A Cationic Barium Hydride Complex Supported by an NNNN‐Type Macrocycle

Zeitschrift für anorganische und allgemeine Chemie, vol. 649

Abstract

Abstract The dibenzyl complex of barium [(Me4TACD)Ba(CH2Ph)2] was prepared by reacting [Ba(CH2Ph)2] with NNNN‐type macrocycle Me4TACD (Me4TACD=1,4,7,10‐tetramethyltetraazacyclododecane) and isolated as yellow crystals. Single crystal X‐ray diffraction revealed η2‐ and η3‐coordination of the benzyl groups. The benzylbarium cation in [(Me4TACD)Ba(CH2Ph)(thf)][B(C6H3‐3,5‐Me2)4] was obtained upon protonolysis of the neutral bariumdibenzyl with the weak Brønsted acid [NEt3H][B(C6H3‐3,5‐Me2)4] and isolated as colorless crystals. When the benzylbarium cation was reacted with H2 (1 bar) in THF at room temperature, colorless crystals of the dinuclear hydride complex [(Me4TACD)2Ba2(μ‐H)2(thf)4][B(C6H3‐3,5‐Me2)4]2 precipitated from the reaction mixture and characterized by single crystal X‐ray diffraction. The structural motif [Ba2(μ‐H)2]2+ was compared with that published in the literature. Hydrogenolysis of the dibenzyl [(Me4TACD)Ca(CH2Ph)2] under the same conditions resulted in decomposition.

Authors 4

1. Thomas Höllerhage Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52056 Aachen Germany

   Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany

2. Thomas P. Spaniol Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52056 Aachen Germany

   Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany

3. Ulli Englert corresponding Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52056 Aachen Germany

   Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany

4. Jun Okuda corresponding Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52056 Aachen Germany

   Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany