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  • Supramolecular chemistry  (2)
  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 959-969 
    ISSN: 1434-1948
    Schlagwort(e): Bipyridyldiphosphane ligands ; Macrocycles ; Metallacyclophanes ; Platinum ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The 5,5′-bis(hydroxyalkyl)-2,2′-bipyridines 4a-c (Scheme 1) were prepared either in one step (4b, 4c) or in four steps (4a) starting with 5,5′-dimethyl-2,2′-bipyridine in each case. Reaction of 4a-c with mesyl chloride afforded the bis(mesylates) [-C5H3N-(CH2)n-CH2-OSO2Me]2 5a-c [n = 1 (a), 2 (b), 3 (c)], which could easily be transformed into the diphosphanes 6a-c by reaction with LiPPh2. Treatment of 6c, 6b with Cl2Pt(NCPh)2 and (RC6H4)2Pt(COD) according to the high-dilution method resulted in the formation of the tetraphosphadiplatinacyclophanes [-C5H3N-(CH2)4-PPh2PtCl2PPh2-(CH2)4-C5H3N-]2 (7c) and [-C5H3N-(CH2)3-PPh2Pt(C6H4R)2PPh2-(CH2)3-C5H3N-]2 (8b, 9b) (8b: R = H, 9b: R = tBu), respectively (Scheme 2). The molecular structures of 8b and 9b were elucidated by X-ray structural analyses. The noncoordinated bipyridine moieties in 8b were employed to encapsulate copper(I) to give the host/guest complex 10b (Scheme 3), which was investigated by FAB-MS, NMR spectroscopy, and cyclovoltammetry. 10b exhibited a quasi-reversible oxidation at E1/2 = -0.31 V and an electrodeposition-redissolution redox system at E1/2 = -0.79 V, owing to the formation of copper at the surface of the working electrode.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 679-685 
    ISSN: 1434-1948
    Schlagwort(e): Cage compounds ; Metallacyclophanes ; P ligands ; Platinum ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of the tris(triflate) 4 (Scheme 1) has been achieved by means of a straightforward three-step reaction sequence. After initial lithiation of mesitylene, treatment of the obtained trilithium compound C6H3(CH2Li)3 (2) with oxirane results in the formation of 1,3,5-tris(3-hydroxypropyl)benzene (3), which is then transformed to 4 by reaction with (CF3SO2)2O in the presence of pyridine. Whereas 4 reacts with Na2[Os(CO)4] in a somewhat complicated manner, similar reactions with Na[Re(CO)5] and LiPPh2 give the hydrocarbon-bridged tris(rhenium) complex C6H3[(CH2)3Re(CO)5]3 (5) and the tris(phosphane) C6H3[(CH2)3PPh2]3 (6), respectively. Employing the high-dilution method, from 6 and Cl2Pt(NCPh)2 the nanoscaled tri- and hexaplatinacyclophanes 7 and 9 are available. Owing to the optimal geometry and flexibility of the cage in 7, 1,2-dichloroethane can be reversibly encapsulated. The molecular structure of 7 · 7 1,2-Cl2C2H4 was determined by an X-ray structure analysis. The utility of the reactive metal centers in 7 has been demonstrated by replacing the chloro ligands by acetonitrile to give the cationic platinacyclophane 8, in which, according to NMR studies, the cage-like structure is preserved.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Einschränkungen Verfügbarkeit
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