期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 48, 页码 17365-17374出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201908572
关键词
18-electron rule; alkaline earth metals; benzene complexes; bonding analysis; matrix isolation spectroscopy
资金
- National Natural Science Foundation of China [21273140, 21688102, 21433005, 21703099]
- Nanjing Tech University [39837123, 39837132]
- SICAM Fellowship from Jiangsu National Synergetic Innovation Center for Advanced Materials
- Natural Science Foundation of Jiangsu Province for Youth [BK20170964]
- Nanjing Tech University
We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)(3) (M=Sr, Ba) in low-temperature Ne matrix. Both complexes are characterized by a D-3 symmetric structure involving three equivalent eta(6)-bound benzene ligands and a closed-shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal-ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the pi MOs of benzene ligands into the vacant (n-1)d AOs of M and strong backdonation from the occupied (n-1)d AO of M into vacant pi* MOs of benzene ligands. The metals in these 20-electron complexes have 18 effective valence electrons, and, thus, fulfill the 18-electron rule if only the metal-ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.
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