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  • 1
    Digitale Medien
    Digitale Medien
    Synthesis, Reactivity, and Molecular Structures of Bis(diphenylphosphanyl)amine- and Bis(diphenylphosphanyl)amide-Bridged Heterobimetallic μ-Isonitrile- and μ-Aminocarbyne Complexes (Fe-Pt) (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 495-499 
    Details
    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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  • 2
    Digitale Medien
    Digitale Medien
    Reactivity of Silyl-Substituted Heterobimetallic Iron-Platinum Hydride Complexes towards Unsaturated Molecules, I Alkyne Insertions into the Platinum-Hydride Bond, Phosphane-Induced σ-Alkenyl-μ-Vinylidene Rearrangements and Formation of μ-Isonitrile Complexes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 241-252 
    Details
    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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  • 3
    Digitale Medien
    Digitale Medien
    Übergangsmetall-Silyl-Komplexe, 44. Darstellung der zweikernigen Silyl-Komplexe (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 durch oxidative Addition von (CO)3(R′R′′HP)Fe(H)SiR3 an (C2H4)Pt(PPh3)2 (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 17-21 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Dinuclear complexes ; Iron complexes ; Platinum complexes ; Silyl complexes ; Phosphide bridges ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Transition Metal Silyl Complexes, 44.  -  Preparation of the Binuclear Silyl Complexes (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 by Oxidative Addition of (CO)3(R′R′′HP)Fe(H)SiR3 to (C2H4)Pt(PPh3)2The complexes (CO)3(R′R′′HP)Fe(H)SiR3 (1) [PHR′R′′ = PHPh2, PH2Ph, PH2Cy; SiR3 = SiPh3, SiPh2Me, SiPhMe2, Si(OMe)3] react with Pt(C2H4)(PPh3)2 to give the dinuclear, silyl-substituted complexes (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 (2) in high yields. Upon reaction of 2 (R = R′ R′′ = Ph) with CO, the PPh3 ligand at Pt being trans to the PPh2 bridge is exchanged, and (CO)3(Ph3Si)Fe(μ-PPh2)Pt(PPh3)CO (3) is formed. Complex 3 is characterized by an X-ray structure analysis. The rather short Fe  -  Si distance [233.9(2) pm] and the infrared spectrum of 3 indicate that the Fe  -  Pt bond is quite polar.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19931260104
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  • 4
    Digitale Medien
    Digitale Medien
    Übergangsmetall-Silyl-Komplexe, 48. Synthese neuartiger heteronuklearer Silyl-Zweikernkomplexe (OC)3(R3Si)Fe(μ-PR′R″)Pt(1,5-COD)(Fe-Pt), Phosphan-Austauschreaktionen an (OC)3 (R3Si)Fe(μ-PR′R″)Pt(PPh3)2(Fe - Pt) und Darstellung der Dihydrido-Komplexe [(OC)3Fe(μ-PPh2)(μ-H)2Pt(PR3)2][BF4](Fe - Pt) (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 295-304 
    Details
    ISSN: 0009-2940
    Schlagwort(e): Heterobimetallic complexes ; Iron complexes ; Platinum complexes ; Silyl complexes ; Phosphido bridges ; Hydrido complexes ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Transition Metal Silyl Complexes, 48[1]. - Synthesis of the New Heterobimetallic Dinuclear Silyl Complexes (OC)3(R3Si)-Fe(μ-PR′R″)Pt(1,5-COD)(Fe-Pt), Phosphane Exchange Reactions of (OC)3(R3Si)Fe(μ-PR′R″)Pt(PPh3)2(Fe-Pt), and Preparation of the Dihydrido complexes [(OC)3Fe(μ-PPh2)(μ-H)2Pt(PR3)2][BF4](Fe-Pt)The dinuclear, silyl-substituted complexes (OC)3(R3Si)Fe(μ-PR′r″)Pt(1,5-COD) (1) [μ-PR′R″ = PPh2, PCY2, PHPh; SiR3 = SiPh3, Si(OMe)3] were prepared in high yields by the oxidative addition of the hydrido complexes (OC)3(PHR′R″)Fe(H)-SiR3 to Pt(1,5-COD)2. Upon reaction of (OC)3(R3Si)Fe(μ-PR′R″)Pt(PPh3)2 [μ-PR′R″ = PPh2, PHCy; SiR3 = SiPh3, SiPh2Me, SiPhMeCl, Si(OMe)3] with two equivalents of PR‴3 (PMe3, PBu3, PEt3) or with one equivalent of chelating di-phosphanes (vdpp, dppe, dppm) both PPh3 ligands are displaced, and (OC)3(R3Si)Fe(μ-PR′R″)Pt(PR‴3)2 or (OC)3(R3Si)-Fe(μ-PR′R″)Pt[(PPh2)2X] (X = C=CH2, C2H4, CH2) are formed, respectively. When one equivalent of PMe3 is used, only the PPh3 ligand trans to the μ-PPh2 bridge is substituted, and (OC)3(Ph3Si)Fe(μ-PPh2)Pt(PPh3)(PMe3 is formed. The 1,5-COD ligand in 1 is displaced by P(OR)3 to give (OC)3-(Ph3Si)Fe(μ-PPh2)Pt[P(OR)3]2 (R = Me, Ph). The complexes (OC)3(Ph3Si)Fe(μ-PPh2)Pt(PMe3)2and (OC)3(Ph3Si)Fe(μ-PPh2)Pt[(PPh2)2C=CH2] were characterized by X-ray structure analysis. The short Fe-Si distances [233.0(2) and 235.6(3) pm] and the infrared v(CO) absorptions indicate that the Fe-Pt bonds are quite polar. Protonation of (OC)3(Me2-PhSi)Fe(μPPh2)Pt(PPh3)2 with CF3COOH gives the hydrido-bridged complex [(OC)3(Me2PhSi)Fe(μ-PPh2)(μ-H)Pt-(PPh3)2][O2CCF3]. Upon addition of an excess of HBF4 · Et2O to (OC)3(R3Si)Fe(μ-PPh2)Pt(PPh3)2 (R = Ph, OMe), (OC)3-Si)Fe(μ-PPh2)Pt[Pt[P(OMe)3]2 or (OC)3(Ph2MeSi)Fe(μ-PPh2)-Pt(dppe) R3SiF is split, and the corresponding μ-dihydrido complexes [(OC)3Fe(μ-PPh2)(μ-H)2Pt(PR3)2][BF4] are obtained.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/cber.19941270204
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