期刊
NATURE COMMUNICATIONS
卷 9, 期 -, 页码 -出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/s41467-017-02581-2
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资金
- University of Duisburg-Essen
- German Research Foundation DFG [SCHU 1069/22-1]
- Alexander von Humboldt Stiftung
- Max-Planck-Gesellschaft
Neutral stibinyl and bismuthinyl radicals are typically short-lived, reactive species. Here we show the synthesis and solid-state structures of two stable stibinyl [L(Cl)Ga](2)Sb center dot 1 and bismuthinyl radicals [L(I)Ga](2)Bi center dot 4, which are stabilized by electropositive metal centers. Their description as predominantly metal-centered radicals is consistent with the results of NMR, EPR, SQUID, and DFT studies. The Lewis-acidic character of the Ga ligands allow for significant electron delocalization of the Sb- and Bi- unpaired radical onto the ligand. Single-electron reduction of [L(Cl)Ga](2)Sb center dot gave LGaSbGa(Cl)L 5, the first compound containing a Ga=Sb double bond. The pi-bonding contribution is estimated to 9.56 kcal mol(-1) by NMR spectroscopy. The bonding situation and electronic structure is analyzed by quantum mechanical computations, revealing significant pi backdonation from the Sb to the Ga atom. The formation of 5 illustrates the high-synthetic potential of 1 for the formation of new compounds with unusual electronic structures.
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