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

ABSTRACT: 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 ?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 ? 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 ?* 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.

SUBMITTER: Wang Q

PROVIDER: S-EPMC6900055 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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

Wang Qian Q Pan Sudip S Wu Yan-Bo YB Deng Guohai G Bian Jian-Hong JH Wang Guanjun G Zhao Lili L Zhou Mingfei M Frenking Gernot G

Angewandte Chemie (International ed. in English) 20191017 48

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. T ...[more]

PMID: 31498532

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Project description:Two new alkaline earth metal-organic frameworks (AE-MOFs) containing Sr(II) (UPJS-15) or Ba(II) (UPJS-16) cations and extended tetrahedral linker (MTA) were synthesized and characterized in detail (UPJS stands for University of Pavol Jozef Safarik). Single-crystal X-ray analysis (SC-XRD) revealed that the materials are isostructural and, in their frameworks, one-dimensional channels are present with the size of ~11 × 10 Å2. The activation process of the compounds was studied by the combination of in situ heating infrared spectroscopy (IR), thermal analysis (TA) and in situ high-energy powder X-ray diffraction (HE-PXRD), which confirmed the stability of compounds after desolvation. The prepared compounds were investigated as adsorbents of different gases (Ar, N2, CO2, and H2). Nitrogen and argon adsorption measurements showed that UPJS-15 has SBET area of 1321 m2 g-1 (Ar) / 1250 m2 g-1 (N2), and UPJS-16 does not adsorb mentioned gases. From the environmental application, the materials were studied as CO2 adsorbents, and both compounds adsorb CO2 with a maximum capacity of 22.4 wt.% @ 0 °C; 14.7 wt.% @ 20 °C and 101 kPa for UPJS-15 and 11.5 wt.% @ 0°C; 8.4 wt.% @ 20 °C and 101 kPa for UPJS-16. According to IAST calculations, UPJS-16 shows high selectivity (50 for CO2/N2 10:90 mixture and 455 for CO2/N2 50:50 mixture) and can be applied as CO2 adsorbent from the atmosphere even at low pressures. The increased affinity of materials for CO2 was also studied by DFT modelling, which revealed that the primary adsorption sites are coordinatively unsaturated sites on metal ions, azo bonds, and phenyl rings within the MTA linker. Regarding energy storage, the materials were studied as hydrogen adsorbents, but the materials showed low H2 adsorption properties: 0.19 wt.% for UPJS-15 and 0.04 wt.% for UPJS-16 @ -196 °C and 101 kPa. The enhanced CO2/H2 selectivity could be used to scavenge carbon dioxide from hydrogen in WGS and DSR reactions. The second method of applying samples in the area of energy storage was the use of UPJS-15 as an additive in a lithium-sulfur battery. Cyclic performance at a cycling rate of 0.2 C showed an initial discharge capacity of 337 mAh g-1, which decreased smoothly to 235 mAh g-1 after 100 charge/discharge cycles.

Dataset Information

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

Publications

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

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