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Arsenic‐Rich Polyarsenides Stabilized by Cp*Fe Fragments
Author(s) -
Schmidt Monika,
Konieczny David,
Peresypkina Eugenia V.,
Virovets Alexander V.,
Balázs Gabor,
Bodensteiner Michael,
Riedlberger Felix,
Krauss Hannes,
Scheer Manfred
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201702903
Subject(s) - chemistry , electron paramagnetic resonance , redox , cyclic voltammetry , arsenic , crystallography , ligand (biochemistry) , nuclear magnetic resonance spectroscopy , mass spectrometry , spectroscopy , crystal structure , stereochemistry , inorganic chemistry , electrochemistry , organic chemistry , nuclear magnetic resonance , biochemistry , physics , receptor , electrode , chromatography , quantum mechanics
The redox chemistry of [Cp*Fe(η 5 ‐As 5 )] ( 1 , Cp*=η 5 ‐C 5 Me 5 ) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η 5 ‐P 5 )]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel As n 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,η 2:2 ‐As 2 )} 2 ] ( 2 ) and the arsenic‐rich complexes [K(dme) 3 ] 2 [(Cp*Fe) 2 (μ,η 4:4 ‐As 10 )] ( 3 ), [K(dme) 2 ] 2 [(Cp*Fe) 2 (μ,η 2:2:2:2 ‐As 14 )] ( 4 ), and [K(dme) 3 ] 2 [(Cp*Fe) 4 (μ 4 ,η 4:3:3:2:2:1:1 ‐As 18 )] ( 5 ). Compound 4 and the polyarsenide complex 5 are the largest anionic As n ligand complexes reported thus far. Complexes 2 – 5 were characterized by single‐crystal X‐ray diffraction, 1 H NMR spectroscopy, EPR spectroscopy ( 2 ), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(η 5 ‐As 5 )] − , which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe) 2 (μ,η 4:4 ‐As 10 )] 2− .