Reactions of aluminium(i) with transition metal carbonyls: scope, mechanism and selectivity of CO homologation.
Reactions of aluminium(i) with transition metal carbonyls: scope, mechanism and selectivity of CO homologation.
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DOI：
10.1039/d1sc04940b
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发表时间：
2021-11-17
期刊：
影响因子：
8.4
通讯作者：
Crimmin MR
中科院分区：
文献类型：
--
作者：
Kong RY;Batuecas M;Crimmin MR
在过去的几十年里，已经发现了许多模型系统，从CO中产生碳-碳键。这些反应与费托工艺（一种将合成气（H2/CO）转化为碳氢化合物混合物的技术）具有潜在的相关性。本文报道了一个由CO构造碳链的均相模型系统。该系统利用了过渡金属络合物和主族还原剂的协同作用。综合验证了C1 → C2 → C3 → C4的完整反应序列。反应性的范围是广泛的，并且包括各种过渡金属（M = Cr、Mo、W、Mn、Re、Co），包括在工业非均相费-托催化剂中发现的那些。过渡金属片段的变化影响链生长步骤的相对速率，从而允许稀有C2中间体的分离和结构表征。碳链增长的选择性也受此变量的影响;观察到C3碳链的两种不同的异构体与不同的过渡金属试剂以不同的比例形成。基于实验（同位素标记研究，中间体的研究）和计算（DFT，NBO，ETS-NOCV）的组合，我们提出了一个完整的链增长机制，涉及在过渡金属和主族中心的定义的反应性。报道了一个由CO构建碳链的均相模型系统。该系统利用了过渡金属络合物和主族还原剂的协同作用。综合验证了C1 → C2 → C3 → C4的完整反应序列。
Over the past few decades, numerous model systems have been discovered that create carbon–carbon bonds from CO. These reactions are of potential relevance to the Fischer–Tropsch process, a technology that converts syngas (H2/CO) into mixtures of hydrocarbons. In this paper, a homogeneous model system that constructs carbon chains from CO is reported. The system exploits the cooperative effect of a transition metal complex and main group reductant. An entire reaction sequence from C1 → C2 → C3 → C4 has been synthetically verified. The scope of reactivity is broad and includes a variety of transition metals (M = Cr, Mo, W, Mn, Re, Co), including those found in industrial heterogeneous Fischer–Tropsch catalysts. Variation of the transition metal fragment impacts the relative rate of the steps of chain growth, allowing isolation and structural characterisation of a rare C2 intermediate. The selectivity of carbon chain growth is also impacted by this variable; two distinct isomers of the C3 carbon chain were observed to form in different ratios with different transition metal reagents. Based on a combination of experiments (isotope labelling studies, study of intermediates) and calculations (DFT, NBO, ETS-NOCV) we propose a complete mechanism for chain growth that involves defined reactivity at both transition metal and main group centres. A homogeneous model system that constructs carbon chains from CO is reported. The system exploits the cooperative effect of a transition metal complex and main group reductant. An entire reaction sequence from C1 → C2 → C3 → C4 has been synthetically verified.
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