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From Dibismuthenes to Three- and Two-Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N Rings through a Combined Experimental and Theoretical Study
Authors: Vránová Iva | Alonso Mercedes | Lo Rabindranath | Sedlak Robert | Jambor Roman | Růžička Aleš | De Proft Frank | Hobza Pavel | Dostál Libor
Year: 2015
Type of publication: článek v odborném periodiku
Name of source: Chemistry - A European Journal
Publisher name: Wiley-VCH
Place: Weinheim
Page from-to: 16917-16928
Titles:
Language Name Abstract Keywords
cze Tří a dvou koordinované bismuthinideny: Vznik aromatického BiC3N kruhu. Experimentální a Teoretická Studie Byly studovány redukce N,C,-chelatovaných bismutitých chloridů [C6H3-2,6-(CH=NR)(2)]BiCl2 [ R=tBu (1), 2',6'-Me2C6H3 (2), 4'-Me2NC6H4 (3)]. Byly připraveny tří a dvou koordinované bismuthinideny, kdy došlo k vzniku aromatického BiC3N kruhu. bismuthinideny; BiC3N; hetrocykly; N ligandy; redukce
eng From Dibismuthenes to Three- and Two-Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N Rings through a Combined Experimental and Theoretical Study The reduction of N,C,-zchelated 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'-iPr(2)C(6)H(3))-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-zchelated 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'-ziPr(2)C(6)H(3))-4,6(tBu)(2)]Bi (9) as an unprecedented two-zcoordinated 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 H-1 and C-13 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 di-bismuthene) 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. aromaticity; bismuth; heterocycles; N ligands; reduction

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