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  • 1
    ISSN: 1434-4475
    Keywords: Keywords. Silyl complexes; Platinum complexes; Ligand exchange.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung.  Umsetzung von cis-(R 3P)2Pt(SiPhMe2)2 mit einem Überschuß an HSi(OMe)3, HSiPh3, HSi3Ph7, HPh2SiSiMe3 oder H2SiPh2 führt zum stufenweisen Austausch der Silylliganden. Der Austausch des ersten SiPhMe2-Liganden erfolgt rascher als der des zweiten. Die Austauschgeschwindigkeit hängt von der Art der Reste R′ in HSiR 3 ′ ab und sinkt in der Reihenfolge HSi(OMe)3≫ H2SiPh2〉HPh2SiSiMe3≫HSi3Ph7〉HSiPh3. Bei der Reaktion von (R 3P)2Pt(SiMe2Ph)2 mit einem Überschuß an HSi(OMe)3 wird der Austausch in Abhängigkeit vom R 3P-Liganden in der Reihenfolge PPh2Me〉PEt3〉PPhMe2 langsamer. Bei der Reaktion des Chelat-Komplexes (Ph3P)(Ph3Si)Pt(PPh2CH2CH2CH2SiMe2) mit HSi(OMe)3 oder H2SiPh2 wird nur Austausch des nichtchelatisierten Silylliganden beobachtet.
    Notes: Summary.  Reaction of cis-(R 3P)2Pt(SiPhMe2)2 with an excess of HSi(OMe)3, HSiPh3, HSi3Ph7, HPh2SiSiMe3, or H2SiPh2 results in a stepwise exchange of the silyl ligands. Exchange of the first SiPhMe2 ligand is faster than that of the second. The exchange rate depends on the nature of the groups R′ in HSiR 3 ′ and decreases in the order HSi(OMe)3≫H2SiPh2〉HPh2SiSiMe3≫HSi3Ph7〉 HSiPh3. The rate of the exchange reaction of (R 3P)2Pt(SiMe2Ph)2 with an excess of HSi(OMe)3 depends on the R 3P ligand and decreases in the order PPh2Me〉PEt3〉PPhMe2. When the chelated complex (Ph3P)(Ph3Si)Pt(PPh2CH2CH2SiMe2) is reacted with HSi(OMe)3 or H2SiPh2, only exchange of the non-chelated silyl ligand is observed.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-1948
    Keywords: Platinum ; Nickel ; Stannyl complexes ; Oxidative addition ; Tin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of Ni(COD)2 (COD = 1,5-cyclooctadiene) with two equivalents of Ph2PCH2CH2SnPh3 or of (Ph3P)2Pt(C2H4) with two equivalents of Ph2PCH2CH2SnR3 (R = Ph, Me, Bu) results in the immediate formation of the complexes (R3SnCH2CH2Ph2P)M[PPh2CH2CH2SnPh2(M-Sn)](R) (M = Ni, Pt) with a cis arrangement of the two phosphorus atoms. The structure of (Me3SnCH2CH2Ph2P)Pt[PPh2CH2-CH2SnMe2(Pt-Sn)](Me) was confirmed by an X-ray structure analysis. In the presence of PPh3, this complex shows dynamic behavior in solution due to Ph2PCH2CH2SnMe3/PPh3 exchange. When the phosphanylalkylstannanes Ph2PCH2CH2SnPh3-xMex (x = 1, 2) are employed in the reaction with Ni(COD)2 or (Ph3P)2Pt(C2H4), the Sn-Ph groups are more prone to oxidative addition than the Sn-Me groups. When Ni(COD)2 is treated with one equivalent of Ph2PCH2CH2SnPh3 and PR′3 (PCy3 or PMe2Ph) each, the complexes (R′3P)M(PPh2CH2CH2SnPh2)(Ph)(M-Sn) are formed. Heating of (Ph3SnCH2CH2Ph2P)Ni[PPh2-CH2CH2SnPh2(Ni-Sn)](Ph) to 70 °C induces the oxidative addition of a Sn-Ph group of the dangling ligand, and cis-Ni[PPh2CH2CH2SnPh2(Ni-Sn)]2 is obtained. The same complex is formed upon reaction of Ni(COD)2 with Ph2PCH2CH2SnPh2H. Reaction of Ni(COD)2 with Ph2PCH2CH2SnMe3 results in the immediate formation of trans-Ni[(PPh2CH2CH2SnMe2(Ni-Sn)]2.
    Type of Medium: Electronic Resource
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