Department of Chemistry
Synthesis and structure of binuclear O/S-bridged organobismuth complexes and their cooperative catalytic effect on CO2 fixation
In the synthesis of binuclear organobismuth complexes (1-6) through treatment of organobismuth chlorides with NaOH or Na 2S·9H 2O, 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 (1-6) show high catalytic efficiency in the synthesis of cyclic carbonates from 2-(chloromethyl)oxirane and CO 2. Compared with their precursor chlorides (7-9), 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 (1-3) are not stable in air and lose their catalytic efficiency because of hydrolysis or CO 2 adsorption (forming organobismuth carbonates in the latter case). Nonetheless, the binuclear organobismuth complexes (4-6) with a sulfur bridge are highly stable in air and can be applied in the synthesis of cyclic carbonates (with the co-presence of Bu 4NI) across various kinds of epoxides, thus exhibiting satisfactory efficiency and selectivity. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Bridging ligands, Carbon dioxide fixation, Cooperative effects, Homogeneous catalysis, Oxygen heterocycles
Source Publication Title
Qiu, Renhua, Zhengong Meng, Shuangfeng Yin, Xingxing Song, Nianyuan Tan, Yongbo Zhou, Kun Yu, Xinhua Xu, Shenglian Luo, Chak-Tong Au, and Wai-Yeung Wong. "Synthesis and structure of binuclear O/S-bridged organobismuth complexes and their cooperative catalytic effect on CO2 fixation." ChemPlusChem 77.5 (2012): 404-410.