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Bromide Anation Kin...
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Elding, Lars IvarLund University,Lunds universitet,Centrum för analys och syntes,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Centre for Analysis and Synthesis,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
(författare)
Bromide Anation Kinetics of Some Platinum(IV) Bromo Aqua Complexes
- Artikel/kapitelEngelska1977
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LIBRIS-ID:oai:lup.lub.lu.se:b3f84f25-a447-4bd0-8c67-b34c9825ae38
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https://lup.lub.lu.se/record/b3f84f25-a447-4bd0-8c67-b34c9825ae38URI
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https://doi.org/10.1016/S0020-1693(00)90919-8DOI
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Språk:engelska
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Sammanfattning på:engelska &svenska
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Bromide anations of PtBr5H2O− in the presence of PtBr42− or bromine, of trans-PtBr4(H2O)2 in the presence of PtBr42− and of cis-PtBr4(H2O)2 in the presence of bromine have been studied in 0.50 M perchloric acid medium at 25 °C. The rate law for the bromide anation of PtBr5H2O−indicates two parallel reaction paths. The term k′Br−2 corresponds to a bromide assisted mechanism. The second term in the rate expression can be accounted for by assuming that a dimeric intermediate is formed from the platinum(IV) substrate and hydrated PtBr42−. The formation of the reaction product PtBr62− is preceded by a substitution of water by bromide in this dimer. A bromide assisted mechanism can also describe the bromide anation kinetics of cis-PtBr4(H2O)2, the rate law determined. The bromide anation of trans-PtBr4(H2O)2 in the presence of PtBr42− occurs by a two-term rate law, indicating two parallel paths, k′ corresponding to formation of PtBr5H2O− and k″ to formation of PtBr62−. Trans-PtBr4(H2O)2 reacts so slowly with bromide in the absence of PtBr42− that no reaction can be observed. The large difference in bromide anation rates for PtBr5H2O− and cis-PtBr4(H2O)2 compared to trans-PtBr4(H2O)2 might indicate that halide assisted anations are possible only for complexes having a halide (or some other effective bridging group) in trans-position to the aqua ligand to be replaced.
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Bromide anations of PtBr5H2O− in the presence of PtBr42− or bromine, of trans-PtBr4(H2O)2 in the presence of PtBr42− and of cis-PtBr4(H2O)2 in the presence of bromine have been studied in 0.50 M perchloric acid medium at 25 °C.The rate law for the bromide anation of PtBr5H2O−indicates two parallel reaction paths. The term k′Br−2 corresponds to a bromide assisted mechanism. The second term in the rate expression can be accounted for by assuming that a dimeric intermediate is formed from the platinum(IV) substrate and hydrated PtBr42−. The formation of the reaction product PtBr62− is preceded by a substitution of water by bromide in this dimer.A bromide assisted mechanism can also describe the bromide anation kinetics of cis-PtBr4(H2O)2, the rate law determined. The bromide anation of trans-PtBr4(H2O)2 in the presence of PtBr42− occurs by a two-term rate law, indicating two parallel paths, k′ corresponding to formation of PtBr5H2O− and k″ to formation of PtBr62−.Trans-PtBr4(H2O)2 reacts so slowly with bromide in the absence of PtBr42− that no reaction can be observed. The large difference in bromide anation rates for PtBr5H2O− and cis-PtBr4(H2O)2 compared to trans-PtBr4(H2O)2 might indicate that halide assisted anations are possible only for complexes having a halide (or some other effective bridging group) in trans-position to the aqua ligand to be replaced.
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Gustafson, LenaLund University
(författare)
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Centrum för analys och syntesKemiska institutionen
(creator_code:org_t)
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Ingår i:Inorganica Chimica Acta22:2, s. 201-2070020-1693
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