1579998-08-5Relevant academic research and scientific papers
Low-coordinate bismuth cations
Schwamm, Ryan J.,Day, Benjamin M.,Coles, Martyn P.,Fitchett, Christopher M.
, p. 3778 - 3787 (2014)
Chloride abstraction from the diamido-bismuth compound Bi(Me 2Si{NAr}2)Cl (1, Ar = 2,6-i-Pr2C 6H3) using MCl3 (M = Al, Ga) is a facile route to cationic species. Stoichiometric reactions afford the tetrachlorometallate salts [Bi(Me2Si{NAr}2)][MCl4] (2a, M = Al; 3a, M = Ga), whereas reaction with 0.5 equiv of the group 13 reagent gives the μ-chlorido bridged cations [{Bi(Me2Si{NAr}2)} 2(μ-Cl)][MCl4] (2b, M = Al; 3b, M = Ga). The crystal structure of 2a shows a formally two-coordinate bismuth cation, with a Bi...Cl contact to the [AlCl4]- anion, whereas the structure of 3b shows a total of three Bi...Cl contacts to [GaCl 4]-. Both species associate as {1:1}2 dimers in the solid state through additional Bi...Cl interactions. Attempted preparation of cationic complexes using either NaBR4 (R = Ph, Et) or [HNEt3][BPh4] were unsuccessful. Instead of forming the borate salts, the neutral compounds Bi(Me2Si{NAr}2)R (4, R = Et; 5, R = Ph) were isolated as a result of aryl/alkyl transfer from boron to bismuth.
