Chiral (1,2)-diphenylethylene-salen complexes of triel metals: coordination patterns and mechanistic considerations in the isoselective ROP of lactide.
The synthesis of enantiomerically pure aluminium, gallium and indium complexes supported by chiral (R,R)-((HH)ONNO(HH)) (1), (R,R)-((MeH)ONNO(HMe)) (2), (R,R)-((tButBu)ONNO(tButBu)) (3), (R,R)-((MeNO2)ONNO(MeNO2)) (4), (R,R)-((HOMe)ONNO(HOMe)) (5) and (R,R)-((ClCl)ONNO(ClCl)) (6) (1,2)-diphenylethylene-salen ligands is described. Several of these complexes have been crystallographically authenticated, which highlights a diversity of coordination patterns. Whereas all Ga complexes form [Ga2(CH2SiMe3)4(ONNO)] bimetallic species (ONNO = 1-3), aluminium [AlR(ONNO)] (R = Me, CH2SiMe3) and indium [In(CH2SiMe3)(ONNO)] derivatives are monometallic for ONNO = 1, 2 and 4-6, and only form the bimetallic complexes [Al2R4(ONNO)] and [In2(CH2SiMe3)4(ONNO)] for the most sterically crowded ligand 3. The [AlMe(ONNO)] complexes react with iPrOH to give [AlOiPr(ONNO)] complexes that are robust towards further iPrOH. The [In(CH2SiMe3)(ONNO)] congeners are inert towards excess alcohol, whereas the Ga compounds decompose easily. All these alkyl complexes, as well as the [AlOiPr(ONNO)] derivatives, catalyse the ring-opening polymerisation (ROP) of racemic lactide (rac-LA). The [AlMe(ONNO)] complexes require additional alcohol to afford controlled reactions, but [AlOiPr(ONNO)] complexes are single-component catalysts for the isoselective ROP of rac-LA, with values of Pm in the range 0.80-0.90. Experimental evidence unexpectedly shows that chain-end control leads to the isoselectivity of these aluminium catalysts; also, the more crowded the coordination sphere, the higher the isoselectivity. The bimetallic Ga complexes do not afford controlled reactions, but the binary [In(ONNO)(CH2SiMe3)/(PhCH2OH)] systems competently mediate non-stereoselective ROP; evidence is given that an activated monomer mechanism is at work. Kinetic studies show that catalytic activity decreases when electronic density and steric congestion at the metal atom increase.
Organometallics: Materials and Catalysis Dept. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex (France).
Nicolas
N
Maudoux
Thierry
T
Roisnel
Vincent
V
Dorcet
Jean-François
JF
Carpentier
Yann
Y
Sarazin
D000535:Aluminum / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D004146:Dioxanes / Q000737:chemistry*; D005029:Ethylenediamines / Q000737:chemistry*; D007204:Indium / Q000737:chemistry*; D008958:Models, Molecular; D058105:Polymerization; D013237:Stereoisomerism; D013343:Styrenes / Q000737:chemistry*
D056831:Coordination Complexes; D004146:Dioxanes; D005029:Ethylenediamines; D013343:Styrenes; D007204:Indium; C011452:disalicylaldehyde ethylenediamine; C091880:dilactide; C007518:1,1-diphenylethylene; D000535:Aluminum
aluminium; indium; ligands; reaction mechanisms; ring-opening polymerisation; stereoselectivity