TY - JOUR
T1 - Di-Zinc-Aryl Complexes: CO2 Insertions and Applications in Polymerisation Catalysis
AU - Romain, Charles
AU - Garden, Jennifer A.
AU - Trott, Gemma
AU - Buchard, Antoine
AU - White, Andrew J. P.
AU - Williams, Charlotte K.
PY - 2017/5/5
Y1 - 2017/5/5
N2 - Two new di-zinc aryl complexes, [LZn2Ph2] and [LZn2(C6F5)2], coordinated by a diphenol tetraamine macrocyclic ligand are prepared and fully characterized, including by single crystal X-ray diffraction experiments. The complexes’ reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, iso-propanol and phenol are investigated using both experimental studies and density functional theory calculations. In particular, [LZn2Ph2] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn2(C6F5)2] does not react. Under these conditions [LZn2Ph2] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide / carbon dioxide (TOF = 20 h-1); cyclohexene oxide / phthalic anhydride (TOF = 33 h-1) and the ring opening polymerisations of rac-lactide (TOF = 99 h-1) and ε-caprolactone (TOF = 5280 h-1).
AB - Two new di-zinc aryl complexes, [LZn2Ph2] and [LZn2(C6F5)2], coordinated by a diphenol tetraamine macrocyclic ligand are prepared and fully characterized, including by single crystal X-ray diffraction experiments. The complexes’ reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, iso-propanol and phenol are investigated using both experimental studies and density functional theory calculations. In particular, [LZn2Ph2] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn2(C6F5)2] does not react. Under these conditions [LZn2Ph2] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide / carbon dioxide (TOF = 20 h-1); cyclohexene oxide / phthalic anhydride (TOF = 33 h-1) and the ring opening polymerisations of rac-lactide (TOF = 99 h-1) and ε-caprolactone (TOF = 5280 h-1).
U2 - 10.1002/chem.201701013
DO - 10.1002/chem.201701013
M3 - Article
SN - 0947-6539
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
ER -