Alkali metal-sulfur dioxide complexes stabilized by halogenated closo-dodecaborate anions.
Alkali metal-sulfur dioxide complexes stabilized by halogenated closo-dodecaborate anions.
复制标题
由卤代近十二硼酸根阴离子稳定的碱金属-二氧化硫络合物。
作者：
Janis Derendorf;Mathias Kessler;C. Knapp;Monika Rühle;Christopher Schulz
用[NEt(3)H](2)[B(12)Cl(12)]与相应的碱金属氢氧化物反应制备了高氯化近十二硼酸盐[B(12)Cl(12)]（2-）的碱金属盐（M = Li, Na， K, Rb, Cs）。从液态二氧化硫中结晶M(2)[B(12)Cl(12)]得到了二氧化硫配合物[Li(2)(SO(2))(8)][B(12)Cl(12)], Na(2)[B(12)Cl(12)]。4 (2), K (2) (B) (12) Cl(12))。8 (2), Rb (2) (B) (12) Cl(12))。4SO(2)和Cs(2)[B(12)Cl(12)]。用x射线单晶衍射对其进行了表征。本文首次报道了碱金属阳离子K（+）和Rb（+）的SO(2)配合物的结构表征。(李的结构(2)((2))(8)][B (12) Cl(12)]包含离散(李(2)((2))(8)](2 +)双阳离子和(B) (12) Cl(12))(2 -)二阶阴离子。基于量子化学计算和固体晶格焓估计的玻恩-哈伯循环解释了固体中离散态[Li(2)(SO(2))(8)]（2+）的稳定性。较重的碱金属形成三维网络，包含金属-阴离子和金属-二氧化硫的接触。Na(2)[B(12)Br(12)]的晶体结构。8SO(2)和Na(2)[B(12)I(12)]。测定8SO(2)，考察卤素取代基对阴离子的影响。它们含有相似的三维网络结构。Na (2) (B) (12) Br(12))。8SO(2)与K(2)[B(12)Cl(12)].8SO(2)是同构的。此外，还研究了配合物Na(2)[B(12)I(12)].8 so (2).H(2)O和Na(2)[B(12)H(12)].6 so(2)的晶体结构。也报道了含有水配体的2H(2)O。根据相应[Oct(3)NH](2)[B(12)X(12)] （X = F, Cl, Br， I）盐的[小nu，希腊，波浪]（N-H）伸展频率比较卤化十二硼酸盐[B(12)X(12)]（X = F - I）盐的（N-H）伸展频率表明，氟化阴离子[B(12)F(12)]（2-）是该系列中碱性最低的阴离子，而碘化阴离子[B(12)I(12)]（2-）是最碱性的阴离子。这些结果与相应系列的高卤化碳硼烷的结果一致，并可以用卤素取代基的极化性来解释。
The alkali metal salts (M = Li, Na, K, Rb, Cs) of the perchlorinated closo-dodecaborate [B(12)Cl(12)](2-) were prepared by reaction of [NEt(3)H](2)[B(12)Cl(12)] with the corresponding alkali metal hydroxide. Crystallization of M(2)[B(12)Cl(12)] from liquid sulfur dioxide gave the sulfur dioxide complexes [Li(2)(SO(2))(8)][B(12)Cl(12)], Na(2)[B(12)Cl(12)].4SO(2), K(2)[B(12)Cl(12)].8SO(2), Rb(2)[B(12)Cl(12)].4SO(2), and Cs(2)[B(12)Cl(12)].SO(2), which were characterized by single crystal X-ray diffraction. In this work structurally characterized SO(2) complexes of the alkali metal cations K(+) and Rb(+) are reported for the first time. The structure of [Li(2)(SO(2))(8)][B(12)Cl(12)] contains discrete [Li(2)(SO(2))(8)](2+) dications and [B(12)Cl(12)](2-) dianions. Born-Haber cycles based on quantum chemical calculations and estimations of lattice enthalpies for the solid state explain the stability of the discrete dication [Li(2)(SO(2))(8)](2+) in the solid state. Heavier alkali metals form three-dimensional networks containing metal-anion and metal-sulfur dioxide contacts. The crystal structures of Na(2)[B(12)Br(12)].8SO(2) and Na(2)[B(12)I(12)].8SO(2) were determined to investigate the influence of the halogen substituent on the anion. They contain similar three-dimensional network structures. Na(2)[B(12)Br(12)].8SO(2) is isostructural to K(2)[B(12)Cl(12)].8SO(2). In addition the crystal structures of the complexes Na(2)[B(12)I(12)].8SO(2).H(2)O and Na(2)[B(12)H(12)].6SO(2).2H(2)O, which contain water ligands, are reported as well. A comparison of halogenated dodecaborates [B(12)X(12)](2-) (X = F, Cl, Br, I) based on [small nu, Greek, tilde](N-H) stretching frequencies of the corresponding [Oct(3)NH](2)[B(12)X(12)] (X = F - I) salts shows that the fluorinated anion [B(12)F(12)](2-) is the least basic and the iodinated anion [B(12)I(12)](2-) is the most basic anion in this series. These findings are in agreement with those for the corresponding series of perhalogenated carboranes and are explained by the polarizability of the halogen substituent.
影响因子：
16.6
作者：
Avelar, Amy;Tham, Fook S.;Reed, Christopher A.
通讯作者：
Reed, Christopher A.
影响因子：
15
作者：
Stoyanov, Evgenii S.;Kim, Kee-Chan;Reed, Christopher A.
通讯作者：
Reed, Christopher A.