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• W2173315031 endingPage "16928" @default.
• W2173315031 startingPage "16917" @default.
• W2173315031 abstract "The reduction of N,C,N-chelated bismuth chlorides [C6H3-2,6-(CH=NR)2]BiCl2 [where R = tBu (1), 2',6'-Me2C6H3 (2), or 4'-Me2NC6H4 (3)] or N,C-chelated analogues [C6H2-2-(CH=N-2',6'-iPr2C6H3)-4,6-(tBu)2]BiCl2 (4) and [C6H2-2-(CH2NEt2)-4,6-(tBu)2]BiCl2 (5) is reported. Reduction of compounds 1-3 gave monomeric N,C,N-chelated bismuthinidenes [C6H3-2,6-(CH=NR)2]Bi [where R = tBu (6), 2',6'-Me2C6H3 (7) or 4'-Me2NC6H4 (8)]. Similarly, the reduction of 4 led to the isolation of the compound [C6H2-2-(CH=N-2',6'-iPr2C6H3)-4,6-(tBu)2]Bi (9) as an unprecedented two-coordinated bismuthinidene that has been structurally characterized. In contrast, the dibismuthene {[C6H2-2-(CH2NEt2)-4,6-(tBu)2]Bi}2 (10) was obtained by the reduction of 5. Compounds 6-10 were characterized by using (1)H and (13)C NMR spectroscopy and their structures, except for 7, were determined with the help of single-crystal X-ray diffraction analysis. It is clear that the structure of the reduced products (bismuthinidene versus dibismuthene) is ligand-dependent and particularly influenced by the strength of the N→Bi intramolecular interaction(s). Therefore, a theoretical survey describing the bonding situation in the studied compounds and related bismuth(I) systems is included. Importantly, we found that the C3NBi chelating ring in the two-coordinated bismuthinidene 9 exhibits significant aromatic character by delocalization of the bismuth lone pair." @default.
• W2173315031 created "2016-06-24" @default.
• W2173315031 creator A5007894568 @default.
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• W2173315031 creator A5073541742 @default.
• W2173315031 creator A5076620253 @default.
• W2173315031 creator A5086331904 @default.
• W2173315031 date "2015-10-05" @default.
• W2173315031 modified "2023-10-06" @default.
• W2173315031 title "From Dibismuthenes to Three- and Two-Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC₃N Rings through a Combined Experimental and Theoretical Study" @default.
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