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  • Titanium complexes  (5)
  • Polymer and Materials Science  (3)
  • Intramolecular C=C bond coordination  (2)
  • Alkyltitanium compounds  (1)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1641-1648 
    ISSN: 0009-2940
    Keywords: Cyclopentadienyl ligand, functionalized ; Half-sandwich complexes ; Cobalt complexes ; Intramolecular C=C bond coordination ; Reductive complexation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermolysis of [1-(3-butenyl)-2,3,4,5-tetramethylcyclopentadienyl]carbonyldiiodocobalt, (η5-C5Me4CH2CH2CH=CH2)-Co(CO)I2 (2), in boiling octane affords the dimeric diiodide [(η5-C5Me4CH2CH2CH=CH2)-COI2]2 (3) without any interference of the 3-butenyl chain with the cobalt center. 2 reacts with various two-electron ligands L (L=P(OMe)3, P(OPh)3, PPh3, PMe3, PMe2Ph, tBuNC] to give a series of cobalt(III) complexes of the general formulae (η5-C5Me4CH2CH2CH=CH2)-Co(L)I2 (4-9). Sodium amalgam reduction of these “open-chain” complexes 4-9 yields novel cobalt(1) complexes containing an intramolecularly coordinated C=C bond (η5:η2-C5Me4CH2CH2CH=CH2)-Co(L). For L=CO (12), P(OMe)3 (13), and P(OPh)3 (14) low-melting crystals are isolated and fully characterized by analytical and spectroscopic methods.
    Additional Material: 1 Ill.
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  • 2
    ISSN: 0009-2940
    Keywords: Titanium complexes ; Bidentate phenoxy ligands ; Bulky phenols ; Lewis acidity ; Pentacoordination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of new titanium complexes of the general type Ti(mbmp)X2 (X = Br, I; OMe, OiPr, OtBu), containing a bidentate bis(phenoxy) ligand derived from 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (mbmpH2), was prepared. The 1H-chemical shifts for the protons of the methylene link were found to vary considerably as a function of the ligand X. Reaction of Ti(OiPr)4 with two equivalents of mbmpH2 gave the C2-symmetric spiro-titanate complex Ti(mbmp)2. The crystalline labile solvent adducts of the dichloro complex Ti(mbmp)Cl2 with THF and DME were isolated and characterized. A single-crystal X-ray structural analysis revealed the THF adduct to be a mono(THF) adduct with a trigonal-bipyramidal configuration, the bidentate mbmp ligand spanning an apical and equatorial site and the THF ligand occupying the remaining apical position.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1649-1651 
    ISSN: 0009-2940
    Keywords: Cyclopentadienyl ligand, functionalized ; Amido ligands ; Titanium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [(tert-Butylamino)dimethylsilyl]cyclopentadienes C5H5-n-(CMe3)n(SiMe2NHCMe3) (n=1, 2) and C5H4(SiMe3)(SiMe2-NHCMe3) have been prepared and the complexation of their lithium derivatives with FeCl2(THF)1.5 and TiCl4(THF)2 investigated.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1645-1647 
    ISSN: 0009-2940
    Keywords: Cobalt carbonyl complexes ; Cyclopentadienyl ligand, functionalized ; Intramolecular C=C bond coordination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 1-(3-butenyl)-2,3,4,5-tetramethylcyclopentadienyl cobalt complexes without and with intramolecular C-C double-bond coordination is reported.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 275-277 
    ISSN: 0009-2940
    Keywords: Titanium complexes ; Amido-cyclopentadienyl ligand ; Tridentate ligand ; Lewis acidity ; Chelate effect ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new titanium complexes of the general type Ti(η5:η1-C5H4SiMe2NCH2CH2X)Cl2 (X = NMe2 OMe), containing a tridentate ligand, were prepared by reaction of Ti(η5-C5H4Si—Me2Cl)Cl3 with the lithium amide Li(NHCH2CH2X) (X = NMe2, OMe). The 1H—NMR chemical shifts for the protons of the ethylene link were found to vary considerably as a function of the temperature, indicating the presence of an equilibrium between the tri- and bidentate bonding mode of the ligand. A single-crystal X-ray structural analysis of Ti(η5:η1—C5H4SiMe2NCH2CH2OMe)Cl2 revealed that the methoxy function is not intramolecularly coordinated in the solid state.
