THEORETICAL PREDICTIONS ON THE STRUCTURE AND d-AO-BASED AROMATICITY OF Re3F , Re3F3X+ (X = Li, Na, AND K), AND Re3F3Y2+ (Y = Be, Mg, AND Ca) CLUSTERS
B. Jin1, Q. Jin2, F.-K. Jin3
1School of Environment and Biology Engineering, Shenyang University of Chemical Technology, Shenyang, P.R. China
jinbiao@syuct.edu.cn
2School of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing, P.R. China
3Liaoning University of Petroleum and Chemical Technology, Fushun, P.R. China
Ключевые слова: rhenium low-fluoride cluster, aromaticity, DFT calculations
Страницы: 1316-1326
Аннотация
The electronic structure and chemical bonding in Re3F clusters are investigated using density functional theory (DFT) calculations. Out research results show that the ground state for the Re3F clusters is found to be triplet state 3 with the D 3 h symmetry, quintet state 5 A ¢ with the Cs symmetry, and quintet state 5 with the D 3 h symmetry, respectively. A detailed molecular orbital (MO) analysis reveals that the Re3F ( D 3 h , 3 ) dication possesses multiple (pF and partial dRe) aromaticity that is respectively responsible for the triangular F3 framework and the triangular Re3 framework in the Re3F ( D 3 h , 3 ) dication. The neutral Re3F3 ( Cs , 5 A ¢) cluster possesses partial d-aromaticity that is responsible for the triangular Re3 framework in the Re3F3 ( Cs , 5 A ¢) cluster. The Re3F ( D 3 h , 5 ) anion possesses multiple (s and partial d) aromaticity that is responsible for the triangular Re3 framework in the Re3F ( D 3 h , 5 ) cluster. We also examined their hexagonal pyramidal-type Re3F3X+ ( C 3 v , 1 ) (X = Li, Na, and K) and Re3F3Y2+ ( C 3 v , 1 ) (Y = Be, Mg, and Ca) complexes containing the Re3F3 ( D 3 h , 1 ) ligand to reveal that the Re3F3 ( D 3 h , 1 ) structural unit is perfectly preserved in these Re3F3X+ ( C 3 v , 1 ) and Re3F3Y2+ ( C 3 v , 1 ) complexes also having the corresponding d -orbital aromatic characters.
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