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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Preparation of stable AsBr4+ and I2AsPI3+ salts. Why didnt we succeed to prepare AsI4+ and As2X5+? A combined experimental and theoretical study
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Preparation of stable AsBr4+ and I2AsPI3+ salts. Why didnt we succeed to prepare AsI4+ and As2X5+? A combined experimental and theoretical study

机译：制备稳定的AsBr4 +和I2AsPI3 +盐。为什么我们没有成功准备AsI4 +和As2X5 +？实验与理论相结合的研究

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In analogy to our successful "PX2+" insertion reactions, an "AsX2+" insertion route was explored to obtain new arsenic halogen cations. Two new salts were prepared: AsBr4(+)[Al(OR)(4)](-), starting from AsBr3, Br-2 and Ag [Al(OR)(4)], and I2As-PI3+[Al(OR)](4) from AsI3, PI3 and Ag[Al(OR)(4)] (R = C(CF3)(3)). The first cation is formally a product of an "AsBr2+" insertion into the Br-2 molecule and the latter clearly a "PI2+" insertion into the As-I bond of the AsI3 molecule. Both compounds were characterized by IR and NMR spectroscopy, the first also by its X-ray structure. Reactions of Ag[Al(OR)(4)] with AsI3 do not lead to ionization and AgI formation but rather lead to a marginally stable Ag(AsI3)(2)(+) [Al(OR)](4) salt. Despite many attempts we failed to prepare other PX-cation analogues such as AsI4+, As2X5+ and P4AsX2+ (X = Br, I). To explain these negative results the thermodynamics of the formation of EX2+, EX4+ and E2X5+ (E = As, P; X = Br, I) was carefully analyzed with MP2/TZVPP calculations and inclusion of entropy and solvation effects. We show that As2Br5+ is in very rapid equilibrium with AsBr2+ and AsBr3 (Delta G degrees((CH2Cl2)) = +30 kJ mol(-1)). The extremely reactive AsBr2+ cation available in the equilibrium accounts for the observed decomposition of the [Al(OR)(4)](-) anion. By contrast, the stability of AsI3 against Ag[Al(OR)(4)] appears to be kinetic and, if prepared by a suitable route, As2I5+ would be expected to have a stability intermediate between the known P2I5+ and P2Br5+.
机译：与我们成功的“ PX2 +”插入反应相似，我们探索了“ AsX2 +”插入途径来获得新的砷卤阳离子。制备了两种新的盐：AsBr4（+）[Al（OR）（4）]（-），从AsBr3，Br-2和Ag [Al（OR）（4）]和I2As-PI3 + [Al（OR）开始）]（4）来自AsI3，PI3和Ag [Al（OR）（4）]（R = C（CF3）（3））。第一个阳离子形式上是在Br-2分子中插入“ AsBr2 +”的产物，而后者显然是在AsI3分子中插入As-1键的“ P​​I2 +”。两种化合物都通过IR和NMR光谱表征，第一个也是通过X射线结构表征。 Ag [Al（OR）（4）]与AsI3的反应不会导致电离和AgI的形成，而是会导致边缘稳定的Ag（AsI3）（2）（+）[Al（OR）]（4）盐。尽管进行了许多尝试，我们仍未能制备其他PX阳离子类似物，例如AsI4 +，As2X5 +和P4AsX2 +（X = Br，I）。为了解释这些负面结果，使用MP2 / TZVPP计算仔细分析了EX2 +，EX4 +和E2X5 +（E = As，P; X = Br，I）形成的热力学，并包含了熵和溶剂化作用。我们显示As2Br5 +与AsBr2 +和AsBr3处于非常快速的平衡状态（ΔG度（（CH2Cl2））= +30 kJ mol（-1））。平衡中可用的极活泼的AsBr2 +阳离子说明了观察到的[Al（OR）（4）]（-）阴离子的分解。相比之下，AsI3对Ag [Al（OR）（4）]的稳定性似乎是动力学的，如果通过合适的方法制备，则As2I5 +的稳定性可望介于已知P2I5 +和P2Br5 +之间。

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