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Cesium and Tetrabutylammonium Salt of the Ethynyl‐ closo ‐dodecaborate Dianion
Author(s) -
Himmelspach Alexander,
Finze Maik,
Vöge Andrea,
Gabel Detlef
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100458
Subject(s) - chemistry , salt (chemistry) , boron , caesium , crystallography , crystal structure , single crystal , nuclear magnetic resonance spectroscopy , cluster (spacecraft) , medicinal chemistry , stereochemistry , inorganic chemistry , organic chemistry , computer science , programming language
Abstract Salts of the ethynyl‐ closo ‐dodecaborate dianion [HC≡C‐ closo ‐B 12 H 11 ] 2– ( 1 ) were synthesized by a microwave‐assisted palladium‐catalyzed cross‐coupling reaction starting from the iodinated cluster [I‐ closo ‐B 12 H 11 ] 2– and Me 3 SiC≡CMgBr. The dianion was characterized in its [ n Bu 4 N] + and Cs + salt by multi‐NMR and vibrational spectroscopy as well as by (–)‐MALDI mass spectrometry. A crystal of [ n Bu 4 N] 2 [HC≡C‐ closo ‐B 12 H 11 ] was studied by X‐ray diffraction. The experimental bond properties and the spectroscopic data are compared to values derived from density functional and (RI)‐MP2 calculations. The charge distribution in the ethynyl substituents of the isoelectronic boron clusters 1 , [12‐HC≡C‐ closo ‐1‐CB 11 H 11 ] – ,and 9‐HC≡C‐ closo ‐1, 2‐CB 11 H 11 is compared. Furthermore, the crystal structure of the [ n Bu 4 N] + salt of the intermediate[Me 3 SiC≡C‐ closo ‐B 12 H 11 ] 2– ( 2 ) is described.