Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 11677-11683 |
| Number of pages | 7 |
| Journal | Chemistry - A European Journal |
| Volume | 23 |
| Issue number | 48 |
| DOIs | |
| Publication status | Published - 2017 Aug 25 |
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Keywords
- Lewis acids
- bismuth
- carbonyl ligands
- coordination modes
- multiple bonds
ASJC Scopus subject areas
- Catalysis
- Organic Chemistry
Cite this
A Multiply Bonded Trigonal-Planar Bismuth(III) Complex : Prodigious Lewis Acidity, Solvatochromism, Etherification, and Semiconducting Characteristics. / Shieh, Minghuey; Yu, Chia Chi; Hsing, Kai Jieah; Chang, Wei Jie.
In: Chemistry - A European Journal, Vol. 23, No. 48, 25.08.2017, p. 11677-11683.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - A Multiply Bonded Trigonal-Planar Bismuth(III) Complex
T2 - Prodigious Lewis Acidity, Solvatochromism, Etherification, and Semiconducting Characteristics
AU - Shieh, Minghuey
AU - Yu, Chia Chi
AU - Hsing, Kai Jieah
AU - Chang, Wei Jie
PY - 2017/8/25
Y1 - 2017/8/25
N2 - 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.
AB - 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.
KW - Lewis acids
KW - bismuth
KW - carbonyl ligands
KW - coordination modes
KW - multiple bonds
UR - http://www.scopus.com/inward/record.url?scp=85028071405&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85028071405&partnerID=8YFLogxK
U2 - 10.1002/chem.201702396
DO - 10.1002/chem.201702396
M3 - Article
AN - SCOPUS:85028071405
VL - 23
SP - 11677
EP - 11683
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 48
ER -