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  • 1
    Electronic Resource
    Electronic Resource
    Heterobimetallic .sigma.,.pi.-Acetylide-Bridged Complexes from Disubstituted 1,3-Butadiynes (1995)
    s.l. : American Chemical Society
    Organometallics 14 (1995), S. 2961-2968 
    Details
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/om00006a046
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  • 2
    Electronic Resource
    Electronic Resource
    Reactions of ε-Caprolactone with (Alkyne)zirconocene Complexes: Investigation of Elemental Steps in Catalytic Ring-Opening Polymerization of Lactones (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1351-1357 
    Details
    ISSN: 1434-1948
    Keywords: ε-Caprolactone complexes ; Zirconocene ; Ring-opening polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of Cp2Zr(L)(η2-Me3SiC2SiMe3) (L = THF, pyridine) with ε-caprolactone, cyclohexanone and cycloheptanone result in an insertion of the carbonyl group into the zirconacyclopropene ring system of the alkyne complexes to yield the five-membered metallacyclic spiro-zirconadihydrofurane complexes 1, 3, 4. The product with ε-caprolactone is not stable at room temperature and was identified only by NMR spectra and chemical reactions. Starting from rac-(ebthi)Zr(η2-Me3SiC2SiMe3) with ε-caprolactone and ethylene carbonate under analogous conditions more stable complexes (2, 5) were obtained. Complexes 2 and 3 were characterized by X-ray crystal-structure analysis. Complexes 1 and 2 react with further ε-caprolactone in a catalytic ring-opening polymerization. The polymerization reactions were monitored by NMR spectroscopy.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Nickel(0)-Komplexe fünfgliedriger Titana- und Zirconacyclocumulene als Zwischenstufen in der C-C-Bindungsspaltung disubstituierter ButadiineDer Max-Planck-Gesellschaft und dem Fonds der Chemischen Industrie danken wir für die finanzielle Unterstützung. (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 108 (1996), S. 1175-1178 
    Details
    ISSN: 0044-8249
    Keywords: Butadiine ; C-C-Bindungsspaltungen ; Nickelverbindungen ; Titanverbindungen ; Zirkoniumverbindungen ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19961081012
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  • 4
    Electronic Resource
    Electronic Resource
    Ferrocene Based Amido «Ligands»; Synthesis of bimetallic bis(aminopyridinato) titanium complexes (1997)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 389-393 
    Details
    ISSN: 0044-2313
    Keywords: Ferrocene ; aminopyridinato ligands ; titanium complexes ; bimetallic complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ferrocen-verbrückte „Amidoliganden“; Synthese von bimetallischen Bis(aminopyridinato)-Komplexen des TitansDer neuartige, Ferrocen-verbrückte „Aminopyridinligand“ fc(Me2SiApH)2 (3). fc(Me2SiApH)2 = 1,1′Bis{[(N-4-methylpyridin-2-yl)amino]dimethyIsilyl}ferrocen, wurde durch die Umsetzung von 1,1′-Bis(chlorodimethylsilyl)ferrocen (1) mit dem Natriumsalz von 4-Methyl-2-aminopyridin in Hexan synthetisiert, Verbindung 1 ist durch die Reaktion von 1,1′-Dilithioferrocen mit einem vierzigfachen Überschuß von Me2SiCl2 zugänglich. Durch Umsetzung von 3 mit jeweils einem Äquivalent Ti(NMe2)4 bzw. CTTi(NMe2)3 wurden die bimetallischen Titankomplexe fc(Me2SiAp)2Ti(NMe2)2 (4) und fc(Me2SiAp)2Ti(NMe2)CI (5), erhalten. Die Ergebnisse der Röntgenkristallstrukturanalyse von 3 werden diskutiert.
