in THF the hydrido(oximato) complexes 20-25 in which the oximato ligand is coordinated via N and O, are formed almost quantitatively. CO opens the three-membered ring by cleavage of the M-N bond. Analogously, the alkenyl(oximato) compounds 28-30 are obtained from M[(E)-CH = CHPh]Cl(CO)[PMe(tBu)2)2]2 (18: M = Os; 27: M = Ru) with Na[N(O) = CRR′].
    Additional Material: 1 Tab.
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  • 10
    ISSN: 0009-2940
    Keywords: 3-Azabicyclo[3.3.1]nonanes ; 1-Azaadamantane derivatives ; Clemmensen reduction ; Dichlorination, geminal ; Radical deoxygenation, dehalogenation, nBu3SnH ; Grob fragmentation, regiospecifity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Azabicyclononanes by Fragmentation, II[1]. - Synthesis of 3-Azabicyclononanes by Regiospecific (Grob) FragmentationClemmensen reduction of the non-enolizable β1-dioxo group in the 1-azaadamantanedione derivative 1 gives the β1-hydroxy ketone 2, which is converted to the thioesters 3. Treatment of 3a or 3b with nBu3SnH/toluene yields the partially deoxygenated monoketone 4. Chlorination of 2 with SOCl2 generates 6 (geminal dichlorination). Dehalogenation with nBu3SnH produces 5. On the other hand, 2 can be monochlorinated to give 7, selectively. Preparative Grob fragmentation of the aza-tricyclic skeleton in 7 regiospecifically provides the 3-azabicyclo[3.3.1]nonane derivative 8. An even better access to 8 from 2 proceeds via an intermediate tosylate.
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