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
N1 - Funding Information:
This work is supported by the Ministry of Science and Technology, Taiwan (Grant No. 104–2113-M-003–004-MY3 to M. Shieh). We thank the NCHC of Taiwan for providing the computer time and the facilities. We also thank the NSRRC of Taiwan for providing the facilities and XAS measurements.
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
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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 -