    Notes: The ferrocene based aminopyridine “ligand” fc(Me2SiApH)2 (3), fc(Me2SiApH)2 = 1,1′-bis{[(N-4-methylpyridin-2-yl)amino]dimethylsilyl}ferrocene, has been synthesized by the reaction of 1,1′-bis(chlorodimethylsilyl)ferrocene (1) with the sodium salt of 4-methyl-2-aminopyridine in hexane. Compound 1 is accessible by the reaction of 1,1′-dilithioferrocene with a fortyfold excess of Me2SiCl2. The reactions of 3 with one equiv of Ti(NMe2)4 or ClTi(NMe2)3, resp. afford the corresponding bimetallic titanium complexes fc(Me2SiAp)2Ti(NMe2)2 (4) or fc(Me2SiAp)2Ti(NMe2Cl (5)), resp. The crystal structure of 3 is reported.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19976230162
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  • 5
    Electronic Resource
    Electronic Resource
    Ring-Enlargement and Ring-Opening Reactions of Benzoxazole, Thiazoles, and Benzisoxazole by Zirconocene-Alkyne Complexes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 207-211 
    Details
    ISSN: 0009-2940
    Keywords: Zirconocene ; Titanocene ; Benzoxazoles ; Thiazoles ; Benzisoxazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zirconocene alkyne complexes Cp2Zr(L)(Me3SiC2R) (L = Py, THF; R = SiMe3 tBu) react with heterocyclic compounds like benzoxazole and related thiazoles to yield ring-expanded adducts (1-3) and (4, 5) by formal C-X (X = O, S) bond cleavage and coupling with the coordinated alkyne. In the case of benziso-xazole, the alkyne is not coupled but eliminated, and with ring-enlargement of the benzisoxazole a N-bridged dimer (6) is formed. The obtained complexes 1, 3, and 6 were characterized by NMR spectra and crystal structure analysis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290214
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  • 6
    Electronic Resource
    Electronic Resource
    Ligand- Substrate Communication in Group 4 Aminopyridinato Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 789-794 
    Details
    ISSN: 0009-2940
    Keywords: Agostic interactions ; Ligand effects ; Titanium ; Zirconium ; Aminopyridinato ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(aminopyridinato) zirconium and ansa-aminopyridinato titanium complexes have been sythesized. The reaction of (TMS-APy)3-Zr-Cl (4-methyl-2-trimethylsilyl-aminopyridine=TMS-APy-H) with trimethylsilylbutadiynyl lithium generated in situ affords (TMS-APy)3—Zr—C≡C—C≡C—TMS (1). (TMS-apy)3-Zr-Me2 (2). Compound 2 shows an agostic interaction of the dimethylamido moiety. The reaction of Ti(NMe,2),4 with silox(Apy-H)21,3-di(4′-picolin-2′-yl-amino)-1,1,3,3-tetraisopropyldisiloxane=silox (APy-H)2] gives rise to silox(Apy)2-Ti-(NMe2)2-Ti-[NMe,2)2 (3). Complex 3 reacts with ε-caprolactam to form a caprolactamato complex (4). X-ray crystal structure analyses of 1, 2, 3 and 4 are reported. The complexes 1, 2, 3 and 4 may be considered to be strained donor-functionalized amido(metal) complexes due to the η2 binding mode of the ligand cores, TMS-APy and silox(APy)2, to meet the requirements of the ancillary coordinated substrates is observed. Thus, aminopyridinato complexes seem to be valuable model compounds for investigations of ligand-substrate communications in early transition metal chemistry.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300618
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  • 7
    Electronic Resource
    Electronic Resource
    Synthesis and Structure of Mononuclear Titanium Complexes Containing ansa-Aminopyridinato Ligands (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1087-1091 
    Details
    ISSN: 0009-2940
    Keywords: ansa-Aminopyridinato ligands ; Strained amido ligands ; Titanium complexes ; Olefin polymerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of siloxane-bridged bis(2-aminopyridines) were synthesized from dichlorosiloxanes and 2-aminopyridines in the presence of a base via nucleophilic substitution reactions. They were used, after deprotonation, as dianionic (ansa-aminopyridinato) ligands to stabilize mononuclear titanium complexes with unusual coordination geometries. An X-ray crystal structure analysis of one of the ligands and of a titanium complex proved mononuclearity and provided information about the binding mode of this novel type of ligands. Ethylene polymerization studies showed low activity, remarkable differences between structurally related complexes, and broad molecular weight distributions. Sterically less demanding substituents and a high basicity of the ligand increase polymerization activity.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290917
