Synthese, Röntgenstrukturanalyse und Multikern-NMR-spektroskopische Untersuchung einiger intramolekular stickstoffstabilisierter Bor-, Aluminium- und Galliumorganyle

The intramolecularly nitrogen stabilized organo-aluminum- and organoboron compounds Me2Al(CH2)(3)NMe2 (1), Me2AlC10H6-8-NMe2 (2), (1)Pr2Al(CH2)(3)NEt2 (3), (CH2)(5)Al(CH2)(3)NMe2 (4), and (CH2)(5)B(CH2)(3)NMe2 (5) are synthesized from Me2AlCl and the corresponding organolithium compounds and from AlCL3 or BCl3, the lithium alkyl and (PrMgCl)-Pr-1 or BrMg(CH2)(5)MgBr,respectively. AlCl3 and GaC1(3) react with Li(CH2)(3)NMe2 Or LiCH2CHMeCH2NMe2 forming Cl2AlCH2CHMeCH2NMe2 (6), Cl2Al(CH2)(3)NMe2 (8), and Cl2Ga(CH2)(3)NMe2 (9). The reaction of 6 and of 8 or 9 with BrMg(CH2)(5)MgBr and BrMg(CH2)(6)MgBr, respectively, yields (CH2)(5)AlCH2CHMeCH2NMe2 (7), (CH2)(6)Al(CH2)(3)NMe2 (10), and (CH2)(6)Ga(CH2)(3)NMe2 (11). MeAlCl2, made by the redistribution reaction of AlCl3 with Me2AlCl, reacts with 2 equivalents of Li(CH2)(3)NMe2 yielding MeAl[(CH2)(3)NMe2](2) (12) and with MeN[(CH2)(3)MgCl](2) under formation of MeAl[(CH2)(3)](2)NMe (13). MeAlCl2, MeGaCl2, or GaCl3 accordingly react with one equivalent of organolithium reagent to give the intramolecularly nitrogen stabilized organoaluminum and organogallium chlorides MeClAl(CH2)(3)NMe2 (14), MeClGa(CH2)(3)NMe2 (15), MeClGaC6H4-2-CH2NMe2 (16) as well as Cl2GaC6H4-2-CHMeNMe2 (17). The compounds were characterized by elemental analyses, mass spectroscopy, H-1, B-11, C-13 and Al-27 NMR investigations. Single crystal Xray structure analyses of 1, 2, 4, 5 and 17 reveal the monomeric molecular structures with intramolecular nitrogen coordination.