Oxidative Rearrangement in Gold Organometallics

The one-electron oxidizing agent [NO]­PF6 was
reacted
with Bu4N­[Au­(C6X5)2] (X
= F, Cl) complexes in CH3CN. The gold­(III) complexes [Au­(C6F5)3(CH3CN)] and cis-[Au­(C6Cl5)2(CH3CN)2]­PF6 were synthesized by the oxidation
of gold­(I) to gold­(III) with the concomitant ligand rearrangement
“oxidative rearrangement”. The supramolecular crystal
packing in the perfluorinated aryl gold­(III) complex is dictated by
the notably short C­(sp2)–F···H­(CH3CN) bond distance. The [Au­(C6Cl5)2(CH3CN)2]­PF6 complex exhibits
antisymbiosis, displaying equal ligands in the cis position. The electrochemical
oxidation of Bu4N­[Au­(C6X5)2] (X = F, Cl) complexes in CH3CN showed two irreversible
peaks at 0.71 and 1.21 V (X = F) and at 0.65 and 0.91 V (X = Cl) vs
Ag/AgCl.

单电子氧化剂（one-electron oxidizing agent）六氟磷酸亚硝鎓（[NO]PF₆）在乙腈（CH₃CN）中与四丁基铵（Bu₄N）[Au(C₆X₅)₂]（X = F、Cl）配合物发生反应。通过将金(I)氧化为金(III)并伴随配体重排的“氧化重排（oxidative rearrangement）”过程，合成了金(III)配合物[Au(C₆F₅)₃(CH₃CN)]与顺式-[Au(C₆Cl₅)₂(CH₃CN)₂]PF₆。全氟芳基金(III)配合物的超分子晶体堆积由显著较短的C(sp²)–F···H(CH₃CN)键距所决定。[Au(C₆Cl₅)₂(CH₃CN)₂]PF₆配合物表现出反共生效应（antisymbiosis），其顺式配位位置的配体完全等价。在乙腈中对Bu₄N[Au(C₆X₅)₂]（X = F、Cl）配合物进行电化学氧化时，相对于Ag/AgCl参比电极，当X=F时在0.71 V和1.21 V处出现两个不可逆峰，当X=Cl时则在0.65 V和0.91 V处出现两个不可逆峰。