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  • Springer  (2)
  • 1
    ISSN: 1572-8862
    Keywords: Iron ; cadmium ; zinc ; indium ; bimetallic complexes ; functional phosphines ; alkoxysilyl ; bridging ligands ; crystal structures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The reactions of K[Fe{Si(OMe)3}(CO)3(P∼Y)][P∼Y=Ph2PCH2C(O)Ph, Ph2PCH2C(O)[(η-C5H4)FeCp] (Cp=η5-C5H5), Ph2P(CH2)2CN] with CdCl2·2.5H2O, ZnX 2 (X=Cl, I) or InCl3 afforded Fe-Cd-Fe or Fe-M(μ-X)2 M-Fe (M=Cd, Zn, In;X=Cl, I) and Fe-InCl2 complexes. Some of them contain an unusual and labile μ-η2-SiO alkoxysilyl bridge which may be associated with a bridging mode for the ketophosphine ligand (first such example structurally established), thus providing original results in bimetallic chemistry on the intramolecular coordination of oxygendonor functions ofchemically different hemilabile ligands firmly attached to a neighboring metal center. The structures of the trinuclear complex (3), of the chlorobenzene solvate of the tetranuclear complex (4a·C6H5Cl) and of [mer-(OC)3{(EtO)3Si} (4e) have been determined by X-ray diffraction. Crystals of 3 are orthorhombic, space groupPbcn, witha=19.010(4),b=11.766(5),c=26.998(7)Å, andZ=4. Crystals of4a·C6H5Cl are monoclinic, space groupC2/c witha=22.455(3),b=17.680(2),c=16.627(4)Å, β=90.80(4)°, andZ=4. Crystals of4e are monoclinic, space groupC2/c witha=25.392(5),b=18.554(6),c=16.28(1)Å, β=120.73(3)°, andZ=4. The structures were solved using direct methods and Fourier difference techniques and refined by blocked full-matrix least squares toR=0.035 (R w =0.049) for 2719 observed reflections, toR=0.042 (R w =0.056) for 3082 observed reflections, and toR=0.057 (R w =0.075) for 1850 observed reflections for3, 4a·C6H5Cl and4e, respectively. The Fe-Zn complexes (9a), (9b) and (9c) were prepared and characterized by spectroscopic methods.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Upon u.v. irradiation of [Fe(CO)4(PR 3 ′ )] with HSiR3 (HSiR3 = HSiMePh2, PR′3 = PPh3; HSiR3 = HSiMe2Cl, PR′3 = PPh3 or PMe2Ph; HSiR3 = HSiMeCl2, PR′3 = PPh3, PMePh2, PMe2Ph or PMe3; HSiR3 = HSiCl3, PR′3 = PPh3, PMePh2, PMe2Ph, PMe3 or PBu 3 n ) the corresponding hydridosilyl complexes [Fe(CO)3H(PR′3)SiR3] are formed. The complexes have themer configuration with acis disposition of the hydride and the silyl ligands. Prolonged irradiation with an excess of silane results in the formation of bis-silyl complexes [Fe(CO)3(PR3)(SiR3)2], if electron density at the metal is not too high. Thus, [Fe(CO)3H(PPh3)SiMePh2] and [Fe(CO)3-H(PMe2Ph)SiMe2Cl] can be obtained but not the corresponding bis-silyl complexes. Most bis-silyl complexes are obtained asmer-isomers with acis-arrangement of the silyl ligands. Only for [Fe(CO)3(PR′3)(SiCl3)2] with small phosphine ligands (PR′3 = PMe3 or PMe2Ph) is thefac-isomer formed.
    Type of Medium: Electronic Resource
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