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The Solvent Path in...
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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
(author)
The Solvent Path in Square-Planar Substitutions. Kinetics and Mechanism for Reactions of Tetrachloroplatinate(II) and Aquachloroplatinates(II) with Halides, Thiocyanate and Dimethyl Sulfoxide
- Article/chapterEnglish1978
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LIBRIS-ID:oai:lup.lub.lu.se:d5947864-e67c-4987-a85f-af381b977ee3
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https://lup.lub.lu.se/record/d5947864-e67c-4987-a85f-af381b977ee3URI
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https://doi.org/10.1016/S0020-1693(00)95010-2DOI
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Language:English
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Summary in:English
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The kinetics for the reactions between the six complexes PtCln(H2O)4-n−2n, n = 0,1,2,3,4 (including cis- and trans-isomers for n=2) and the entering ligands Y = Cl−, Br−, I−, SCN−, and DMSO have been studied. The experiments with PtCl42− and trans- PtCl2(H2O)2 give the usual two-term rate constant kexp = k1 + k2[Y], when no extra chloride has been added to the solutions. The parameter k1 can be identified as the acid hydrolysis rate constant for PtCl42− and trans-PtCl2(H2O)2, respectively. It is shown that both PtCl3H2O− and PtCl(H2O)3+ are sufficiently reactive for all Y to be the intermediates in the k1- paths of these two reactions. An associative process with the solvent is therefore probable. The entering ligand order for H2O as leaving ligand is DMSO < Cl− < Br− < SCN− < I− (approximately 0.3:1:4:40:100) for the substrate complexes studied. DMSO is a bad entering ligand in spite of its large trans-effect. The relative trans-effect Cl−/H2O and the relative efficacy of H2O and Cl− as leaving ligands depend on the nature of the entering ligand Y, whereas the relative cis-effect Cl-/H2O is independent of Y. This is compatible with an associative mechanism via a trigonal bipyramidal intermediate.
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Gröning, Ann-BrittLund University
(author)
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Centrum för analys och syntesKemiska institutionen
(creator_code:org_t)
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In:Inorganica Chimica Acta31:2, s. 243-2500020-1693
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