The Chemistry of Yellow Arsenic

Abstract

The generation and handling of the light-sensitive and metastable yellow arsenic (As4) is extremely challenging. In view of recent breakthroughs in synthesizing As4 storage materials and transfer reagents, the more intensive use of yellow arsenic as a source for further reactions can be expected. Given these aspects, the current stage of knowledge of the direct use of As4 is comprehensively summarized in the present review, which lists the activation of As4 by main group elements as well as transition metal compounds (including the f-block elements). Moreover, it also partly compares the reaction outcomes in relation to the corresponding reactions of P4. The possibility of using alternative sources for generating arsenic moieties and compounds is also discussed. The release of As4 molecules from precursor compounds and the use of transfer reagents for polyarsenic entities open up new synthetic pathways to avoid the direct generation of yellow arsenic solutions and to ensure its smooth usage for subsequent reactions.

Recent Advances in Rare‐Earth Polypnictides

“…On the other hand, yellow arsenic has also been found to be an effective precursor for the preparation of polyarsenides . For example, the inverse sandwich complex {(DippForm) 2 Sm} 2 (μ 2 ‐ŋ 4 :ŋ 4 ‐As 4 ), featuring a 6π‐aromatic cyclo ‐As 4 2– dianion can be obtained from the reaction of (DippForm) 2 Sm(THF) 2 and As 4 (Figure C).…”

Coordination Behavior of [Cp″2Zr(µ1:1-As4)] towards Lewis Acids

“…The interest in the activation of small molecules, such as H 2 , N 2 , NH 3 , etc., has increased notably in recent years [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 ]. A special focus lies on the activation of cage compounds such as white phosphorus and yellow arsenic by transition metals and main group compounds [ 9 , 10 , 11 , 12 ]. While the synthesis and isolation of polyphosphorus complexes have been intensively investigated [ 9 , 10 , 11 ], polyarsenic complexes are much less known, and hence the number of comparable polyarsenic complexes is quite limited [ 12 ].…”

“…A special focus lies on the activation of cage compounds such as white phosphorus and yellow arsenic by transition metals and main group compounds [ 9 , 10 , 11 , 12 ]. While the synthesis and isolation of polyphosphorus complexes have been intensively investigated [ 9 , 10 , 11 ], polyarsenic complexes are much less known, and hence the number of comparable polyarsenic complexes is quite limited [ 12 ]. This can be attributed to the very challenging handling of As 4 due to its pronounced air- and light-sensitivity, time-consuming preparation, and to the lack of knowledge regarding its toxicitiy.…”

Zugang zu (tBuCP)n‐Gerüsten (n=2, 4) durch P‐C‐Bindungsspaltung von Di‐tert‐butyldiphosphatetrahedran

“…[3] Das schwerere Homologe As 4 und die gemischte Interpniktogenverbindung AsP 3 sind ebenfalls synthetisch zugänglich. [4] Entsprechend der Schrägbeziehung von Kohlenstoff und Phosphor sind auch rein kohlenstoffbasierte Tetrahedrane wohlbekannt. [5] Tatsächlich war die Synthese von (tBuC) 4 im Jahr 1978 ein Meilenstein in der organischen Synthesechemie.…”

“…[4] Entsprechend der Schrägbeziehung von Kohlenstoff und Phosphor sind auch rein kohlenstoffbasierte Tetrahedrane wohlbekannt. [5] Tatsächlich war die Synthese von (tBuC) 4 im Jahr 1978 ein Meilenstein in der organischen Synthesechemie. [5] Im Gegensatz dazu wurden die ersten gemischten C/P-Tetrahedrane erst letztes Jahr beschrieben.…”