Magnesium‐μ‐(9,10‐dihydro‐9,10‐anthrylen)‐aluminate; Komplexe des „Anthracenmagnesiums”︁

Das schwerlosliche „Anthracenmagnesium” 1a ⋅ n THF reagiert in THF mit Dialkylaluminiumhydriden zu den Magnesium-μ-(9,10-dihydro-9,10-anthrylen)-dialkylhydridoaluminaten 2a – c, mit Aluminiumtrihydrid zum entsprechenden -trihydridoaluminat 2d und mit Ethoxydiethyl-aluminium zum -ethoxydiethylaluminat 6. Die Konstitutionen der Komplexe 2a – c und 6 in THF wurden mittels NMR-Spektroskopie bestimmt. Nach dem Ergebnis der Rontgenstrukturanalyse von 2b (Alkyl = Et) besetzen Al und Mg im 9,10-Dihydro-9,10-anthrylen-System axiale Positionen, und es besteht bindende Wechselwirkung zwischen dem Mg⊕-Kation und dem Hydridwasserstoff des Aluminat-Anions. Analoge Komplexe 3 mit Trialkylaluminium lassen sich nur erhalten, wenn 1a ⋅ n THF mit mindestens (n + 1) AlR3 (R = Me, Et) in nicht-Lewis-basischen Losungsmitteln umgesetzt wird. Ether spalten die Komplexe 3 wieder in Trialkylaluminium-etherat, z. B. 4 oder 5, und 1a. In Diethylether ist letzteres nicht stabil und zerfallt in Magnesium und Anthracen. Magnesium-μ-(9,10-dihydro-9,10-anthrylene)-aluminates; Complexes of “Anthracenemagnesium” The relatively insoluble “anthracenemagnesium” 1a ⋅ n THF reacts in THF with dialkylaluminium hydrides to give magnesium-μ-(9,10-dihydro-9,10-anthrylene)-dialkylhydridoaluminates 2a – c, with aluminium trihydride the corresponding -trihydridoaluminate 2d and with ethoxydiethylaluminium the -ethoxydiethylaluminate 6. The structures of the compounds 2a – c and 6 dissolved in THF were determined by NMR spectroscopy. An X-ray crystallographic investigation of 2b (alkyl = ethyl) shows that Al and Mg occupy axial positions in a 9,10-dihydro-9,10-anthrylene system. The Mg⊕ cation interacts with the hydride of the aluminate anion. Analogous complexes 3 with trialkylaluminium can only be obtained if 1a ⋅ n THF is reacted with (n + 1) AIR3 (R = methyl, ethyl) in non-Lewis base solvents. Ether cause the cleavage of 3 into trialkylaluminium etherate, e. g. 4 or 5, and 1a, which is unstable in diethyl ether and decomposes into magnesium and anthracene.

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