Synthesis and characterization of new intramolecularly nitrogen-stabilized organoaluminium- and organogallium alkoxides

The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me2Al{mu-O(CH2)(3)NMe2}](2) (1a), Me2AlOC6H2(CH2NMe2)(3)-2,4,6 (2a), [(S)-Me2Al {mu-OCH2CH(i-Pr)NH-i-Pr}](2) (3a) and [(S)-Me2Al {mu-OCH2CH(i-Pr)NHCH2Ph}](2) (4) are formed by reacting equimolar amounts of AlMe3 and Me2N(CH2)(3)OH, C6H2[(CH2NMe2)(3)-2,4,6]OH, (S)-i-PrNHCH(i-Pr)CH2OH, or (S)-PhCH2NHCH(i-Pr)CH2OH, respectively. An excess of AlMe3 reacts with Me2N(CH2)(2)OH, Me2N(CH2)(3)OH, C6H2[(CH2NMe2)(3)-2,4,6]OH, and (S)-i-PrNHCH(i-Pr)CH2OH producing the pick-a-back complexes [Me2AlO(CH2)(2)NMe2](AlMe3) (5), [Me2AlO(CH2)(3)NMe2](AlMe3) (1b), [Me2AlOC6H2(CH2NMe2)(3)-2,4,6](AlMe3)(2) (2b), and [(S)-Me2AlOCH2CH(i-Pr)NH-i-Pr](AlMe3) (3b), respectively The mixed alkyl- or alkenylchloroaluminium alkoxides [Me(Cl)Al{mu-O(CH2)(2)NMe2}](2) (6) and [{CH2=C(CH3)}-(Cl)Al{mu-O(CH2)(2)NMe2}](2) (8) are to obtain from Me2AlCl and Me2N(CH2)(2)OH and from [Cl2Al{mu-O(CH2)(2)NMe2}](2) (7) and CH2=C(CH3)MgBr, respectively. The analogous dimethylgallium alkoxides [Me2Ga{mu-O(CH2)(3)NMe}](2) (9), [(S)-Me2Ga{mu-OCH2CH(i-Pr)NH-i-Pr}](n) (10), [(S)-Me2Ga{mu-OCH2CH(i-Pr)NHCH2Ph}](n) (11), [(S)-Me2Ga{mu-OCH2CH(i-Pr)N(Me)CH2Ph}](n) (12) and [(S)-Me2Ga{mu-OCH2(C4H7NHCH2Ph)}](n) (13) result from the equimolar reactions of GaMe3 with the corresponding alcohols. The new compounds were characterized by elemental analyses, H-1, C-13- and Al-27-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.