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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 223 (1994), S. 1-11 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After a general classification of the cationic ring-opening polymerizations (CROP's) according to their polymerization mechanism, a number of examples of tailored polymers based on CROP are presented. The monomers used for the synthesis of these tailored structures are tetrahydrofuran (THF), N-tert-butyl aziridine (TBA), 2-methyl-1,3-oxazoline (MeOX) and 1,3-dioxolane (DXL).The polymer structures include different block and graft copolymers, macromonomers, star-shaped polymers, polymer networks and interpenetrating polymer networks (IPNs).
    Additional Material: 1 Tab.
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  • 2
    ISSN: 0009-2940
    Keywords: Trichlorosilylation ; Chlorophosphanes ; Silylphosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of Silicon-Silicon Bonds, 2[1]. - Trichlorosilylations of tert-Butyldichlorophosphane and tert-Butylbis(trimethylsilyl)phosphane with Hexachlorodisilane: Synthesis of New Bifunctional (Trichlorosilyl)phosphanesDi-tert-butyl(trimethylsilyl)phosphane (1) and tert-butylbis(trimethylsilyl)phosphane (3) react with one equivalent of hexachlorodisilane with exchange of one trimethylsilyl group by a trichlorosilyl group under mild conditions to give di-tert-butyl(trichlorosilyl)phosphane (2) and tert-butyl(trichlorosilyl)(trimethylsilyl)phosphane (4) in fair yields. tert-Butylbis(trichlorosilyl)phosphane (5) is available from tert-butyldichlorophosphane without organometallic reagents and solvents by simple reductive trichlorosilylation with the help of two equivalents of hexachlorodisilane. 5 is a useful precursor for phosphaalkane synthesis: with pivaloyl chloride, 5 leads to tert-butyl-[tert-butyl(trichlorosilyloxy)methylene]phosphane (6). From 4 with pivaloyl chloride mainly 6 and some known tert-butyl[tert-butyl(trimethylsilyloxy)methylene]phosphane (7) are formed.
    Additional Material: 1 Tab.
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  • 3
    ISSN: 0009-2940
    Keywords: Reductive silylation ; Aminochlorophosphanes ; Silylphosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of alkyl(diorganylamino)chlorophosphanes R(R2′N)PCl 1 (1a: R = tBu, R′ = Et, 1b: R = iPr, R′ = iPr; 1c: R = iPr, R′ = Ph) with hexachlorodisilane, afforded alkyl(diorganylamino)trichlorosilylphosphanes R(R2′N)PSiCl3 2 (2a: R = tBu, R′ = Et; 2b: R = iPr, R′ = iPr; 2c: R = iPr, R′ = Ph) and silicon tetrachloride. An intermediate formed in the reaction of 1b with hexachlorodisilane, the adduct iPr(iPr2N)(Cl)P-Si(Cl)3-SiCl3 (3b = 1b · Si2Cl6), was detected by 31P- and 29Si-NMR spectra that indicate pentacoordinated silicon bound to tetracoordinated phosphorus and tetracoordinated silicon. Trichlorosilylphosphanes 2 are also available from 1 under very mild conditions by reductive trichlorosilylation with trichlorosilane in the presence of triethylamine. Compounds 2 were identified analytically, by mass spectroscopy, multinuclear NMR, and an X-ray structure determination of 2c.
    Additional Material: 1 Ill.
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  • 4
    ISSN: 0009-2940
    Keywords: Trichlorosilylation ; Dichlorophosphanes ; Silylphosphanes ; Amino(silyl)phosphanes ; Silicon /Reductions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of hexachlorodisilane and of trichlorosilane/triethylamine with alkyl-and dialkylaminodichlorophosphanes RPCl2 1a-i [R = iPr: a; (Me3Si)2CH: b; R=1-adamantly: c: R=tBu: d; R=Et2N: e; R=iPr2M: f] furnish bis(trichlorosilyl)-phosphanes RP(SiCl3)2 3a-f. However, when less bulky substituents are attached to the phosphorus atom, so that there is little steric crowding, the double reductive silylations leading from 1 to 3 are accompanied by side reactions and decomposition of 3. Therefore, only 3b, 3c, 3d, and 3f wre isolated in a pure state. These compounds are more readily prepared by the; trichlorosilane/triethylamine method. 1H-, 31P- and 29Si-Nmr spectra confirm their constitution. The structure of solid 3f, the first aminobis(trichlorosilyl)phosphane, was determined by X-ray crystallography. 3f contains a phosphorus atom in a pyramidal environment surrounded by two silicon atoms and a planar nitrogen atom of the diisopropylamino group.
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0009-2940
    Keywords: Dichlorogermylene ; Trichlorogermylphosphanes ; Insertion ; Silver bromide complex ; Carbene homologues ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chlorophosphanes RR'PCl (1a: R,R' = 1b: R = tBu, R' = iPr, 1c: R = iPr, R' = Et2N, 1d: R = Et2N react with the dichlorogermylene dioxane complex 2 furnishing trichlorogermylphosphanes RR'PGeCl3 4a-d. In the cases of 1c/4c and 1d/4d the insertion reaction remain incomplete; similarly, 4a always contains, shortly after isolation in pure state, small amounts of 1a that can be detected by NMR. A provided by the reaction of trichlorosilylphosphane tBu(Et2N)PSiCl3 (5d) with GeCl4. The alkyl(dialkylamino) trichlorogermylphosphane 4d exists only in an equilibrium with chlorophosphane 1d, which coordinates GeCl2 leading to the dichlorogermylene complex 3d. A 1:1 mixture of 4a with 1a is formed by the novel cleavage (“chlorogermylation”) of the P-P bond of tetraisopropyldiphosphane with germanium tetrachloride. Di-tert-butyl(trichlorogermyl)phosphane 4e (R, R' = tBu) reacts with silver bromide providing a crystalline silver complex 7. A structure determination by X-ray diffraction reveals that 7 is [Ag4Br4(tBu2PCl)2(tBu2PGeCl3)2]. 2C7H8. Two of the Ag atoms of the cubane-like (AgBr)4 core of 7 are coordinated by chlorophosphane 1e, the other two by trichlorogermylphosphane 4e.
