Platinum(IV) Bromo Aqua Complexes. Acid Hydrolysis Equilibria and Kinetics of Bromiide Anation
(1971) In Inorganica Chimica Acta 5. p.643-649- Abstract
- The stepwise stabililty constants, Kn for the bromo aqua complexes PtBrn−1(H2O)7−n5−n; n=4, 5, 6, formed in the successive acid hydrolyses of PtBr62−, have been determined to be K6=(.19±0.1) x 103 M−1, K5= (1.0±0.2) x 104 M−1 and K4=(1.1±0.2) x 105 M−1. A bromide assisted mechanism is proposed for the bromide anations of PtBr4(H2O)2 and PtBr5H2O-. Both these reactions are found to be first order with respect to platinum complex. The dependence of the observed rate constant on the bromide concentration can be described by the eqn.
kexp=κ′[Br−]+κ″[Br−]2
The last term is probably due to a reaction path via a bromide associated outer sphere complex, which might also be involved in the path described by the first term. A... (More) - The stepwise stabililty constants, Kn for the bromo aqua complexes PtBrn−1(H2O)7−n5−n; n=4, 5, 6, formed in the successive acid hydrolyses of PtBr62−, have been determined to be K6=(.19±0.1) x 103 M−1, K5= (1.0±0.2) x 104 M−1 and K4=(1.1±0.2) x 105 M−1. A bromide assisted mechanism is proposed for the bromide anations of PtBr4(H2O)2 and PtBr5H2O-. Both these reactions are found to be first order with respect to platinum complex. The dependence of the observed rate constant on the bromide concentration can be described by the eqn.
kexp=κ′[Br−]+κ″[Br−]2
The last term is probably due to a reaction path via a bromide associated outer sphere complex, which might also be involved in the path described by the first term. A spectrophotometric method has been used. To suppress the protolysis of the aqua complexes, 0.50 M perchloric acid was used as the ionic medium. The temperature was 25.0 °C. (Less) - Abstract (Swedish)
- The stepwise stabililty constants, Kn for the bromo aqua complexes PtBrn−1(H2O)7−n5−n; n=4, 5, 6, formed in the successive acid hydrolyses of PtBr62−, have been determined to be K6=(.19±0.1) x 103 M−1, K5= (1.0±0.2) x 104 M−1 and K4=(1.1±0.2) x 105 M−1. A bromide assisted mechanism is proposed for the bromide anations of PtBr4(H2O)2 and PtBr5H2O-. Both these reactions are found to be first order with respect to platinum complex. The dependence of the observed rate constant on the bromide concentration can be described by the eqn.
kexp=κ′[Br−]+κ″[Br−]2
The last term is probably due to a reaction path via a bromide associated outer sphere complex, which might also be involved in the path described by the first term. A... (More) - The stepwise stabililty constants, Kn for the bromo aqua complexes PtBrn−1(H2O)7−n5−n; n=4, 5, 6, formed in the successive acid hydrolyses of PtBr62−, have been determined to be K6=(.19±0.1) x 103 M−1, K5= (1.0±0.2) x 104 M−1 and K4=(1.1±0.2) x 105 M−1. A bromide assisted mechanism is proposed for the bromide anations of PtBr4(H2O)2 and PtBr5H2O-. Both these reactions are found to be first order with respect to platinum complex. The dependence of the observed rate constant on the bromide concentration can be described by the eqn.
kexp=κ′[Br−]+κ″[Br−]2
The last term is probably due to a reaction path via a bromide associated outer sphere complex, which might also be involved in the path described by the first term. A spectrophotometric method has been used. To suppress the protolysis of the aqua complexes, 0.50 M perchloric acid was used as the ionic medium. The temperature was 25.0 °C. (Less)
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- author
- Elding, Lars Ivar LU and Gustafson, Lena
- organization
- publishing date
- 1971
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Platinum(IV), Bromo-aqua complexes, Stability constants, Bromide anation, Kinetics, Bromide assisted substitution
- in
- Inorganica Chimica Acta
- volume
- 5
- pages
- 7 pages
- publisher
- Elsevier
- external identifiers
-
- scopus:25744465291
- ISSN
- 0020-1693
- DOI
- 10.1016/S0020-1693(00)96002-X
- language
- English
- LU publication?
- yes
- id
- 40be3e9b-f1ad-475e-a7f7-67ec7fc8216f
- date added to LUP
- 2017-02-19 19:36:53
- date last changed
- 2021-01-03 09:23:44
@article{40be3e9b-f1ad-475e-a7f7-67ec7fc8216f, abstract = {{The stepwise stabililty constants, Kn for the bromo aqua complexes PtBrn−1(H2O)7−n5−n; n=4, 5, 6, formed in the successive acid hydrolyses of PtBr62−, have been determined to be K6=(.19±0.1) x 103 M−1, K5= (1.0±0.2) x 104 M−1 and K4=(1.1±0.2) x 105 M−1. A bromide assisted mechanism is proposed for the bromide anations of PtBr4(H2O)2 and PtBr5H2O-. Both these reactions are found to be first order with respect to platinum complex. The dependence of the observed rate constant on the bromide concentration can be described by the eqn.<br/><br/> kexp=κ′[Br−]+κ″[Br−]2<br/><br/>The last term is probably due to a reaction path via a bromide associated outer sphere complex, which might also be involved in the path described by the first term. A spectrophotometric method has been used. To suppress the protolysis of the aqua complexes, 0.50 M perchloric acid was used as the ionic medium. The temperature was 25.0 °C.}}, author = {{Elding, Lars Ivar and Gustafson, Lena}}, issn = {{0020-1693}}, keywords = {{Platinum(IV); Bromo-aqua complexes; Stability constants; Bromide anation; Kinetics; Bromide assisted substitution}}, language = {{eng}}, pages = {{643--649}}, publisher = {{Elsevier}}, series = {{Inorganica Chimica Acta}}, title = {{Platinum(IV) Bromo Aqua Complexes. Acid Hydrolysis Equilibria and Kinetics of Bromiide Anation}}, url = {{http://dx.doi.org/10.1016/S0020-1693(00)96002-X}}, doi = {{10.1016/S0020-1693(00)96002-X}}, volume = {{5}}, year = {{1971}}, }