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Slinger, Brady_L; Zhu, Jiaqi; Widenhoefer, Ross_A (, ChemPlusChem)Abstract Reaction of (P)AuOTf [P=P(t‐Bu)2o‐biphenyl] with indenyl‐ or 3‐methylindenyl lithium led to isolation of gold η1‐indenyl complexes (P)Au(η1‐inden‐1‐yl) (1 a) and (P)Au(η1‐3‐methylinden‐1‐yl) (1 b), respectively, in >65 % yield. Whereas complex1 bis static, complex1 aundergoes facile, degenerate 1,3‐migration of gold about the indenyl ligand (ΔG≠153K=9.1±1.1 kcal/mol). Treatment of complexes1 aand1 bwith (P)AuNTf2led to formation of the corresponding cationic bis(gold) indenyl complexestrans‐[(P)Au]2(η1,η1‐inden‐1,3‐yl) (2 a) andtrans‐[(P)Au]2(η1,η2‐3‐methylinden‐1‐yl) (2 b), respectively, which were characterized spectroscopically and modeled computationally. Despite the absence of aurophilic stabilization in complexes2 aand2 b, the binding affinity of mono(gold) complex1 atoward exogenous (P)Au+exceed that of free indene by ~350‐fold and similarly the binding affinity of1 btoward exogenous (P)Au+exceed that of 3‐methylindene by ~50‐fold. The energy barrier for protodeauration of bis(gold) indenyl complex2 awith HOAc was ≥8 kcal/mol higher than for protodeauration of mono(gold) complex1 a.more » « less
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