TY - JOUR
T1 - Structural study of the reaction of methylzinc amino alcoholates with oxygen
AU - Hollingsworth, Nathan
AU - Johnson, Andrew
AU - Kingsley, A
AU - Kociok-Kohn, Gabriele
AU - Molloy, Kieran C
PY - 2010/8/9
Y1 - 2010/8/9
N2 - Reaction of ZnMe2 with 1,3-bis(dimethylamino)propan-2-ol (Hbdmap) in 2.1 ratio forms both [MeZn-(bdmap)center dot 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 O-2 at low temperatures with controlled insertion into one of the Zn-C bonds of the coordinated ZnMe2 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-center dot)], 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
AB - Reaction of ZnMe2 with 1,3-bis(dimethylamino)propan-2-ol (Hbdmap) in 2.1 ratio forms both [MeZn-(bdmap)center dot 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 O-2 at low temperatures with controlled insertion into one of the Zn-C bonds of the coordinated ZnMe2 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-center dot)], 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
UR - http://www.scopus.com/inward/record.url?scp=77955163813&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1021/om100449t
U2 - 10.1021/om100449t
DO - 10.1021/om100449t
M3 - Article
SN - 0276-7333
VL - 29
SP - 3318
EP - 3326
JO - Organometallics
JF - Organometallics
IS - 15
ER -