Rubidium and caesium aluminyls: synthesis, structures and reactivity in C-H bond activation of benzene
Rubidium and caesium aluminyls: synthesis, structures and reactivity in C-H bond activation of benzene
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DOI：
10.1039/d1cc05379e
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发表时间：
2022-01-07
影响因子：
4.9
通讯作者：
Mulvey, Robert E.
中科院分区：
文献类型：
--
作者：
Gentner, Thomas X.;Evans, Matthew J.;Mulvey, Robert E.
扩展低价铝化学的知识，报道了铷和铯铝基化合物以完成第1族（Li-Cs）金属铝基化合物的集合。这两种化合物结晶为接触的二聚体对，由MMIDLINE HORIZONTAL ELLIPSIS PI（芳烃）相互作用支持，在铝基单元之间具有明显的扭曲。密度泛函理论计算表明，M和Al原子之间的对称成键，与Al为中心的孤对捐赠到空置的Rb和Cs轨道。有趣的是，尽管它们的结构相似的Cs铝基使苯的C-H键活化，但不是Rb铝基，这反映了碱金属在这些杂环体系中的重要性。
Expanding knowledge of low valent aluminium chemistry, rubidium and caesium aluminyls are reported to complete the group 1 (Li-Cs) set of metal aluminyls. Both compounds crystallize as a contacted dimeric pair supported by MMIDLINE HORIZONTAL ELLIPSIS pi(arene) interactions with a pronounced twist between aluminyl units. Density functional theory calculations show symmetrical bonding between the M and Al atoms, with an Al centred lone-pair donating into vacant Rb and Cs orbitals. Interestingly, despite their structural similarity the Cs aluminyl enables C-H bond activation of benzene, but not the Rb aluminyl reflecting the importance of the alkali metal in these heterobimetallic systems.