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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 91-92 
    ISSN: 0009-2940
    Keywords: Boranes, amino(imino) ; Iron, tricarbonyl(butanone) ; Diiron, [(boryloxy)allyl]hexacarbonyl ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Formation of a Fe2(CO)6 Complex with a (Boryloxy)allyl BridgeThe amino(imino)borane Me3Si(tBu)N=B=NtBu (1) reacts with (benzylideneacetone)tricarbonyliron (2) in 1:2 molar ratio to give a 50% yield of the hexacarbonyldiiron complex 3 with a fly-over (boryloxy)allyl bridge, which crystallizes in the space group P21/c. The structure of 3 can be described as a pyramid with Fe(CO)3 at the apex and a non-planar pentagon [-Fe(CO)3-O(BXX′)-C(Me)-CH-C(Ph)-] [X = NHtBu, X′ = N(SiMe3)tBu] as the basis, but there is no bond between the apex and the O atom.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1619-1620 
    ISSN: 0009-2940
    Keywords: Silanolate ; Aminosilanolate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithium (dimethylamino)dimethylsilanolate (1) is obtained from trimeric dimethylsiloxane and lithium dimethylamide in quantitative yield. In the crystal 1 is a hexamer [LiOSiMe2(NMe2)]6 with crystallograpic C3i (S6, 3) symmetry. The molecule of 1 consists of a hexagonal prismatic (LiO)6 core and an N,O-chelating anion.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1565-1569 
    ISSN: 0009-2940
    Keywords: Boranes, amino(imino)- ; Boranes, alkylidene(amino)- ; Tantalum, alkylidene complexes ; Azadiboracyclobutanes ; [2 + 2] Cycloadditions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Further Reactions of the Amino(imino)borane Me3Si(tBu)N*B*NtBu and the Alkylidene(amino)borane Me3Si(tBu)-N=B=CHtBuThe alkylidenetantalum complexes [tBuHC=TaCl3(THF)2] (1b), [PhHC=TaCl3(PMe3)2] (1c), and [tBuHC=Ta(CH2tBu)3] (1d) were treated with the amino(imino)borane Me3Si(t-Bu)N*B*NtBu (2d). From 1b and 2d, the alkylidene(amino)borane Me3Si(tBu)N=B=CHtBu (7) is formed by metathesis. The 1:2 reaction of 1c with 2d gives the azadiboracyclobutane [-N(tBu)-B(X)-CHPh-B(X)-] [6d, X=Me3Si(tBu)N]. The six-membered ring compound [-N(tBu)=BR-N(tBu)-SiMe2-CH2-TaR(CHtBu)-] (8, R=CH2tBu) is obtained from 1d and 2d; the product 8 crystallizes in the space group P 21/c. The borane 7 is attacked at the BC double bond by Et2NH, tBuCHO, and Me3SiN3 giving the diamino(neopentyl)borane 9 by protolysis, the oxaboracyclobutane 10 by [2 + 2] cycloaddition, and the azaboracyclopropane 11 by cycloaddition and elimination of N2, respectively.
    Additional Material: 1 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1401-1404 
    ISSN: 0009-2940
    Keywords: 1H-Borole, 2,5-dihydro- ; 4-Boratricyclo[5.2.1.02,6]dec-2(6)-ene ; Bicyclo[2.2.1]heptane, 2,3-dimethylene- ; Bicyclo[2.2.1]heptane, 3-methyl-2-methylene- ; Bicyclo[2.2.1]hept-2-ene, 2,3-dimethyl- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Borolenes with Diastereotopic Faces: Synthesis of 4-(Dialkylamino)-4-boratricyclo[5.2.1.02,6]dec-2(6)-enes and Structure of the Dimethylamino DerivativeTwo syntheses of 2,5-dihyro-1H-borole derivatives with diastereotopic faces are described. 2,3-Dimethylenenorbornane (2) is transformed into the zirconocene complex 5 (≡ Cp2Zr · 2) in a large-scale preparation; 5 reacts with dichloro-(dialkylamino)boranes BCl2(NR2) to give 4-(dialkylamino)-4-boratricyclo[5.2.1.02,6]dec-2(6)-enes 1 (R = Me, iPr). Alternatively, 2,3-dimethylnorbornene (santene) (3) or 3-methyl-2-methylenenorbornane (4) can be kaliated by means of Lochmann-Schlosser base to give a dimetallation product 6 (≡ K2 2); treatment of 6 with BCl2(NR2) also affords the boratricycles 1 (R = Et, iPr). The structure of the dimethylamino derivative 1a has been determined by X-ray diffraction.
    Additional Material: 1 Ill.
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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    ISSN: 1434-1948
    Keywords: Aluminum ; Alkoxides ; Lactone ; Ring-opening ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of trialkylaluminum Al2R6 (R = Me, Et) with 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (mbmpH2) gives the dimeric mono(alkyl) complex [Al(mbmp)R]2 with bridging oxygen atoms. Reaction of [Al(mbmp)R]2 with one equiv. of 2-propanol results in the formation of the dimeric isopropoxide [Al(mbmp)(μ-OiPr)]2. Single-crystal X-ray analysis shows a C2h-symmetric structure with a planar Al2O2 core. Monomeric methylbis(2,6-di-tert-butyl-4-methylphenolato)aluminum, AlMe(OC6H2-2,6-tBu2-4-Me)2 (MAD), was found to react with one equiv. of 2-propanol to give a dimeric isopropoxide [AlMe(OC6H2-2,6-tBu2-4-Me)(μ-OiPr)]2 in which the bulky phenolate, instead of the methyl group, has been displaced. According to the single-crystal X-ray structure analysis, the molecule contains a similar Al2O2 core, but the two 2,6-di-tert-butyl-4-methylphenolato ligands are cis- and orthogonally arranged to each other. ε-Caprolactone is polymerized at 50 °C in toluene in a controlled manner by [Al(mbmp)(μ-OiPr)]2, to give poly(ε-caprolactone) with high molecular weights and narrow molecular weight distributions (Mw/Mn 〈 1.50). The low efficiency values (number of polymer chains initiated per aluminum atom) imply that [Al(mbmp)(μ-OiPr)]2 exists in a monomer-dimer equilibrium. The polymerization of ε-caprolactone by [AlMe(OC6H2-2,6-tBu2-4-Me)(μ-OiPr)]2 is faster, but somewhat less controlled.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1263-1268 
    ISSN: 1434-1948
    Keywords: Cluster chemistry ; Silaborane clusters ; Carbonyl complexes ; Silicon coordination ; Ruthenium complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction between three equivalents of the silaborate [NEt4][MeSiB10H12] (2) and one equivalent of [Ru3(CO)12] resulted in almost quantitative formation of the mononuclear transition metal complex [NEt4][Ru(CO)3(η5-MeSiB10H10)] (5), which was characterized by X-ray structure analysis. The trinuclear ruthenium complex [NEt4][Ru3(CO)8(η5-MeSiB10H10)] (7) was synthesized in high yield from the reaction of one equivalent of 2 and [Ru3(CO)12]. The cluster 7 reacts with two equivalents of PMe2Ph with substitution of two carbonyl groups to give the substitution product [NEt4][Ru3(CO)6(PMe2Ph)2(η5-MeSiB10H10)] (8).
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  • 10
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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