[NO][HCB11Cl11] - Synthesis, Characterization, Crystal Structure, and Reaction with P4
[NO][HCB11Cl11] - Synthesis, Characterization, Crystal Structure, and Reaction with P4
复制标题
DOI：
10.1002/zaac.201100448
复制
发表时间：
2012-03-01
影响因子：
1.4
通讯作者：
Knapp, Carsten
中科院分区：
文献类型：
--
作者：
Bolli, Christoph;Koechner, Tobias;Knapp, Carsten
阳离子单电子氧化剂 [NO]+ 和 [O2]+ 的 [HCB11Cl11] 盐的热力学稳定性通过基于量子化学计算和晶格焓估计的 BornHaberFajans 循环进行估计。 [NO][HCB11Cl11] 预计是一种稳定的化合物，而 [O2][HCB11Cl11] 应分解为 O2 和 HCB11Cl11（中心点）自由基。因此，Na[HCB11Cl11]和[NO][BF4]在液体二氧化硫中通过复分解反应可以制备[NO][HCB11Cl11]，而合成[O2][HCB11Cl11]的尝试失败了。 [NO][HCB11Cl11] 已通过 NMR 和振动光谱进行了充分表征。从液体二氧化硫溶液中获得[NO][HCB11Cl11]中心点SO2的单晶。晶体结构测定揭示了几个分子间阳离子阴离子接触，这些接触明显短于各个原子的范德华半径之和。 [NO][HCB11Cl11]与白磷在CH2Cl2溶液中反应，得到含有[P4NO]+阳离子的黄橙色[P4NO][HCB11Cl11]。原位核磁共振波谱研究表明反应混合物中存在同多原子磷阳离子 [P9]+。
The thermodynamic stability of the [HCB11Cl11] salts of the cationic one-electron oxidizers [NO]+ and [O2]+ was estimated by BornHaberFajans cycles based on quantum-chemical calculations and lattice enthalpy estimations. [NO][HCB11Cl11] is predicted to be a stable compound, whereas [O2][HCB11Cl11] should decompose into O2 and the HCB11Cl11(center dot) radical. Consequently, [NO][HCB11Cl11] can be prepared by metathesis reaction from Na[HCB11Cl11] and [NO][BF4] in liquid sulfur dioxide, while attempts to synthesize [O2][HCB11Cl11] failed. [NO][HCB11Cl11] has been fully characterized by NMR and vibrational spectroscopy. Single crystals of [NO][HCB11Cl11]center dot SO2 were obtained from liquid sulfur dioxide solution. The crystal structure determination revealed several intermolecular cationanion contacts, which are significantly shorter than the sum of the van der Waals radii of the respective atoms. [NO][HCB11Cl11] reacts with white phosphorus in CH2Cl2 solution to give yellow-orange [P4NO][HCB11Cl11] containing the [P4NO]+ cation. An in-situ NMR spectroscopic study indicates the presence of the homopolyatomic phosphorus cation [P9]+ in the reaction mixture.