Journal
CHEMPLUSCHEM
Volume 77, Issue 5, Pages 404-410Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cplu.201200030
Keywords
bridging ligands; carbon dioxide fixation; cooperative effects; homogeneous catalysis; oxygen heterocycles
Categories
Funding
- NSF of Hunan Province [10JJ1003]
- NSFC [21003040, 20973056]
- National 863 Program of China [2009AA05Z319]
- Program for New Century Excellent Talents in Universities [NCET-10-0371]
- Fundamental Research Funds for the Central Universities
- Hong Kong Baptist University [FRG/08-09/II-09]
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In the synthesis of binuclear organobismuth complexes (16) through treatment of organobismuth chlorides with NaOH or Na2S center dot 9H2O, the two 5,6,7,12-tetrahydrodibenz [c,f][1,5]azabismocine frameworks are cross-linked by either a sulfur or an oxygen atom. The complexes (16) show high catalytic efficiency in the synthesis of cyclic carbonates from 2-(chloromethyl)oxirane and CO2. Compared with their precursor chlorides (79), methoxide 10 and methanethioate 11 which are mononuclear organobismuth complexes, the binuclear organobismuth complexes show higher cooperative catalytic effect. However, the complexes with an oxygen bridge (13) are not stable in air and lose their catalytic efficiency because of hydrolysis or CO2 adsorption (forming organobismuth carbonates in the latter case). Nonetheless, the binuclear organobismuth complexes (46) with a sulfur bridge are highly stable in air and can be applied in the synthesis of cyclic carbonates (with the co-presence of Bu4NI) across various kinds of epoxides, thus exhibiting satisfactory efficiency and selectivity.
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