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COUPLING REACTIONS OF YNAMINES - SYNTHESES, STRUCTURAL CHARACTERIZATION AND ELECTROCHEMISTRY OF SOME NIDO AND CLOSO FERRACYCLOPENTADIENE COMPLEXES

JOURNAL OF ORGANOMETALLIC CHEMISTRY. Bd. 441. H. 1. 1992 S. 81 - 97

Erscheinungsjahr: 1992

ISBN/ISSN: 0022-328X

Publikationstyp: Zeitschriftenaufsatz

Doi/URN: 10.1016/0022-328X(92)80193-2

Volltext über DOI/URN

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Inhaltszusammenfassung


The reaction of [Fe2(CO)7{C(Ph)C(NEt2)}] (1) With ynamines RC=CNEt2 (R = Me, C3H5, or CH2Ph) at 20-degrees-C yielded dinuclear ferracyclopentadiene complexes [Fe2(CO)6{C(Ph)C(NEt2) C-(NEt2)(CR)}] (R = Me (2), R = CH2Ph (3), R = C3H5 (4)). Complex 5, [Fe2(CO)6{C(C3H5)C(NEt2) C-(NEt2)C(C3H5)}], was obtained directly from the reaction Of C3H5C=CNEt2 with [Fe2(CO)9]. All complexes were characterized by a combination of microanalytical and spectroscopic techniques. The molecular structure of 4 was...The reaction of [Fe2(CO)7{C(Ph)C(NEt2)}] (1) With ynamines RC=CNEt2 (R = Me, C3H5, or CH2Ph) at 20-degrees-C yielded dinuclear ferracyclopentadiene complexes [Fe2(CO)6{C(Ph)C(NEt2) C-(NEt2)(CR)}] (R = Me (2), R = CH2Ph (3), R = C3H5 (4)). Complex 5, [Fe2(CO)6{C(C3H5)C(NEt2) C-(NEt2)C(C3H5)}], was obtained directly from the reaction Of C3H5C=CNEt2 with [Fe2(CO)9]. All complexes were characterized by a combination of microanalytical and spectroscopic techniques. The molecular structure of 4 was determined X-ray crystallographically: triclinic, P1BAR, a = 8.820(2) angstrom, b = 9.261(2) angstrom, c = 18.470(2) angstrom, alpha = 89.40(1)-degrees, beta = 81.81(1)-degrees, gamma = 70.23(2)-degrees, R(w) = 0.0406 for 2580 reflections. The nido complexes 4 and 5 transformed to the closo tripledecker compounds [Fe3(CO)8 {C(Ph)C(NEt2)C(NEt2)C(R)}] (R = Ph (6); R = C3H5 (7)) by an excess of [Fe2(CO)9] in refluxing hexane. Both complexes were characterized by IR, H-1 NMR, mass spectra and chemical analysis. The X-ray structure of 6 was carried out: monoclinic, P2(1)/c, a = 14.900(3), b = 11.149(2), c = 18.453(4) angstrom, beta = 91.14(2)-degrees, R(w) = 0.0414 for 2304 reflections. Only one isomer could be isolated for the nido compounds. The nido-closo transformation did not modify the coupling within the butadiene moiety. Electrochemistry of the nido and closo complexes is reported. The closo compounds showed two reversible one-electron reduction waves whereas the nido species were completely irreversibly reduced. » weiterlesen» einklappen

Autoren


HEIM, B (Autor)
DARAN, JC (Autor)
JEANNIN, Y (Autor)
EBER, B (Autor)
HUTTNER, G (Autor)

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