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A Cationic Barium Hydride Complex Supported by an NNNN‐Type Macrocycle
Author(s) -
Höllerhage Thomas,
Spaniol Thomas P.,
Englert Ulli,
Okuda Jun
Publication year - 2023
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.202200315
Subject(s) - protonolysis , hydride , chemistry , cationic polymerization , hydrogenolysis , crystallography , crystal structure , barium , decomposition , medicinal chemistry , stereochemistry , inorganic chemistry , hydrogen , polymer chemistry , catalysis , organic chemistry
The dibenzyl complex of barium [(Me 4 TACD)Ba(CH 2 Ph) 2 ] was prepared by reacting [Ba(CH 2 Ph) 2 ] with NNNN‐type macrocycle Me 4 TACD (Me 4 TACD=1,4,7,10‐tetramethyltetraazacyclododecane) and isolated as yellow crystals. Single crystal X‐ray diffraction revealed η 2 ‐ and η 3 ‐coordination of the benzyl groups. The benzylbarium cation in [(Me 4 TACD)Ba(CH 2 Ph)(thf)][B(C 6 H 3 ‐3,5‐Me 2 ) 4 ] was obtained upon protonolysis of the neutral bariumdibenzyl with the weak Brønsted acid [NEt 3 H][B(C 6 H 3 ‐3,5‐Me 2 ) 4 ] and isolated as colorless crystals. When the benzylbarium cation was reacted with H 2 (1 bar) in THF at room temperature, colorless crystals of the dinuclear hydride complex [(Me 4 TACD) 2 Ba 2 (μ‐H) 2 (thf) 4 ][B(C 6 H 3 ‐3,5‐Me 2 ) 4 ] 2 precipitated from the reaction mixture and characterized by single crystal X‐ray diffraction. The structural motif [Ba 2 (μ‐H) 2 ] 2+ was compared with that published in the literature. Hydrogenolysis of the dibenzyl [(Me 4 TACD)Ca(CH 2 Ph) 2 ] under the same conditions resulted in decomposition.