The study of radical cations of Me3С–SiMe3 and Me3С–GeMe3 in alkane solutions using the method of time-resolved magnetic field effect and DFT calculations.

Radical cations of Me3СSiMe3 and Me3СGeMe3 were detected in hexane solution using the method of time-resolved magnetic field effect. The structures and electronic distributions of neutral molecules Me3CEMe3 and their radical cations: Me3СEMe3·+ (E = C, Si, Ge, Sn) were investigated by DFT PBE/TZ2P calculations. The calculated and the experimental hyperfine coupling constants a(H) are in good agreement. The structures of Me3СSiMe3·+, Me3СGeMe3+·, and Me3СSnMe3+· are in essence a tight radical cation pairs of the type CMe3·/EMe3+. [Copyright &y& Elsevier]