Conformational Switching through the One‐Electron Reduction of an Acridinium‐based, γ‐Cationic Phosphine Gold Complex
Wei‐Chun Liu, Young‐Min Kim, François P. Gabbaı̈
Abstract
Abstract Our efforts in the chemistry of gold complexes featuring ambiphilic phosphine‐carbenium L/Z‐type ligand have led us to consider the reduction of the carbenium moiety as a means to modulate the gold–carbenium interaction present in these complexes. Here, it was shown that the one‐electron reduction of [( o ‐Ph 2 P(C 6 H 4 )Acr)AuCl] + (Acr=9‐ N ‐methylacridinium) produces a neutral stable radical, the structure of which showed a marked increase in the Au–Acr distance. Related structural changes were observed for the phosphine oxide analogue [( o ‐Ph 2 P(O)(C 6 H 4 )Acr] + , the reduction of which interfered with the P=O→carbenium interaction. These structural effects, driven by a reduction‐induced change in the electronic and electrostatic characteristics of the compounds, showed that the charge and accepting properties of the carbenium unit can be modulated. These results highlight the redox‐noninnocence of carbenium Z‐type ligand, a feature that can be exploited to induce specific conformational changes.