Size Matters: Synthesis of Group 13 Metal-Substituted Dipnictanes by E-C Bond Homolysis

Article abstract of DOI:10.1002/ejic.202000747

Pnictanes Cp*(Ph)ECl (E = As 1, Sb 2; Cp* = C₅Me₅) react with group 13 diyls LM (M = Al, Ga, In; L = HC[C(Me)N(Dip)]₂, Dip = 2,6-iPr₂C₆H₃) with oxidative addition of the E-Cl bond to a unique series of metalylpnictanes [L(Cl)M](Ph)ECp* (E = As, M = Al 3, Ga 4, In 5; E = Sb, M = Al 6, Ga 7, In 8). Thermal treatment of 4 and 6–8 results in homolytic E-C bond scission with Cp* radical liberation, yielding the corresponding dipnictanes {[L(Cl)M](Ph)E}₂ (E = As, M = Ga 9; E = Sb, M = Al 10, Ga 11, In 12). Compounds 1–12 were characterized by NMR (¹H, ¹³C) and IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction (3–12).