Schütz Max, Gemel Christian, Muhr Maximilian, Jandl Christian, Kahlal Samia, Saillard Jean-Yves, Fischer Roland A
Department of Chemistry, Technical University Munich Lichtenbergstrasse 4 D-85748 Garching Germany
Catalysis Research Centre, Technical University Munich Ernst-Otto-Fischer Strasse 1 D-85748 Garching Germany.
Chem Sci. 2021 Apr 1;12(19):6588-6599. doi: 10.1039/d1sc00268f.
Cluster growth reactions in the system Cu + Al (Mes = mesitylene, Cp* = pentamethylcyclopentadiene) were explored and monitored by LIFDI-MS and H-NMR. Feedback into experimental design allowed for an informed choice and precise adjustment of reaction conditions and led to isolation of the intermetallic cluster CuAl(Mes) (). Cluster reacts with excess 3-hexyne to yield the triangular cluster CuAl (). The two embryonic CuAl(Mes) and CuAl clusters and , respectively, were shown to be intermediates in the formation of an inseparable composite of the closely related clusters CuAl (), HCuAl () and CuAl (), which just differ by one Cu core atom. The radical nature of the open-shell superatomic CuAl cluster is reflected in its reactivity towards addition of one Cu core atom leading to the closed shell superatom CuAl (, and as well by its ability to undergo σ(C-H) and σ(Si-H) activation reactions of CHCH (toluene) and (TMS)SiH (TMS = tris(trimethylsilyl)).
通过激光诱导荧光解离质谱（LIFDI-MS）和氢核磁共振（H-NMR）对体系Cu + Al（Mes = 均三甲苯，Cp* = 五甲基环戊二烯）中的簇生长反应进行了探索和监测。反馈到实验设计中有助于明智地选择和精确调整反应条件，并导致金属间簇CuAl(Mes)的分离（）。簇与过量的3-己炔反应生成三角形簇CuAl（）。已表明两个初始的CuAl(Mes)和CuAl簇分别是形成紧密相关簇CuAl（）、HCuAl（）和CuAl（）的不可分离复合物的中间体，这些簇仅相差一个铜核心原子。开壳层超原子CuAl簇的自由基性质体现在其对添加一个铜核心原子形成闭壳层超原子CuAl（）的反应性上，也体现在其对CHCH（甲苯）和(TMS)SiH（TMS = 三（三甲基硅基））进行σ(C-H)和σ(Si-H)活化反应的能力上。
