Structural Study of the Reaction of Methylzinc Amino Alcoholates with Oxygen

Reaction of ZnMe2 with 1,3-bis(dimethylamino)propan-2-ol (Hbdmap) in 2:1 ratio forms both [MeZn(bdmap)·ZnMe2]2 (2) and [MeZn(bdmap)]3·ZnMe2 (3) depending on the concentration of the reaction. In the former, ZnMe2 is coordinated to a free N-donor of the bdmap ligand and rather more loosely to the oxygen of the alkoxide. In 3, the ZnMe2 is coordinated to two free N-donors of the bdmap ligand. 2 reacts with O2 at low temperatures with controlled insertion into one of the Zn−C bonds of the coordinated ZnMe2 group to form the peroxide [MeZn(bdmap)]2MeZnOOMe (4). 4 decomposes slowly, and the hydroxide [MeZn(bdmap)]2MeZnOH (5) was isolated; in addition to 5, two other decomposition products have been unambiguously identified, namely, (MeZn)5(bdmap)3O (6) and (MeZn)4(bdmap)4ZnO (7). The formation of these species can be linked to reactions of the hydroxide (5), or its associated radical [MeZn(bdmap)]2MeZn(O•)], with species such as ZnMe2 or MeZn(bdmap), present is solution as a result of operating Schlenk equilibria. The structure of [MeZn(bdmap)]4 (1) is also reported.