Simon Sengupta, Phil Liebing, Matthias Westerhausen
{"title":"In situ Grignard metalation method (iGMM) for the preparation of alkynyl magnesium and calcium compounds","authors":"Simon Sengupta, Phil Liebing, Matthias Westerhausen","doi":"10.1016/j.poly.2024.117256","DOIUrl":null,"url":null,"abstract":"<div><div>In the in situ Grignard Metalation Method (iGMM), intermediately formed ethylmagnesium bromide as well as ethylcalcium and ethylstrontium iodide metalate trialkylsilylethyne in THF. For Me<sub>3</sub>Si<img>C<img>C<img>MgBr (<strong>1a</strong>) a temperature-dependent Schlenk equilibrium is operative and this heteroleptic compound coexists with the homoleptic congeners Mg(C<img>C<img>SiMe<sub>3</sub>)<sub>2</sub> (<strong>1b</strong>) and MgBr<sub>2</sub>. The reaction enthalpy ΔH and entropy ΔS adopt characteristic values. Initially formed Me<sub>3</sub>Si<img>C<img>C<img>CaI (<strong>2a</strong>) is quantitatively converted to the homoleptic compound Ca(C<img>C<img>SiMe<sub>3</sub>)<sub>2</sub> (<strong>2b</strong>) and CaI<sub>2</sub>. With increasing size of the alkaline-earth metal increasing amounts of the degradation product Me<sub>3</sub>Si<img>C<img>C<img>SiMe<sub>3</sub> hamper isolation of analytically pure compounds of strontium and barium. The molecular structures of [(thf)<sub>3</sub>Mg(C<img>C<img>SiMe<sub>3</sub>)<sub>2</sub>] (<strong>1b</strong>) and [(thf)<sub>3</sub>Ca(µ<img>C<img>C<img>SiMe<sub>3</sub>)I]<sub>2</sub> (<strong>2a</strong>) have been determined by single-crystal X-ray diffraction.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"264 ","pages":"Article 117256"},"PeriodicalIF":2.4000,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polyhedron","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0277538724004327","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
In the in situ Grignard Metalation Method (iGMM), intermediately formed ethylmagnesium bromide as well as ethylcalcium and ethylstrontium iodide metalate trialkylsilylethyne in THF. For Me3SiCCMgBr (1a) a temperature-dependent Schlenk equilibrium is operative and this heteroleptic compound coexists with the homoleptic congeners Mg(CCSiMe3)2 (1b) and MgBr2. The reaction enthalpy ΔH and entropy ΔS adopt characteristic values. Initially formed Me3SiCCCaI (2a) is quantitatively converted to the homoleptic compound Ca(CCSiMe3)2 (2b) and CaI2. With increasing size of the alkaline-earth metal increasing amounts of the degradation product Me3SiCCSiMe3 hamper isolation of analytically pure compounds of strontium and barium. The molecular structures of [(thf)3Mg(CCSiMe3)2] (1b) and [(thf)3Ca(µCCSiMe3)I]2 (2a) have been determined by single-crystal X-ray diffraction.
期刊介绍：
Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry.
Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.
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