The 2‐Arsaethynolate Anion: Synthesis and Reactivity Towards Heteroallenes

Abstract

The synthesis and isolation of the 2‐arsaethynolate anion, AsCO−, and its subsequent reactivity towards heteroallenes is reported. Reactions with ketenes and carbodiimides afford four‐membered anionic heterocycles in formal [2+2] cycloaddition reactions. By contrast, reaction with an isocyanate yielded a 1,4,2‐diazaarsolidine‐3,5‐dionide anion and the unprecedented cluster anions As10 2− and As12 4−. These preliminary reactivity studies hint at the enormous potential synthetic utility of this novel anion, which may be employed as an arsenide (As−) source.

Triple Bonds Between Iron and Heavier Group 15 Elements in AFe(CO)3− (A=As, Sb, Bi) Complexes

“…In each spectrum, the most intense peak is due to the 17-electron Fe(CO) 4 À . [21] As shown in Figure 1, carbonyl complexes with the chemical formula of AFe(CO) 3 À (A = As,Sb, Bi)are observed to be the most intense heteronuclear carbonyl complexes in the mass spectra. Previously,only the AsCO À anion was experimentally reported, with the analogous SbCO À and BiCO À anions predicted to be stable.…”

Synthese und Reaktivität von Nickel‐stabilisierten μ2:η2,η2‐P2‐, As2‐ und PAs‐Einheiten

“…[21] Der [P(IMes)] À -Ligand ist nahezu äquidistant zu beiden Nickelatomen (2.269 (1) (4b)). (7), Ni1-As1 2.3405 (13),N i1-As1' 2.3450 (16), C1-O1 1.127 (12), As1-As1 ' 2.3006(18),N i1···Ni1' 3.055 (2);C1-Ni1-C2 107.3(4), C1-Ni1-As1 95.9(3), C1-Ni1-As1' 154.5(3), C2-Ni1-As1 154.5(2), C2-Ni1-As1' 97.1(2), As1-Ni1-As1' 58.81 (5). Die As-As-Bindung (2.301 (2) ) ist um 0.225 länger als die P-P-Bindung in 1a,was mit dem erhçhten Kovalenzradius von Arsen einhergeht (r As Àr P = 0.12 ).…”

“…[4] Allerdings wurde erst im Jahr 2014 eine verlässliche und skalierbare Synthese dieses Anions verçffentlicht. [12] Der zuletzt beschriebene Reaktionsmodus ist der interessanteste fürPnCO À (Pn = P, As) und bildet zugleich den Schwerpunkt dieser Arbeit. [11] Das erst seit kurzem synthetisch zugängliche Arsen-Analogon AsCO À verliert ebenfalls bereitwillig Kohlenstoffmonoxid.…”

A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions

“…[2b, 4-6] Related anions in which the nitrogen atom is replaced by ah eavier pnictogen element are also relatively rare.T he lithium salt of the 2-phosphaethynolate anion (PCO À )was first reported by Becker and co-workers in 1992, [7] however due to difficulties associated with its manipulation, its chemistry remained dormant for decades. [9][10][11] Theh eavier arsenic-containing ion, AsCO À ,w as first isolated in 2016 by our research group, [12] and promises to be as imilarly versatile reagent in chemical synthesis,h aving already been employed for the synthesis of several novel molecules. [8] Over the course of the last four years it has received significant attention as av iable precursor to rare (often unprecedented) phosphorus-containing compounds.…”