|
Z. Naturforsch. 2014,
69b, 655 – 664
doi:10.5560/ZNB.2014-4033
Strukturen von polaren Magnesiumorganylen: Synthese und Struktur von Basen-Addukten des Bis(pentamethylcyclopentadienyl)magnesiums
Institut für Anorganische und Angewandte Chemie der Universität, Martin-Luther-King-Platz 6, D-20146 Hamburg, Germany
Reprint requests to Prof. Dr. Ulrich Behrens. Fax: +49-(0)40/42838-2893. E-mail:
ubehrens@chemie.uni-hamburg.de
Received February 18, 2014 / published online June 7, 2014
The syntheses and structures of six new pentamethylcyclopentadienyl magnesium complexes are reported. The structure of the known Mg(C5Me5)2 (1) was re-determined to afford more precise distances and angles. When Mg(C5Me5)2 is crystallized from dioxane the complex co-crystallizes with dioxane not bound to magnesium (2). The magnesium complexes [Mg(C5Me5)(OCH2CH2CH2CH2C5Me5)(THF)]2 (3), [Mg(C5Me5)(OMe)(THF)]2 (4) and [Mg(C5Me5)(OOC5Me5)(TMEDA)] (5) were obtained in
low yield by reacting Mg(C5Me5)2 with tetrahydrofuran (THF), dimethoxyethane, and tetramethylethylenediamine (TMEDA)/oxygen, respectively. All compounds 3, 4 and 5 have a (C5Me5)Mg unit with Mg–O contacts to the cleavage or oxidation products. The compound [Mg(C5Me5)(15-crown-5)][C5Me5] · 15-crown-5 · toluene (6) was synthesized from Mg(C5Me5)2 and the crown ether 15-crown-5 in toluene. Here one C5Me5 ring was removed from the Mg(II) ion and replaced by a crown ether ligand. Both C5Me5-ligands could be cleaved from the magnesium cation by reacting
Mg(C5Me5)2 with dimethylsulfoxide (DMSO) to give the salt [Mg(DMSO)6]2+ 2[C5Me5]− (7).
Key words: Magnesium, Pentamethylcyclopentadienyl, Crystal Structure