A theoretical study on the formation of EX4+ and E2X5+ (E = P, As; X = Br, I) from Ag+ and EX3/X2†
Abstract
The mechanism and the thermodynamics of the formation of EX2+, EX4+ and E2X5+
(E = As, P; X = Br, I) was carefully analyzed with MP2/TZVPP calculations and inclusion of entropy and solvation effects (COSMO model approximating CH2Cl2). Thus, as likely intermediates the complexes of Ag+ and one or two EX3 as well as EX3/X2 were optimized. The global minimum isomers of the Ag(EX3)2+ intermediates were found to be P-coordinated Ag(PI3)2+ and (BrPBr2)Ag(PBr3)+ but exclusively