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Reactivity of N,C,N-Chelated Antimony(III) and Bismuth(III) Chlorides with Lithium Reagents: Addition vs Substitution
Year: 2015
Type of publication: článek v odborném periodiku
Name of source: Organometallics
Publisher name: American Chemical Society
Place: Washington
Page from-to: 534-541
Titles:
Language Name Abstract Keywords
cze Reaktivita N,C,N-Chelatovaných antimonitých a bismutitých chloridů : Adice vs. Substituce Byla studována reaktivita N,C,N-Chelatovaných antimonitých a bismutitých chloridů (LMCl2)-M-1,2 (1-4: L-1, M = Sb (1), Bi (3); L-2, M = Sb (2), Bi (4)), kde L-1 = C6H3-2,6-(CH=N-t-Bu)(2) a L-2 = C6H3-2,6-(CH=N-2',6'-Me2C6H3)(2)). Reaktivita; N,C,N-Chelatované; antimonité chloridy; bismutité chloridy; adice; substituce
eng Reactivity of N,C,N-Chelated Antimony(III) and Bismuth(III) Chlorides with Lithium Reagents: Addition vs Substitution N,C,N-chelated antimony(III) and bismuth(III) chlorides (LMCl2)-M-1,2 (1-4: for L-1, M = Sb (1), Bi (3); for L-2, M = Sb (2), Bi (4)) containing ligands L-1,L-2 (where L-1 = C6H3-2,6-(CH=N-t-Bu)(2), L-2 = C6H3-2,6-(CH=N-2',6'-Me2C6H3)(2)) were prepared by reactions of lithium precursors with SbCl3 or BiCl3. The identities of 1-4 were established both in solution (H-1 and C-13 NMR spectroscopy) and, in the case of 1-3, in the solid state using single-crystal X-ray diffraction analysis. Treatment of antimony derivatives 1 and 2 with 2 molar equiv of R'Li (R = Me, n-Bu, Ph) yielded the set of substituted 1,3-(R')(2)-2-R-7-(CH=NR)-1H-2,1-benzazastiboles 5-10 (where R = t-Bu, 2,6-Me2C6H3 and R' = Me, n-Bu, Ph) as a result of a nucleophilic attack of one of the lithium compounds across the imino C=N functionality. In contrast, analogous reactions between bismuth congeners 2 and 4 and R'Li (2 equiv, R' = Me, Ph) gave (LBiR2)-Bi-1,2' (11-13: for L-1, R' = Me (11), Ph (12); for L-2, R' = Me (13)) as products of substitution of chlorine atoms. Compounds 5-13 were characterized by the help of H-1 and C-13 NMR spectroscopy. The molecular structures of 8, 9, and 13 were unambiguously established using single-crystal X-ray diffraction analysis. bond covalent radii; organobismuth(iii) dihalides; ligand; organoantimony(iii); cleavage; halides; ncn; derivatives; complexes; oxidation

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