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1429-1431 
    ISSN: 0009-2940
    Keywords: Titanium complexes ; Amido-cyclopentadienyl ligand ; Optically active complexes ; Asymmetric hydrogenation catalysts ; Conformational rigidity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically active titanium complexes of the formula Ti(η5:η1-C5R4SiMe2NCHMePh)Cl2 (R = H, Me), containing the cyclopentadienyl ligand linked to a chiral 1-phenylethylamido moiety, were synthesized and characterized in both enantiomerically pure forms. A single-crystal X-ray structural analysis of (S)—(—)Ti(η5:η1-C5H4SiMe2NCHMePh)Cl2 shows a conformation in which the phenyl group is turned away from the metal center. NOE measurements suggest that a related structure is retained in solution. Upon activation with n-butyllithium, these complexes show hydrogenation activity toward imines with slight enantioselectivity.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 209-215 
    ISSN: 0009-2940
    Keywords: Titanium ; Amidocyclopentadienyl ligand ; Alkyltitanium compounds ; Lewis acids ; Agostic interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Titanium complexes of the general type Ti(η5:η1-C5H4Si-Me2NCH2C6H3X2-2,5)Cl2 (X=H, F), containing a linked benzylamido-cyclopentadienyl ligand, were prepared by reaction of Ti(η5-C5H4SiMe2Cl)Cl3 with lithium amide Li(NHCH2C6H3X2-2,5). A single-crystal X-ray structural analysis of Ti(η5: η1-C5H4SiME2NCH2C6H3F2-2,5)Cl2 revealed a conformation in the solid state in which the aryl ring is turned away from the metal center. Ti(η5:η1-C5H4SiMe2NCH2C6H5)Cl2 can be alkylated with a variety of reagents to form extremely sensitive complexes of the type Ti(η5-C5H4SiMe,2NCH2C6H5)R2 (R=Me, CH2 C6H5, CH2SiME3, CH2CMe2C6H5). Reaction of Li2[C5Me4SiMe2NCH2C6H5] with TiCl3(THF)3 gave Ti(η5: η1-C5Me4SiMe2NCH2C6H5)Cl2, which can also be alkylated to form dialkyl complexes of the type Ti(η5:η1-C5Me4SiMe2NCH2C6H5)R2(R=Me, CH2C6H5, CH2SiMe3, C6H5).A single-crystal X-ray structural analysis of Ti(η5:η1-C5Me4SiMe2NCH2C6H5)(CH2C6H5)2 suggests the presence of α-agostic bonding of one of the titanium-bound CH2C6H5 groups to the titanium center.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1571-1578 
    ISSN: 0887-624X
    Keywords: half-sandwich metallocenes ; mono-Cp-amido complexes ; homogeneous catalysis ; ethene-styrene copolymers ; polymerization kinetics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethene was copolymerized with styrene using five different methylalumoxane (MAO) activated half-sandwich complexes of the general formula Me2Si(Cp)(N—R)MCl2, varying the substituents on the cyclopentadienyl ring and the substituent on the amide (Cp = tetramethylcyclopentadiene CBT, 1-indenyl IBT, 3-trimethylsilyl-1-indenyl SIBT, or fluorenyl FBZ, R = tert-butyl (complexes CBT, IBT, SIBT, FBZ) or benzyl CAT), as well as the metal center (M = Ti, except FBZ: M = Zr). Polymerization behavior was analyzed with respect to catalyst activity and polymerization kinetics, styrene incorporation, copolymer microstructure, and molecular weight. All complexes produced random poly(ethene-co-styrene) without any regioregular or stereoregular microstructure. Complex CBT showed the highest catalytic activity, the fluorenyl-substituted complex FBZ produced the highest molecular weight polymer, and complexes SIBT and CAT promoted high styrene incorporation. Cp-substitution pattern influenced deactivation of the catalytic system with bulky substituents of the Cp-ring slowing down deactivation at the expense of styrene incorporation. Moreover, deactivation was accelerated with increasing styrene concentration. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1571-1578, 1997
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 237-244 
    ISSN: 1434-1948
    Keywords: Titanium complexes ; Amido-cyclopentadienyl ligand ; Titanium alkyl ; Intramolecular coordination ; Ethene polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Titanium complexes containing a linked isopropyl- or benzylamido(tetramethylcyclopentadienyl) ligand C5Me4SiMe2NR (R = iPr, CH2Ph,) and one bidentate organyl group C6H4(CH2NMe2)-2, CH2C6H4(NMe2)-2, and {η5-C5H3(CH2NMe2)-2}Fe(η5-C5H5) were prepared by salt metathesis of the corresponding dichloro complex Ti(η5:η1-C5Me4SiMe2NR)Cl2 with the lithium organyl. Single crystal X-ray structural analysis of Ti(η5:η1-C5Me4SiMe2NCH2Ph)- {C6H4(CH2NMe2)-2}Cl and of Ti(η5:η1-C5Me4SiMe2NiPr){CH2C6H4(NMe2)-2}Cl revealed the presence of intramolecular coordination with square pyramidal geometry around titanium. In the ferrocenyl derivative Ti(η5:η1-C5Me4SiMe2NCH2Ph)[{η5-C5H3(CH2NMe2)-2}Fe(η5-C5H5)]Cl the NMe2 group is not bonded at the titanium atom. Ethene polymerization catalyzed by these complexes upon activation with methylaluminoxane was examined.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 18 (1997), S. 809-815 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chiral heterobimetallic complexes Li[Ln(η5 : η1-C5R41SiMe2NCH2CH2R2)2] (Ln = Y, Lu; C5R41 = C5Me4, C5H4, 3-C5H3 t Bu; R2 = OMe, NMe2; Me: methyl; tBu: tert-butyl) have been found to polymerize ∊-caprolactone to give a polymer of high molecular weight (M̄n 〈 20 000) and moderate polydispersity (M̄w/M̄n 〈 2.0). Failure to observe a correlation between monomer/initiator ratio and molecular weight suggests a polymerization mechanism different from a pseudo-anionic mechanism.
    Additional Material: 1 Ill.
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