Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me 2 Al{μ‐O(CH 2 ) 3 NMe 2 }] 2 ( 1a ), Me 2 AlOC 6 H 2 (CH 2 NMe 2 ) 3 ‐2,4,6 ( 2a ), [( S )‐Me 2 Al{μ‐OCH 2 CH( i ‐Pr)NH‐ i ‐Pr}] 2 ( 3a ) and [( S )‐Me 2 Al{μ‐OCH 2 CH( i ‐Pr)NHCH 2 Ph}] 2 ( 4 ) are formed by reacting equimolar amounts of AlMe 3 and Me 2 N(CH 2 ) 3 OH, C 6 H 2 [(CH 2 NMe 2 ) 3 ‐2,4,6]OH, ( S )‐ i ‐PrNHCH( i ‐Pr)CH 2 OH, or ( S )‐PhCH 2 NHCH( i ‐Pr)CH 2 OH, respectively. An excess of AlMe 3 reacts with Me 2 N(CH 2 ) 2 OH, Me 2 N(CH 2 ) 3 OH, C 6 H 2 [(CH 2 NMe 2 ) 3 ‐2,4,6]OH, and ( S )‐ i ‐PrNHCH( i ‐Pr)CH 2 OH producing the “pick‐a‐back” complexes [Me 2 AlO(CH 2 ) 2 NMe 2 ](AlMe 3 ) ( 5 ), [Me 2 AlO(CH 2 ) 3 NMe 2 ](AlMe 3 ) ( 1b ), [Me 2 AlOC 6 H 2 (CH 2 NMe 2 ) 3 ‐2,4,6](AlMe 3 ) 2 ( 2b ), and [(S)‐Me 2 AlOCH 2 CH( i ‐Pr)NH‐ i ‐Pr](AlMe 3 ) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH 2 ) 2 NMe 2 }] 2 ( 6 ) and [{CH 2 =C(CH 3 )}(Cl)Al{μ‐O(CH 2 ) 2 NMe 2 }] 2 ( 8 ) are to obtain from Me 2 AlCl and Me 2 N(CH 2 ) 2 OH and from [Cl 2 Al{μ‐O(CH 2 ) 2 NMe 2 }] 2 ( 7 ) and CH 2 =C(CH 3 )MgBr, respectively. The analogous dimethylgallium alkoxides [Me 2 Ga{μ‐O(CH 2 ) 3 NMe 2 }] 2 ( 9 ), [( S )‐Me 2 Ga{μ‐OCH 2 CH( i ‐Pr)NH‐ i ‐Pr}] n ( 10 ), [( S )‐Me 2 Ga{μ‐OCH 2 CH( i ‐Pr)NHCH 2 Ph}] n ( 11 ), [( S )‐Me 2 Ga{μ‐OCH 2 CH( i ‐Pr)N(Me)CH 2 Ph}] n ( 12 ) and [( S )‐Me 2 Ga{μ‐OCH 2 (C 4 H 7 NHCH 2 Ph)}] n ( 13 ) result from the equimolar reactions of GaMe 3 with the corresponding alcohols. The new compounds were characterized by elemental analyses, 1 H‐, 13 C‐ and 27 Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.