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2325-2327 
    ISSN: 0009-2940
    Keywords: Diselenide, torsion angle/NMR, 77Se/Selenenyl halide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis[tris(trimethylsilyl)methyl] Diselenide: An Unusual Diselenide with Sterically Enforced trans-C2h ConformationDeselenation of bis[tris(trimethylsilyl)methyl] triselenide (1) with copper occurs with formation of bis[tris(trimethylsilyl)-methyl] diselenide (2) and minor amounts of 3,3,5,5-tetrakis(trimethylsilyl)-1,2,4-triselenolane (3). The structures of 2 and 3 have been studied by multinuclear NMR spectroscopy and by X-ray crystallography. The C—Se—Se—C moiety of 2 adopts an unusual antiperiplanar conformation. Cleavage of the Se — Se bond by iodine providing iodo[tris(trimethylsilyl)-methyl]selane (5) is complete with 2, but reversible with 1.
    Additional Material: 2 Ill.
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  • 7
    ISSN: 0009-2940
    Keywords: Chalcogen-chalcogen bonds ; Selenium ; Selenide (2,4,6-tri-tert-butylphenyl)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Properties of Chalcogen-Chalcogen Bonds, XV1). - Lithium 2,4,6-Tri-tert-butylphenylselenide: Synthesis, Structure, and Reactions with Formation of Se - P, Se - C, Se - Si, Se - Sn, and Se - Au BondsBis(2,4,6-tri-tert-butylphenyl)diselenide (1) is reduced by lithium triethylhydridoborate to give lithium 2,4,6-tri-tert-butyl-phenylselenide (2) in high yield. 2 crystallizes with three molecules of tetrahydrofuran coordinated to lithium ([2(THF)3] ≡ 2a, space group P&1macr; Z =4). The monomeric compound 2a contains four-coordinate lithium bonded to two-coordinate selenium. 2 (LiSeR) reacts with the nonmetal and metal halides tBu2PCl, CH2Cl2, Me3SiCl, Me3SnCl, and Ph3PAuCl to give tBu2PSeR (3), RSeCH2Cl (4), (RSe)2CH2 (5), Me3SiSeR (6), Me3SnSeR (7), and the novel gold(I) selenophenolate derivative Ph3PAuSeR (8)(R = 2,4,6-tri-tert-butylphenyl).
    Additional Material: 1 Ill.
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  • 8
    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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  • 9
    ISSN: 0009-2940
    Keywords: Disulfanes ; Trisulfanes ; Bond conformations, S—S ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Properties of Chalcogen-Chalcogen Bonds, XVII[1]. - Di-and Trisulfanes with Sterically Congested Alkyl Substituents: The First trans1-DialkyldisulfaneBis[tris(trimethylsilyl)methyl]trisulfane (1) is obtained from tris(trimethylsilyl)methyllithium and sulfur with subsequent oxidation by oxygen or from tris(trimethylsily)methanethiol with sulfur dichloride. The solid trisulfane contains a transoid (helical) C—S-S—S-C backbone without severe distortion from steric strain. Desulfuration of the byproduct bis[tris(trimethylsilyl)methyl]tetrasulfane (2) with mercury provides 1, but further desulfuration of 1 to bis[tris(trimethylsilyl)1-methyl]disulfane (3) has not been achieved. 3 was isolated after oxidation of lithium tris(trimethylsilyl)methanethiolate with bromine. 3 contains a trans1-C—S-S—C moiety with an unusually long S—S bond (210-211 pm). The less crowded bis(triphenylmethyl)disulfane (4) contains a “normal” C—S-S—C moiety with anticlinal conformation (torsion angle - 110°).
    Additional Material: 3 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1765-1770 
    ISSN: 0009-2940
    Keywords: Phosphinic acid ; Phosphaindole bromination and chlorination ; Layer structure ; Hydrogen bonds ; Bromine-bromine interaction ; Phosphorus heterocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bromination of 1-ethoxy-1-oxophosphindolin-3-one (1) with two equivalents oi bromine occurs with elimination of hydrogen bromide and ethyl bromide, providing 2,2-di- bromo-1-hydroxy-1-oxophosphindolin-3-one (4) in high yield. In the presence of triethylamine this process leads to 2,2-dibromo-1-ethoxy-1-Oxophosphindolin-3-one (3) instead. Triethylamine deprotonates 4, providing the solid triethylammonium salt 5. Silylation of 4 with chlorotrimethylsilane leads to the trimethylsilyl ester 6. Monobromination in a two-phase reaction allows the isolation of a mixture of isomers of 2-bromo-1-ethoxy-1-oxophosphindolin-3-one (2a, b). Chlorination with chlorine furnishes 2,2-dichloro-1-ethoxy-1-oxo-phosphindolin-3-one (7). The new compounds 2-7 were characterized analytically and spectroscopically (EI-MS, 1H, 13C and 31P NMR). The crystal structure of acid 4 was determined by X-ray diffraction. Solid 4 consists of aryl stacks connected by chains of P—OH…O==P hydrogen bonds and secondary Br…Br contacts.
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