Syntheses and Structures of Solvent-Free bis(Trimethylsilyl)methyl Complexes of the Heavy Alkaline-Earth Metals

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-20 DOI:10.1021/acs.organomet.6c00241

Angus C. G. Shephard, Dawid Jędrzkiewicz, Bastian Rösch, Jens Langer, Christian Färber, Sjoerd Harder

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Abstract

Ether-free alkylmetal reagents are important precursors in organometallic chemistry. With few exceptions, there are hardly any heavier, ether-free group 2 alkylmetal complexes. Herein we describe facile synthetic methods for the synthesis of solvent-free Ae[CH(SiMe₃)₂]₂ complexes (Ae = Ca, Sr, Ba) and discuss their structural and spectroscopic features. All complexes can be synthesized by salt metathesis procedures. Reaction of two equivalents of KCH(SiMe₃)₂ with one equivalent of AeI₂ in Et₂O and subsequent removal of all solvents under high vacuum gave ether-free Ae[CH(SiMe₃)₂]₂ in yields of 78% (Ca), 56% (Sr) and 80% (Ba).The Ca and Sr reagents could also be obtained by a solvent-free solid state synthetic route, i.e. by ball-milling KCH(SiMe₃)₂ and AeI₂ in a 2:1 ratio and subsequent extraction by benzene. Facile access to highly reactive, ether-free heavier Ae metal alkyl precursors is important for further development of the rapidly growing field of group 2 organometallic chemistry.

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重碱土金属无溶剂双（三甲基硅基）甲基配合物的合成与结构

无醚烷基金属试剂是金属有机化学中重要的前体。除了少数例外，几乎没有较重的不含醚的2族烷基金属配合物。本文介绍了无溶剂Ae[CH(SiMe3)2]2配合物（Ae = Ca, Sr, Ba）的简易合成方法，并讨论了它们的结构和光谱特征。所有配合物均可通过盐分解法合成。两种当量的KCH(SiMe3)2与一种当量的AeI2在Et2O中反应，然后在高真空下去除所有溶剂，得到无醚的Ae[CH(SiMe3)2]2收率为78% (Ca), 56% （Sr）和80% （Ba）。Ca和Sr试剂也可以通过无溶剂的固态合成路线得到，即以2:1的比例球磨KCH(SiMe3)2和aei2，然后用苯萃取。快速获得高活性、不含醚的较重Ae金属烷基前体对于快速发展的第二族有机金属化学领域的进一步发展具有重要意义。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.