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Photocatalysis of chloroform degradation by μ-dichlorotetrachlorodipalladate(II)

Authors
Journal
Inorganica Chimica Acta
0020-1693
Publisher
Elsevier
Publication Date
Volume
363
Issue
7
Identifiers
DOI: 10.1016/j.ica.2010.01.032
Keywords
  • Tetrachloropalladate(Ii)
  • Hexachlorodipalladate(Ii)
  • Chloroform
  • Photocatalysis
  • Photodecomposition

Abstract

Abstract Unlike other chlorometallate complexes that catalyze the photodecomposition of haloalkanes through photodissociation of a chlorine atom, both PdCl 4 2 - and Pd 2 Cl 6 2 - catalyze chloroform decomposition through a process that appears to involve C–H bond breakage from an excited state association complex with chloroform. This would account for the greatly retarded rate of decomposition in CDCl 3 and for the generation of CCl 4 as a side product. In chloroform, Pd 2 Cl 6 2 - and PdCl 4 2 - are in slow equilibrium with each other. The rate for the conversion of Pd 2 Cl 6 2 - – PdCl 4 2 - in chloroform at 23 °C obeys the expression (0.03 M −1 s −1) [ PdCl 4 2 - ][Cl −]. The equilibrium constant, K = [ Pd 2 Cl 6 2 - ][Cl −] 2/[ PdCl 4 2 - ] 2, was estimated to be 3 × 10 −3 M in CHCl 3.

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