Synthesis and structure of binuclear O/S-bridged organobismuth complexes and their cooperative catalytic effect on CO 2 fixation

Renhua Qiu, Zhengong Meng, Shuangfeng Yin*, Xingxing Song, Nianyuan Tan, Yongbo Zhou, Kun Yu, Xinhua Xu, Shenglian Luo, Chak Tong AU, Wai Yeung WONG

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

25 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)404-410
Number of pages7
JournalChemPlusChem
Volume77
Issue number5
DOIs
Publication statusPublished - May 2012

Scopus Subject Areas

  • Chemistry(all)

User-Defined Keywords

  • Bridging ligands
  • Carbon dioxide fixation
  • Cooperative effects
  • Homogeneous catalysis
  • Oxygen heterocycles

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