A series of zinc phenoxides of the general formula (2,6-R2C6H3O)2Zn(base)2 [R = Ph, tBu, iPr,
base = Et2O, THF, or propylene carbonate] and (2,4,6-Me3C6H2O)2Zn(pyridine)2 have been synthesized and
characterized in the solid state by X-ray crystallography. All complexes crystallized as four-coordinate monomers
with highly distorted tetrahedral geometry about the zinc center. The angles between the two sterically
encumbering phenoxide ligands were found to be significantly more obtuse than the corresponding angles
between the two smaller neutral base ligands, having average values of 140° and 95°, respectively. In a
noninteracting solvent such as benzene or methylene chloride at ambient temperature, the ancillary base ligands
are extensively dissociated from the zinc center, with the degree of dissociation being dependent on the base
as well as the substituents on the phenolate ligands. That is, stronger ligand binding was found in zinc centers
containing electron-donating tert-butyl substituents as opposed to electron-withdrawing phenyl substituents.
In all instances, the order of ligand binding was pyridine > THF > epoxides. These bis(phenoxide) derivatives
of zinc were shown to be very effective catalysts for the copolymerization of cyclohexene oxide and CO2 in
the absence of strongly coordinating solvents, to afford high-molecular-weight polycarbonate (M
w ranging
from 45 × 103 to 173 × 103 Da) with low levels of polyether linkages. However, under similar conditions,
these zinc complexes only coupled propylene oxide and CO2 to produce cyclic propylene carbonate. Nevertheless,
these bis (phenoxide) derivatives of zinc were competent at terpolymerization of cyclohexene oxide/propylene
oxide/CO2 with little cyclic propylene carbonate formation at low propylene oxide loadings. While CO2 showed
no reactivity with the sterically encumbered zinc bis(phenoxides), e.g., (2,6-di-tert-butylphenoxide)2Zn(pyridine)2,
it rapidly inserted into one of the Zn−O bonds of the less crowded (2,4,6-trimethylphenoxide)2Zn(pyridine)2
to provide the corresponding aryl carbonate zinc derivative. At the same time, both sterically hindered and
sterically nonhindered phenoxide derivatives of zinc served to ring-open epoxide, i.e., were effective catalysts
for the homopolymerization of epoxide to polyethers. The relevance of these reactivity patterns to the initiation
step of the copolymerization process involving these monomeric zinc complexes is discussed.
