Samarium Polyarsenides Derived from Nanoscale Arsenic

Zintl phases of arsenic and molecular compounds containing Zintl-type polyarsenide ions are of fundamental interest in basic and applied sciences. Unfortunately, the most obvious and reactive arsenic source for the preparation of defined molecular polyarsenide compounds, yellow arsenic As4 , is very inconvenient to prepare and neither storable in pure form nor easy to handle. Herein, we present the synthesis and reactivity of elemental As0 nanoparticles (As0Nano , d=7.2±1.8 nm), which were successfully utilized as a reactive arsenic source in reductive f-element chemistry. Starting from [Cp*2 Sm] (Cp*=η5 -C5 Me5 ), the samarium polyarsenide complexes [(Cp*2 Sm)2 (μ-η2 :η2 -As2 )] and [(Cp*2 Sm)4 As8 ] were obtained from As0nano , thereby generating the largest molecular polyarsenide of the f-elements and circumventing the use of As4 in preparative chemistry.