Transition-Metal Chemistry of Alkaline-Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr, Ba). 2019

Qian Wang, and Sudip Pan, and Yan-Bo Wu, and Guohai Deng, and Jian-Hong Bian, and Guanjun Wang, and Lili Zhao, and Mingfei Zhou, and Gernot Frenking
Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.

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 D3 symmetric structure involving three equivalent η6 -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.

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