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  • 1
    ISSN: 1434-1948
    Keywords: Boron ; Transition metals ; Sandwich complexes ; Boratabenzene ; Pinene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes of pinene-fused boratabenzene ligands [(1R,9R)6,10,10-trimethyl-4-boratatricyclo[7.1.1.02,7]undeca-2,4,6trienes] C13H17BX (with a: X = NMe2; b: X = OMe; c: X = Me) are described. The lithium salt Li(C13H17BNMe2) [Li(1a)] reacts with [Cp*Fe(NCMe)3]PF6 and with Mn(CO)3Br(py)2 to give diastereomeric mixtures FeCp*(C13H17BNMe2) (4a) and Mn(CO)3(C13H17BNMe2) (7). The mixture 4a undergoes solvolysis in methanol to produce methoxy compounds 4b, which in turn react with LiMe in Et2O to give methyl derivatives 4c. The lithium salts Li(C13H17BX) [Li(1a-c)] react with ZrCl4 in toluene or Et2O to give exo,exo-ZrCl2(C13H17BX)2 complexes (8a-c). The dimethyl derivative exo,exo-ZrMe2(C13H17BNMe2)2 (9) can also be prepared from 8a/LiMe in Et2O. NOE difference spectra have been analyzed to determine the configurations of the diastereomers and to establish a chemical shift criterion for assessing the configuration of the metal-ligand coordination. An independent confirmation of the product stereochemistries has been obtained by single-crystal X-ray structure determinations of exo-4a and 8a.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Iron complexes ; Radicals, organometallic ; Ring expansion ; Sandwich complexes ; Solvolysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Reaction of (Benzene)(cyclopentadienyl)iron Complexes with Organic Halides and the Ring Expansion of the Chloromethyl Derivatives of (Benzene)(cyclopentadiene) iron and (Cyclohexadienyl)(cyclopentadienyl)iron ComplexesThe 19-e complexes CpFe(C6R6), 1 (a: R = Me, b: R = H), react with organic halides R′X to form salts 1 · X, (benzene)(cyclopentadiene)iron complexes (C6R6)Fe(exo-5-R′C5H5), 2, and (cyclohexadienyl)(cyclopentadienyl)iron derivatives CpFeexo-5-R′C6H6), 3. The chloromethyl derivatives (C6R6)Fe[exo-5-(ClCH2)C5H5], 5a, b, readily undergo a ring expansion reaction, either as solids at ambient temperature or in methanol solution, to give ionic (benzene)(cyclohexadienyl)iron chlorides, 7a, b · Cl. The isomeric compounds CpFe[exo-6-(ClCH2)C6R6], 6a, b, solvolyze in methanol at 40°C to produce (cyclopentadienyl)(cycloheptatriene)iron chlorides, 8a, b · Cl.
    Notes: Die 19-e-Komplexe CpFe(C6R6), 1 (a: R = Me, b: R = H), reagieren mit organischen Halogeniden R′X unter Bildung von Salzen 1 · X, (Benzol)(cyclopentadien)eisen-Komplexen (C6R6)Fe(exo-5-R′C5H5), 2, und (Cyclohexadienyl)(cyclopentadienyl)eisen-Derivaten CpFeexo-5-R′C6H6), 3. Die Chlormethyl-Derivate (C6R6)Fe[exo-5-(ClCH2)C5H5], 5a, b, gehen als Feststoffe bei Raumtemperatur oder in methanolischer Lösung leicht eine Ringerweiterungsreaktionen ein und ergeben dabei ionische (Benzol)(cyclohexadienyl)eisen-chloride 7a, b, Cl. Die isomeren Verbindungen CpFe[exo-6-(ClCH2)C6R6], 6a, b, solvolysieren in Methanol bei 40°C zu (Cyclopentadienyl)(cycloheptatrien)eisen-chloriden, 8a, b · Cl.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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