Organozinc Aminoalcoholates: Synthesis, Structure, and Materials Chemistry

A series of novel organozinc aminoalcoholates have been synthesized by the reaction of the amino alcohols HOCHx(CH2NMe2)3−x (x = 2, Hdmae; 1, Hbdmap; 0, Htdmap) with R2Zn (R = Me, Et). The 1:1 reaction with Hdmae leads to the tetramers [RZn(dmae)]4 [R = Me (1), Et (2)], while with Htdmap, dimeric [RZn(tdmap)]2 [R = Me (7), Et (8)] are produced. Reaction with Hbdmap only yields [MeZn(bdmap)]n (3), an oil which mass spectral data suggests contains a mixture of Zn2 - Zn7 species, when a 2-fold excess of ligand is used. Crystals of dimeric [Zn(bdmap)2·Hbdmap]2 (4) deposit from this oil on prolonged standing. Reaction of Et2Zn with Hbdmap (1:1) affords [EtZn(bdmap)]n (5), also an oil made up of Zn3 and Zn4 clusters on the basis of mass spectral evidence. Crystals of EtZn3(bdmap)5 (6) are formed within the oil that is 5 on standing. [MeZn(tdmap)]2 (7) has been used as a single-source precursor for hexagonal ZnO films under low pressure chemical vapor deposition (LPCVD) conditions and a substrate temperature of 500 °C.