A Multiply Bonded Trigonal-Planar Bismuth(III) Complex: Prodigious Lewis Acidity, Solvatochromism, Etherification, and Semiconducting Characteristics

Minghuey Shieh*, Chia Chi Yu, Kai Jieah Hsing, Wei Jie Chang

*此作品的通信作者

研究成果: 雜誌貢獻期刊論文同行評審

8 引文 斯高帕斯(Scopus)

摘要

The formation of a hitherto unknown 4-center, 6π–conjugated trigonal-planar complex, [Bi{Cr(CO)5}3] (1), is reported, in which the oxidation state of the Bi atom is +3, as evidenced by XAS, XPS, and DFT calculations. The BiIII atom in 1 has dual donor and acceptor properties in its bonding mode. In contrast to the mild Lewis acidity of BiIII, the central Bi in 1 functions as a prodigious Lewis acid site to exhibit strong affinity toward F ions, unique solvatochromic properties, intriguing etherification through the C−O bond cleavage of alcohols, and surprising semiconducting characteristics with an ultra-narrow optical band gap of 1.02 eV, which can be attributed to the intermolecular Bi⋅⋅⋅O and O⋅⋅⋅O interactions in the solid state. The tetrahedral Fe(CO)4-adduct [{Fe(CO)4}Bi{Cr(CO)5}3]3− (1-Fe) allowed the selective demetallation to afford the isoelectronic multiply bonded BiCr3-complex 1 and the BiCr2Fe-complex, [Bi{Cr(CO)5}2{Fe(CO)4}] (2), which may open a novel pathway for the design of the heterometal-incorporated trigonal-planar Bi-Cr complexes.

原文英語
頁(從 - 到)11677-11683
頁數7
期刊Chemistry - A European Journal
23
發行號48
DOIs
出版狀態已發佈 - 2017 八月 25

ASJC Scopus subject areas

  • 催化
  • 有機化學

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