NDLI: Alkali metal - sulfur dioxide complexes stabilized by halogenated closo-dodecaborate anions

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Alkali metal - sulfur dioxide complexes stabilized by halogenated closo-dodecaborate anions

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Alkali metal - sulfur dioxide complexes stabilized by halogenated closo-dodecaborate anions

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Schulz, Christoph Derendorf, Janis Kessler, Mathias Rühle, Monika Knapp, Carsten
Description	Author Affiliation: Derendorf J ( Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104, Freiburg i. Br., Germany.)
Abstract	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 $_{N–H}$ 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.
ISSN	14779226
Issue Number	37
Journal	Dalton Trans.
Volume Number	39
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2010-10-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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