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  • 1
    Electronic Resource
    Electronic Resource
    Addition of protic molecules to coordinated 2-pyridinecarboxaldehyde in gold(III), palladium(II), and platinum(II) complexes (2000)
    Springer
    Transition metal chemistry 25 (2000), S. 485-489 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reactions of AuIII, PtII and PdII complexes with 2-pyridinecarboxaldehyde (2CHO-py) have been examined in protic (H2O, MeOH, EtOH) and aprotic (DMF, CH2Cl2) solvents. Compounds in which the pyridine ligand is N-coordinated, either in the original aldehydic form or in a new form derived from addition of one or two protic molecules, have been isolated, namely: [Au(2CHO-py · H2O)Cl3], [Au(2CHO-py · MeOH)Cl3], [Au(2CHO-py · 2EtOH)Cl3], cis-[Pt(2CHO-py)2Cl2], trans-[Pd(2CHO-py)2Cl2], trans-[Pt(dmso)(2CHO-py)Cl2], [Pt{C5H4N-(CH2SMe)}Cl(2CHO-py)](ClO4), [Pt(terpy)(2CHOpy)](ClO4)2, [Pt(terpy)(2CHO-py · H2O)](ClO4)2 (terpy = 2,2′:6′,2′′-terpyridine). 1H-n.m.r. experiments show that the addition of the protic molecule(s) to the PtII and PdII complexes is reversible. The effects of the nature of the metal ion and the ancillary ligands as well as of the total charge of the complexes on the relative stability of the addition products are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007093227025
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  • 2
    Electronic Resource
    Electronic Resource
    A comparison of nucleophilicity and lability of thiazoles and pyridines in substitution reactions at platinum(II) complexes (1997)
    Springer
    Transition metal chemistry 22 (1997), S. 46-52 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The second order rate constants, k2, for the displacement of chloride by nitrogen donors L (L = thiazoles, pyridines, amines) from [Pt(S-S)Cl2] [S-S = 1, 2-bis-(phenylsulfanyl) ethane] and [Pt(SNS)Cl]+ [SNS=2, 6-bis- (methylsulfanylmethyl)pyridine] are linearly related to their proton basicity according to a free-energy relationship of the type logk2 = α(pKa) + β. In the reverse reactions, i.e. the displacement by chloride of the coordinated nitrogen donors, the lability depends not only upon ligand basicity but also upon the nature of the group to be displaced in the order thiazoles 〈 pyridines. This behaviour, attributed to different π interactions in the ground state, is confirmed in the solvolytic displacement of the organic bases from complexes of the type trans-[Pt(dmso)(L)Cl2]. Steric retardation, owing to the presence of a methyl group ortho to the nitrogen in the aromatic rings, is considerably less for entering thiazoles as compared to pyridines.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018469819983
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