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 (As⁰_Nano, d=7.2±1.8 nm), which were successfully utilized as a reactive arsenic source in reductive f‐element chemistry. Starting from [Cp*₂Sm] (Cp*=η⁵‐C₅Me₅), the samarium polyarsenide complexes [(Cp*₂Sm)₂(μ‐η²:η²‐As₂)] and [(Cp*₂Sm)₄As₈] were obtained from As⁰_nano, thereby generating the largest molecular polyarsenide of the f‐elements and circumventing the use of As₄ in preparative chemistry.     

Samarium Polystibides Derived from Highly Activated Nanoscale Antimony

Zintl ions in molecular compounds are of fundamental interest for basic research and application. Two reactive antimony sources are presented that allow direct access to molecular polystibide compounds. These are Sb amalgam (Sb/Hg) and ultrasmall Sb⁰ nanoparticles (d=6.6±0.8 nm), which were used independently as precursors for the synthesis of the largest f‐element polystibide, [(Cp*₂Sm)₄Sb₈]. Whereas the reaction of the nanoparticles with [Cp*₂Sm] directly led to [(Cp*₂Sm)₄Sb₈], Sm/Sb/Hg intermediates were isolated when using Sb/Hg as the precursor. These Sm/Sb/Hg intermediates [{(Cp*₂Sm)₂Sb}₂(μ‐Hg)] and [{(Cp*₂Sm)₃(μ⁴,η^1:2:2:2‐Sb₄)}₂Hg] were synthetically trapped and structurally characterized, giving insight in the formation mechanism of polystibide compounds.