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Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz) 3 (M=Sr, Ba)
Author(s) -
Wang Qian,
Pan Sudip,
Wu YanBo,
Deng Guohai,
Bian JianHong,
Wang Guanjun,
Zhao Lili,
Zhou Mingfei,
Frenking Gernot
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201908572
Subject(s) - chemistry , alkaline earth metal , barium , transition metal , strontium , benzene , valence (chemistry) , valence electron , ligand (biochemistry) , metal , crystallography , singlet state , electronic structure , electron configuration , inorganic chemistry , chemical bond , electron , computational chemistry , ion , excited state , atomic physics , catalysis , organic chemistry , biochemistry , physics , receptor , quantum mechanics
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 η 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 π 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 π* 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.