Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments

Angewandte Chemie
Monika SchmidtManfred Scheer

Abstract

The redox chemistry of [Cp*Fe(η5 -As5 )] (1, Cp*=η5 -C5 Me5 ) 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, 1 H 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- .

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Citations

Apr 21, 2018·Angewandte Chemie·Fabian SpitzerManfred Scheer
Oct 5, 2018·Chemical Communications : Chem Comm·Yi WangBryan Eichhorn
Feb 6, 2020·Angewandte Chemie·Martin PieschManfred Scheer
May 29, 2020·Angewandte Chemie·Helena BrakeManfred Scheer
Oct 8, 2020·Chemical Communications : Chem Comm·Fabian SpitzerManfred Scheer
Oct 1, 2020·Chemistry : a European Journal·Christoph RiesingerManfred Scheer
Mar 30, 2021·Inorganic Chemistry·Maria HaimerlManfred Scheer
Jun 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Veronika HeinlManfred Scheer
May 18, 2021·The Journal of Physical Chemistry. a·Sviatoslav BaranetsSvilen Bobev
Mar 23, 2019·Chemical Reviews·Michael SeidlManfred Scheer
Dec 18, 2021·Chemical Communications : Chem Comm·Xiaofei SunPeter W Roesky

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