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  • 1
    ISSN: 1572-8862
    Schlagwort(e): Iron ; cadmium ; zinc ; indium ; bimetallic complexes ; functional phosphines ; alkoxysilyl ; bridging ligands ; crystal structures
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau , Physik
    Notizen: 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.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 495-499 
    ISSN: 1434-1948
    Schlagwort(e): Heterobimetallics ; μ-Isonitrile complexes ; μ-Aminocarbyne complexes ; Bis(diphenylphosphanyl)amine ; Iron ; Platinum ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Addition of isonitriles to [(OC)3Fe(μ-CO)(μ-Ph2PNHPPh2)Pt(PPh3)] 1 produces the μ-isonitrile complexes [(OC)3Fe(μ-C=NR)(μ-Ph2PNHPPh2)Pt(PPh3)] 2, which are transformed to the μ-aminocarbyne complexes [(OC)3Fe{μ-CN(El)R}(μ-Ph2PNHPPh2)Pt(PPh3)]+;3 and 4 by electrophilic addition of [El][BF4] or [El][OSO2CF3] (El = H, Me). The dppa backbone of 4 is readily deprotonated by KOSiMe3 to yield the very stable zwitterionic aminocarbyne complex [(OC)3Fe{μ-CN(Me)2,6-xylyl}(μ-Ph2PNPPh2)Pt(PPh3)] 5.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1434-1948
    Schlagwort(e): Heterobimetallics ; Hydride complexes ; Alkenyl complexes ; μ-Isonitrile complexes ; Silicon ; Iron ; Platinum ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The heterobimetallic hydride complexes [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(H)(PR3)] (1a: X = CH2, PR3 = PPh3; 1b: X = NH, PR3 = PPh3; 1c: X = CH2, PR3 = PMePh2) have been prepared by the oxidative addition of [(OC)3Fe(H){Si(OMe)3}(η1-Ph2PXPPh2)] to [Pt(H2C=CH2)(PPh3)2] or by reaction of K[(OC)3Fe{Si(OMe)3}(η1-dppm)] with trans-[Pt(Cl)(H)(PPh3)2]. The solid-state structure of compound 1b has been determined by single-crystal X-ray diffraction. 1-Alkynes such as methylpropiolate or phenylacetylene insert in a regiospecific manner into the Pt-H bond of 1 to yield the σ-alkenyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-Ph2PXPPh2)Pt{C(R)=CH2}] (2a: X = CH2, R = CO2Me; 2b: X = NH, R = CO2Me; 3a: X = CH2, R = Ph). Addition of the Pt-H bond of 3a across the triple bond of [D1]phenylacetylene affords [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pt{C(Ph)=C(D)H}] (3a*) having the deuteron trans to platinum (cis addition). This insertion reaction is accompanied by dissociation of the platinum-bonded PR3 ligand and saturation of the vacant coordination site by a dative μ-η2-Si-O→Pt interaction. When 3 is treated with PR3 again, a subsequent phosphane-induced rearrangement leading to vinylidene-bridged complexes [(OC)3Fe{μ-C=C(H)R′}(μ-Ph2PXPPh2)Pt(PR3)] (4a: X = CH2, R′ = Ph, PR3 = PPh3; 4b: X = NH, R′ = Ph, PR3 = PPh3; 4c: X = CH2, R′ = Ph, PR3 = PMePh2; 4d: X = CH2, R′ = p-tolyl, PR3 = PPh3) occurs. Upon purging a solution of 3a with carbon monoxide, the labile CO adduct [(OC)3Fe{Si(OMe)3}(μ-dppm)-Pt(CO){C(Ph)=CH2}] 5a is formed, addition of 2,6-xylyl isocyanide to 2a and 3a affords the isonitrile adducts [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(CNxylyl){C(R)=CH2}] (5b: R = CO2Me; 5c: R = Ph), respectively. When hydride complex 1a is allowed to react with stoichiometric amounts of aromatic isonitriles, formal elimination of HSi(OMe)3 occurs, yielding the heterodinuclear isonitrile-bridged complexes [(OC)3Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (6a: R = 2,6-xylyl; 6b: R = o-anisyl; 6c: R = p-anisyl; 6d: R = p-C6H4NH2) and the bis(isonitrile) complexes [(OC)2(RN≡C)Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (7a: R = 2,6-xylyl; 7b: R = p-anisyl). Single-crystal X-ray diffraction studies perfomed on 6a and 6b reveal that the molecular structures of these μ-isonitrile complexes closely resemble the μ-vinylidene complexes 4. The two metal centers are bridged in a symmetric manner by strongly bent CNR ligands, the aromatic groups R being oriented towards the Fe(CO)3 moiety. Electrophilic addition of HBF4 to the basic nitrogen atom of the μ-CNR ligand transforms 6 to the cationic μ-aminocarbyne complexes [(OC)3Fe{μ-CN(H)R}(μ-dppm)Pt(PPh3)][BF4] (8a: R = 2,6-xylyl; 8b: R = p-anisyl; 8c: R = p-C6H4NH2).
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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