The reaction of the neutral diphosphanide [((Cl)Im(Dipp))P-P(Cl)(Dipp)] (6) ((Cl)Im(Dipp) = 4,5-dichloro-1,3-bis(Dipp)-imidazol-2-yl; Dipp = 2,6-di-iso-propylphenyl) with methyl triflate (MeOTf) leads to the formation of cationic diphosphane [((Cl)Im(Dipp))(Me)P-P(Cl)(Dipp)](+) (8+) in a stereoselective methylation. In contrast, reacting with the Lewis acid GaCl3 yields cationic diphosphene [((Cl)Im(Dipp))P=P(Dipp)](+) (7+), which is explained by a low P-Cl bond dissociation energy. The significantly polarized P=P double bond in 7+ allows for its utilization as an acceptor for nucleophiles - the reaction with Cl(-) regenerates diphosphanide and the reaction with PMe3 gives cation [((Cl)Im(Dipp))P-P(PMe3)(Dipp)] (9+). In depth DFT investigation provides detailed insights into the bonding situation of the reported compounds.
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