Structural Study of the Reaction of Methylzinc Amino Alcoholates with Oxygen

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