In situ Grignard metalation method (iGMM) for the preparation of alkynyl magnesium and calcium compounds

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2024-10-14 DOI:10.1016/j.poly.2024.117256

Simon Sengupta, Phil Liebing, Matthias Westerhausen

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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.

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原位格氏金属化法（iGMM）制备炔基镁和钙化合物

在原位格氏金属化法（iGMM）中，在四氢呋喃中立即形成了乙基溴化镁以及乙基钙和乙基碘化锶金属化三烷基硅烷基乙炔。对于 Me3SiCCMgBr (1a)，与温度有关的 Schlenk 平衡正在起作用，这种异性化合物与同性同系物 Mg(CCSiMe3)2 (1b) 和 MgBr2 共存。反应焓 ΔH 和熵 ΔS 采用特征值。最初形成的 Me3SiCCCaI (2a) 被定量转化为同性化合物 Ca(CCSiMe3)2 (2b) 和 CaI2。随着碱土金属体积的增大，降解产物 Me3SiCCSiMe3 的数量也在增加，这妨碍了锶和钡分析纯化合物的分离。单晶 X 射线衍射测定了 [(thf)3Mg(CCSiMe3)2] (1b) 和 [(thf)3Ca(µCCSiMe3)I]2 (2a) 的分子结构。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

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.