Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments. / Schmidt, Monika; Konieczny, David; Peresypkina, Eugenia V. и др.
в: Angewandte Chemie - International Edition, Том 56, № 25, 12.06.2017, стр. 7307-7311.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
}
TY - JOUR
T1 - Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments
AU - Schmidt, Monika
AU - Konieczny, David
AU - Peresypkina, Eugenia V.
AU - Virovets, Alexander V.
AU - Balázs, Gabor
AU - Bodensteiner, Michael
AU - Riedlberger, Felix
AU - Krauss, Hannes
AU - Scheer, Manfred
N1 - © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2017/6/12
Y1 - 2017/6/12
N2 - The redox chemistry of [Cp*Fe(η5-As5)] (1, Cp*=η5-C5Me5) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η5-P5)]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel Asn scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme)2][{Cp*Fe(μ,η2:2-As2)}2] (2) and the arsenic-rich complexes [K(dme)3]2[(Cp*Fe)2(μ,η4:4-As10)] (3), [K(dme)2]2[(Cp*Fe)2(μ,η2:2:2:2-As14)] (4), and [K(dme)3]2[(Cp*Fe)4(μ4,η4:3:3:2:2:1:1-As18)] (5). Compound 4 and the polyarsenide complex 5 are the largest anionic Asn ligand complexes reported thus far. Complexes 2–5 were characterized by single-crystal X-ray diffraction, 1H NMR spectroscopy, EPR spectroscopy (2), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(η5-As5)]−, which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe)2(μ,η4:4-As10)]2−.
AB - The redox chemistry of [Cp*Fe(η5-As5)] (1, Cp*=η5-C5Me5) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η5-P5)]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel Asn scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme)2][{Cp*Fe(μ,η2:2-As2)}2] (2) and the arsenic-rich complexes [K(dme)3]2[(Cp*Fe)2(μ,η4:4-As10)] (3), [K(dme)2]2[(Cp*Fe)2(μ,η2:2:2:2-As14)] (4), and [K(dme)3]2[(Cp*Fe)4(μ4,η4:3:3:2:2:1:1-As18)] (5). Compound 4 and the polyarsenide complex 5 are the largest anionic Asn ligand complexes reported thus far. Complexes 2–5 were characterized by single-crystal X-ray diffraction, 1H NMR spectroscopy, EPR spectroscopy (2), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(η5-As5)]−, which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe)2(μ,η4:4-As10)]2−.
KW - arsenic
KW - DFT calculations
KW - iron
KW - polyarsenides
KW - reduction
KW - ANIONS
KW - FERROCENE
KW - CRYSTAL-STRUCTURE
KW - COMPLEXES
KW - ELECTRON-DIFFRACTION
KW - DIMERIZATION
KW - LIGANDS
KW - PENTAPHOSPHAFERROCENE
KW - FULLERENE
KW - CHEMISTRY
UR - http://www.scopus.com/inward/record.url?scp=85019884615&partnerID=8YFLogxK
U2 - 10.1002/anie.201702903
DO - 10.1002/anie.201702903
M3 - Article
C2 - 28508464
AN - SCOPUS:85019884615
VL - 56
SP - 7307
EP - 7311
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 25
ER -
ID: 10191396