agents and σ donors towards a variety of hard acceptors. The reactivity of the parent cyclo-tetra(stibinophosphonium) tetracation, [10(Me)]4+, is directed by high charge concentration and strong polarization of the P–Sb bonds. The former explains the observed facility for reductive elimination to yield elemental antimony and the latter enabled activation of P–Cl and P–H bonds to give phosphinophosphonium
从 [ (R 3 P ) 3 Sb] 3+、 [ 8(R) ] 3+中的高亲电子 Sb III中心还原消除[R 3 PPR 3 ] 2+、 [ 11(R) ] 2+、得到含有阳离子 [(R 3 P)Sb] 1+ , [ 9(R) ] 1+的Sb I,其组装成被识别为环四(stibinophonium)四阳离子的框架,[(R 3 P) 4 Sb 4 ] 4 + , [ 10(R) ] 4+。提出了一种膦催化机制将
氟锑配合物 [(R 3 P) 2 SbF] 2+、[ 7(R) ] 2+转化为 [ 10(R) ] 4+,并介绍了关键中间体的表征。这些结果证明了硬缺电子受体配位层中膦的新型
配体激活途径。相关反应物和产物的表征支持了早期(尽管不太明确)对 Cu III和 Tl III配合物中类似
膦配体活化的检测,证明这些原型
配体可以同时充当还原剂和针对各种硬受体的 σ 供体。母体环四(
锑基
鏻)四阳离子