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  • 1
    ISSN: 0009-2940
    Keywords: 1,3-Diborolyl complexes, bis[η5-cyclopentadienyl)cobalt] ; 1,3-Diborolane, 4,5-diisopropylidene- and 2,4,5-triisopropylidene- ; Benzo-1,3-diborafulvene ; Electrochemistry ; ESR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Routes to Bis[(cyclopentadienyl)cobalt]-μ-(η5-2,3-dihydro-1,3-diborolyl) Triple-Decker Complexes by Hydrogen Shift Reactions in Derivatives of 4,5-Diisopropylidene-1,3-diborolane, 2,4,5-Triisopropylidene-1,3-diborolane, and Benzo-1,3-diborafulveneThe 31 VE dicobalt triple-decker complexes 6, 7a, 7b, c, 8a, b, and 9a, b with bridging 2,3-dihydro-1,3-diborolyl ligands are prepared. The reaction of the 1,3-diborole 1 with [(C5Me5)-Co(C2H4)2] leads to the sandwich complex 5, which is treated with [(C5H5)Co(C2H4)2] to yield unsymmetrical 6. The 4,5-diisopropylidenetrimethyl-1,3-diborolane 3 undergoes a metal-induced 1,5-hydrogen shift and reacts with [(C5H5)Co(C2H4)2] to form the triple-decker 7a. The reaction of the 2,4,5-triisopropylidene-1,3-diborolane 4 with [(C5H5)Co(C2H4)2] leads to a mixture of the triple-deckers 7b/c, formed by intermolecular hydrogen shift. The benzo-1,3-diborafulvene derivatives 2b and 2c also react with [(C5H5)Co(C2H4)2] to give the triple-decker 8b and a mixture of 9a, b. In addition, the trinuclear complex 8c is obtained in low yield. The new paramagnetic triple-decker complexes have been analyzed by NMR and ESR spectroscopic measurements as well as by electochemistry. The constitutions of 7b/c, 8b, 8c, and 9a/b have been confirmed by X-ray structure analyses. The complexes are iso-structural, the Co - Co distances range from 3.277(1) (7b/c) to 3.316(1) Å for 8c.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-1948
    Keywords: Arene complexes ; Catalysis ; Diazadiene complexes ; Iron ; Metal vapour ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two different routes to novel [(diene)(η6-2,6-dimethylpyridine)Fe] complexes are reported, both of which utilize metal vapour reactions. The presence of two small substituents on the 2,6-position of pyridine is essential for the η6-coordination of the heterocycle. Investigations on the reactivity and stability of the [(diene)(η6-arene)Fe] complexes are presented, including those of the benzene, phosphinine, and pyridine derivatives. These investigations give some hints to the relevant factors for determining the interaction between an iron atom and a π-coordinated neutral arene ligand, and their modification by a nitrogen or a phosphorus atom. Selective substitution of the 1,5-cyclooctadiene (COD) ligand of [(COD)(η6-arene)Fe] complexes by some 1,4-diaza-1,3-diene (DAD) derivatives is possible in the case of the benzene or phosphinine arene ligands, and [(DAD)(η6-arene)Fe] complexes are formed, but all DAD derivatives tested so far cause the complete disintegration of [(COD)(η6-2,6-dimethylpyridine)Fe]. [(DAD)(η6-arene)Fe] complexes exhibit a catalytic potential, which was evaluated by experiments on the catalytic cyclodimerization of 1,3-butadiene in the presence of [(Et2AlOEt)2] as a co-catalyst. This reaction yields up to 92% of 1,5-cyclooctadiene, and an almost quantitative butadiene conversion is possible in the presence of less than 0.1% of the catalyst. Structural investigations on [(N,N′-bis(cyclohexyl)ethylenediimine)(η6-toluene)Fe] 5a reveal some details of the Fe-DAD interaction. An effective electron back-donation from occupied iron d-orbitals into the π*-LUMO of the DAD is indicated.
    Type of Medium: Electronic Resource
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