Revisiting the synthesis of trans-[Pt(dmso)2ClMe] and cis-[Pt(dmso)2Me2]: Experimental and DFT studies

Authors
Baquero Velasco, Edwin ArleyUniversity of Alcalá Author; Rodriguez Zuñiga, Ana; Flores Serrano, Juan C.; Temprado Morena, ManuelUniversity of Alcalá Author; Jesús Alcañiz, Ernesto deUniversity of Alcalá Author
Identifiers
Permanent link (URI): http://hdl.handle.net/10017/38268
DOI: 10.1016/j.jorganchem.2019.06.002
ISSN: 0022-328X
Date
2019-06-07
Embargo end date
2020-07-12
Affiliation
Universidad de Alcalá. Departamento de Química Orgánica y Química Inorgánica; Universidad de Alcalá. Departamento de Química Analítica, Química Física e Ingeniería Química
Bibliographic citation
Journal of Organometallic Chemistry, 2019, v. 896, p. 108-112
Keywords
Platinum
Alkyl complexes
Synthesis
DFT calculations
Project
CTQ2017-85203-P y CTQ2016-80600-P (Ministerio de Ciencia, Innovación y Universidades
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Rights
Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
© Elsevier 2019
Access rights
info:eu-repo/semantics/openAccess
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Abstract
The preparation of trans-[Pt(dmso)2ClMe] (2) and cis-[Pt(dmso)2Me2] (3) from cis-[Pt(dmso)2Cl2] (1) and SnMe4has been reexamined (dmso = dimethyl sulfoxide). The information obtained from experimental and DFT studies has permitted the improvement of previously reported methods for the synthesis of both complexes in terms of reaction times, reaction yields, and atom economy. These studies show that complex 1reacts with a first equiv of SnMe4to form trans-[Pt(dmso)2ClMe] (2) as an intermediate that quickly reacts with a second equiv of SnMe4to yield cis-[Pt(dmso)2Me2] (3). When only 1 equiv of the organostannane reagent is added, the comproportionation of 3with the excess of unreacted 1leads the reaction back to the formation of trans-[Pt(dmso)2ClMe] (2). The mechanism of this comproportionation has been studied using DFT calculations.
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