• Structure and reactivity of palladium and platinum arylazooximates

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      https://www.ias.ac.in/article/fulltext/jcsc/093/04/0741-0751

    • Keywords

       

      Palladium arylazooximates; platinum arylazooximates; selective bond cleavage; cone angles; fluxional behaviour; aromatic hydroxylation

    • Abstract

       

      The structure and selected reactions of the title compounds are reviewed. Some highlights are as follows (L = conjugate base of phenylazoacetaldoxime). While PtL2 exist in cis and trans forms, PdL2 occurs only in thetrans form. In the crystalline state cis-PtL2 consists of weakly held dimers (Pt. Pt 3.151 A) buttrans-PtL2 consists of stacks of discrete molecules in the solid state.Trans- PdL2 displays a surprisingly large tetrahedral distorsion. The different metal-ligand bonds undergo selective cleavage by different reagents. Thus HCl and tertiary phosphines respectively cleave the M-N (oxime) and M-N (azo) bonds. Phosphine cleavage leads to interesting situations such as cone angle-dependent equilibria and fluxional behaviour. A rich redox chemistry consisting of successive reductions of the azo groups and of the metal are revealed electrochemically.Cis-PtL2 unliketrans- PtL2 undergoes a facile one-electron oxidation at low potentials. Another very curious reaction of cis-PtL2 is the process in which an aromatic ring is thermally hydroxylated at the expense of an oximato oxygen atom. The meaning and significance of the observations are discussed.

    • Author Affiliations

       

      Animesh Chakravorty1

      1. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Calcutta - 700 032, India
    • Dates

       
  • Journal of Chemical Sciences | News

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