Hinz Alexander, Rothe Julia, Schulz Axel, Villinger Alexander
Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany.
Dalton Trans. 2016 Apr 14;45(14):6044-52. doi: 10.1039/c5dt02711j. Epub 2015 Aug 24.
A reaction of antimonytrichloride SbCl3 with potassium bis(terphenylimino)phosphide K[(TerN)2P] smoothly afforded a novel class of mixed diazadipnictanes, namely dichloro(diaza-phospha)stibane [Ter2N2P((III))Sb((III))Cl2], which is considered to exist as open chain-like and cyclic isomers in an equilibrium. [Ter2N2PSbCl2] is a versatile starting material for reduction and halide abstraction experiments. Halide abstraction led to the formation of a cyclic diazastibaphosphenium cation P(μ-NTer)2SbCl. Upon reduction of [Ter2N2PSbCl2], the transient existence of the novel mixed biradicaloid [P(μ-NTer)2Sb] was proven by a trapping experiment with an alkyne, while reduction in the absence of trapping agents afforded the eight-membered heterocycle [Sb2-{μ-(TerN)2P}2]. This constitutional isomer of a dimerized biradicaloid features a bonding situation that indicates the presence of a donor-stabilized Sb2 ion.
三氯化锑（SbCl₃）与双（三联苯基亚氨基）磷化钾（K[(TerN)₂P]）反应顺利生成了一类新型的混合二氮二磷杂环化合物，即二氯（二氮磷）锑烷[Ter₂N₂P((III))Sb((III))Cl₂]，它被认为以开链状和环状异构体的形式处于平衡状态。[Ter₂N₂PSbCl₂]是用于还原和卤化物提取实验的通用起始原料。卤化物提取导致形成环状二氮锑磷鎓阳离子P(μ-NTer)₂SbCl。在还原[Ter₂N₂PSbCl₂]时，通过与炔烃的捕获实验证明了新型混合双自由基[P(μ-NTer)₂Sb]的短暂存在，而在没有捕获剂的情况下进行还原则得到八元杂环[Sb₂-{μ-(TerN)₂P}₂]。这种二聚双自由基的结构异构体具有一种键合情况，表明存在供体稳定的Sb₂离子。