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  • 8
    Electronic Resource
    Electronic Resource
    Reactions of Lactams with Titanocene- and Zirconocene-Alkyne Complexes as Elemental Steps in Catalytic Anionic Ring-Opening Polymerization of Lactams (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1281-1285 
    Details
    ISSN: 0009-2940
    Keywords: Zirconocenes ; Titanocenes ; N-Methyl-ε-caprolactam ; β-Propiolactam ; ε-Caprolactam ; Ring-opening polymerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Depending on the nature of the metal and the ring size, lactams react with titanocene and zircocene complexes of bis-(trimethylsilyl)acetylene Cp2Ti(Me3SiC2SiMe3) and Cp2Zr-(L)(Me3SiC2SiMe3) (L = Py, THF) to yield different products. In the reaction of Cp2Zr(Py)(Me3SiC2SiMe3) with N-methyl-€-caprolactam a simple ligand exchange reaction occurs and the complex Cp2Zr(Me3SiC2SiMe3)[O=H2)5] (1) was isolated. With β-propiolactam the alkenyl-amido complex Cp2)(SiMe3)][-NH2] (2) was obtained, which indicates that an agostic metal-hydrogen interaction has taken place. The reaction of Cp2Ti(Me3-SiC2SiMe3) with €-caprolactam gives after elimination of the alkyne and molecular hydrogen the first early transition metal complex with a deprotonated coordinated €-caprolactam in a η2-amidate bonding fashion (3). The obtained complexes were characterized by NMR spectra (1, 2) and crystal structure analysis (1-3) and discussed as elemental steps in anionic ring-opening polymerization of lactams catalyzed by metallocene-alkyne complexes.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961291022
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  • 9
    Electronic Resource
    Electronic Resource
    Mixed Chloro(dialkylamido) Complexes of Zirconium and Hafnium (1995)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 2021-2024 
    Details
    ISSN: 0044-2313
    Keywords: Amido complexes, zirconium, hafnium, X-ray crystal structure, reversible THF binding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Gemischte Chloro-(Dialkylamido)-Komplexe des Zirconiums und HafniumsChloro-(Dialkylamido)-Komplexe des Types (R2N)2MCl2(THF)2 (R = Me, Et; M = Zr und R = Me; M = Hf) wurden in einer Metathesereaktion durch Zugabe einer äquimolaren Menge des M(NR2)4 zu einer Ethersuspension des entsprechenden MCl4 in Gegenwart von THF synthetisiert. Die Röntgenkristallstrukturanalysen von (Et2N)2ZrCl2 · (THF)2 (1 a) und (Me2N)2ZrCl2(THF)2 (1 b) ergaben gestörte oktaedrische Koordination, wobei die sterisch anspruchsvollen Dialkylamidliganden die Chlorid und die THF Liganden aus der idealen Koordinationsposition herausdrücken. Dynamische NMR-Untersuchungen belegen ein Gleichgewicht eines Komplexes mit gebundenem THF bei tiefen Temperaturen und Chloro-Amido-Komplexen an denen kein THF koordiniert bei höheren Temperaturen. Bei den „Tieftemperaturstrukturen“ wird eine übereinstimmung mit der entsprechenden Röntgenkristallstruktur vermutet.
    Notes: Chloro(dialkylamido) complexes of the type (R2N)2MCl2(THF)2 (R = Me, Et; M = Zr and R = Me; M = Hf) were synthesized in a conproportionation reaction by adding an equimolar amount of the corresponding M(NR2)4 to an ether slurry of MCl4 in the presence of THF. X-ray crystal structure determinations of (Et2N)2ZrCl2(THF)2 (1 a) and (Me2N)2ZrCl2 · (THF)2 (1 b) reveal a distorted octahedral coordination geometry where the sterically demanding dialkylamide ligands force the chloride and the THF ligands out of their ideal position. Dynamic NMR investigations indicate an equilibrium of complexes with coordinated THF at low temperature in accordance with the structure determined by X-ray crystallography and of chloro-amido complexes that do not bind THF (at higher temperature).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19956211207
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  • 10
    Electronic Resource
    Electronic Resource
    Nickel(0) Complexes of Five-Membered Titana- and Zirconacyclocumulenes as Intermediates in the Cleavage of C—C Bonds of Disubstituted ButadiynesThis work was supported by the Max-Planck-Gesellschaft and the Fonds der Chemischen Industrie.Dedicated to Professor Paul Binger on the occasion of his 65th birthday (1996)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 1112-1115 
    Details
    ISSN: 0570-0833
    Keywords: butadiynes ; C—C bond cleavage ; nickel compounds ; titanium compounds ; zirconium compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.199611121
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