Comparison of nucleophilic- and radical-based routes to the formation of manganese-main group element single bonds

摘要: Using the stable metalloradical Mn(CO)3(CNArDipp2)2, we report formation of manganese-main group complexes via single-electron functionalization main halides. The reactions occur in a simple 1 : 1 stoichiometry, and demonstrate utility using open-shelled organometallics as precursors for metal-main compounds. This has enabled preparation manganese bearing terminal –EXn substituents, shown through isolation Mn(SnCl)(CO)3(CNArDipp2)2 Mn(BiCl2)(CO)3(CNArDipp2)2 from SnCl2 BiCl3, respectively. Through this approach, have also isolated Mn(SbF2)(CO)3(CNArDipp2)2 SbF3, which serves unique example –SbF2 complex. Although binary halides provides desired adduct yields comparable to nucleophilic activation manganate Na[Mn(CO)3(CNArDipp2)2], former approach is be far more atom-economical with respect Mn. Additionally, found that Mn(CO)3(CNArDipp2)2 convenient precursor MnF(CO)3(CNArDipp2). latter an analogue elusive monofluoride FMn(CO)5.