The isolation of the first diarsene radical anion by reduction of a neutral diarsene is presented. Comprehensive characterisation in conjunction with DFT calculations reveals unpaired spin density residing in the antibonding π*-orbital with involvement of the terphenyl ligands. First reactivity studies reveal no pronounced radical, but rather reducing properties.
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From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications.
Chemistry
May 2024
Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, 45141, Essen, Germany.
Diarsene [L(MeO)GaAs] (L=HC[C(Me)N(Ar)], Ar=2,6-PrCH, 4) reacts with MeOTf and NHC (NHC=1,3,4,5-tetra-methylimidazol-2-ylidene) to the diarsene [L(TfO)GaAs] (5) and the carbene-coordinated diarsene [L(MeO)GaAsAs(NHC)Ga(OMe)L] (6). The NHC-coordination results in an inversion of the redox properties of the diarsene 4, which shows only a reversible reduction event at E=-2.06 V vs Fc, whereas the carbene-coordinated diarsene 6 shows a reversible oxidation event at E=-1.
View Article and Find Full Text PDFA diarsene radical anion.
Chem Commun (Camb)
August 2022
Chemistry Department, Philipps-University, Hans-Meerwein-Str. 4, 35043 Marburg, Germany.
The isolation of the first diarsene radical anion by reduction of a neutral diarsene is presented. Comprehensive characterisation in conjunction with DFT calculations reveals unpaired spin density residing in the antibonding π*-orbital with involvement of the terphenyl ligands. First reactivity studies reveal no pronounced radical, but rather reducing properties.
View Article and Find Full Text PDFOxidation of carbene-stabilized diarsenic: diarsene dications and diarsenic radical cations.
J Am Chem Soc
February 2013
Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, Georgia 30602-2556, USA.
Oxidation of carbene-stabilized diarsenic, L:As-As:L [L: = :C{N(2,6-(i)Pr(2)C(6)H(3))CH}(2)] (1), with gallium chloride in a 1:4 ratio in toluene affords the dicationic diarsene complex [L:As═As:L](2+)([GaCl(4)](-))(2) (2(2+)[GaCl(4)](2)), while oxidation of 1 with GaCl(3) in a 1:2 ratio in Et(2)O yields the monocationic diarsenic radical complex [L:AsAs:L](•+)[GaCl(4)](-) (2(•+)[GaCl(4)]). Strikingly, complex 2(•+) is the first arsenic radical to be structurally characterized in the solid state. The nature of the bonding in these complexes was probed computationally and spectroscopically.
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