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Kinetics and Mechanism of Formation of Tetrahaloplatinate(II) Ion in the Reactions of Bis (oxalato)‐platinate(II) Ion with Chloride and Bromide Ions in Acid Media
Author(s) -
Banerjea D.,
Banerjee P.
Publication year - 1973
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19734010210
Subject(s) - oxalate , chemistry , ion , bromide , dissociation (chemistry) , chloride , halide , inorganic chemistry , kinetics , medicinal chemistry , ligand (biochemistry) , oxalic acid , organic chemistry , receptor , biochemistry , physics , quantum mechanics
The rate of transformation of bis(oxalato)platinate(II) ion, Pt(Ox) 2 2− , into tetrahaloplatinate(II) ion, PtX 4 2− , in acid media containing the halide ion (X − = Cl − , Br − ) has been investigated spectrophotometrically. The observed rate law is: Rate = {k′ + k″[H + ]} [X − ][Pt(Ox) 2 2− ]. Activation parameters corresponding to k′ and k″ have been evaluated. The results are consistent with a mechanism which involves association of X − with Pt(Ox) 2 2−followed by dissociation of an oxalate ligand through acid independent and acid dependent paths. Fast addition of X − to the Pt(Ox)X − gives an intermediate Pt(Ox)X 2 −2from which the oxalate is replaced in a fast step by X − ions under the trans influence of the bound X − ligands forming the product PtX 4 2− .