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  • 1
    Electronic Resource
    Electronic Resource
    Synthesis and Reactivity of Functionalized Dimethylsilyl Complexes of the Formula (η5-C5H5)Re(NO)(PPh3)(SiMe2X); New Base-Stabilized Silylene Complexes, Novel Lewis Acid Adducts, and Evidence for Base-Free Silylene Complexes (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 309-320 
    Details
    ISSN: 0009-2940
    Keywords: Rhenium complexes ; Silylene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of (η5-C5H5)Re(NO)(PPh3)(SiMe2H) (1) and CHCl3, CBr4, and CHI3 give halosilyl complexes (η5-C5H5)Re(NO)-(PPh3)(SiMe2X) [X = Cl (2), Br (3), I (4); 66-84%]. Addition of Me3SiOTf to 2 gives triflate (η5-C5H5)Re(NO)(PPh3)(SiMe2OTf) (5; 97%), which in turn reacts with (Me2N)3S⊕ [SiMe3F2]⊖ to give (η5-C5H5)Re(NO)(PPh3)(SiMe2F) (6; 77%). Reaction of 5 and pyridine gives the base-stabilized silylene complex [(η5-C5H5)Re(NO)(PPh3){SiMe2(NC5H5)}]⊕ TfO⊖ (7; 84%). CH2Cl2 solutions of (η5-C5H5)Re(NO)(PPh3)(CH3) (8) or 2 and Lewis acids are studied by IR and NMR. As assayed by IR, 8/ECl3 solutions (E = B, Al) show ReNO-ECl3 (major) and Re-ECl3 (minor) adducts. Solutions of 2/BCl3 show analogous adducts (-78°C), and in the presence of excess BCl3 (η5-C5H5)Re-(NO-BCl3)(PPh3)(SiMe2Cl) (11) crystallizes. Solutions of 2/AlCl3 show uncomplexed 2 and Re-AlCl3 (major) and ReNO-AlCl3 (minor) adducts. In contrast to 2-7 and 2/BCl3, 1H- and 13C-NMR spectra of 2/AlCl3 suggest an equilibrium with the base-free silylene complex [(η5-C5H5)Re(NO)(PPh3)-( = SiMe2)]⊕ X⊖.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240211
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  • 2
    Electronic Resource
    Electronic Resource
    Synthesis, Structure, and Reactivity of Chiral Rhenium Cycloalkene Complexes of the Formula ; Facile Vinylic Deprotonation of a Coordinated Alkene (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 729-742 
    Details
    ISSN: 0009-2940
    Keywords: Cycloalkene ligands ; Cyclopentylidene ligands ; Deprotonotion reactions ; Rhenium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of [(η5-C5H5)Re(NO)(PPh3)(ClC6H5)]+BF-4 and (n = 5, a; 6, b; 7, c; 8, d) give cycloalkene complexes (6a - d, 94 to 79%). A crystal structure of the methylcyclopentadienyl analog of 6a shows the Re - plane and Re - PPh3 bond to be coplanar, with the vinyl protons syn to the cyclopentadienyl ligand. Reaction of 6a and tBuO-K+ leads to the vinyl complex (9a, 90%) instead of expected allyl complex (10a) Analogous reactions of 6b - d give varying mixtures of 9b - d/10b - d. HBF4 · OEt2 and 9a react to form the cyclopentylidene complex (10+ BF-4, 96%), the stability of which precludes any intermediacy in the deprotonation of 6a. A crystal structure of 11+ PF-6 shows the Re=C—C planes to be perpendicular to the Re - P bond. Spectroscopic features of compounds 6 are analyzed in detail, and NMR data show a high barrier to cyclopentylidene ligand rotation in 11+ BF-4 (ΔG≢ (110°C) ≥ 19 kcal/mol).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240410
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    Paper (German National Licenses)
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