Abstract
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•Cr(III)L produces 93.3% of trans-1,4 selectivity.•Fe(III)L and Fe(II)L both show equal cis-1,4 and trans-1,4 with 10% 1,2 selectivity.•The selectivity from cis-1,4 to 1,2 can be tuned by Co(II)L.•Controlling of microstructure of polybutadiene is achievable.
Tridentate complexes Cr(III)Cl3L, [L=2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine], Fe(III)Cl3L, Fe(II)Cl2L and Co(II)Cl2L have been prepared and fully characterized. The solid structures of Cr(III)Cl3L, Fe(III)Cl3L and Co(II)Cl2L have been revealed by single crystal X-ray diffraction, and the Cr(III)Cl3L and Fe(III)Cl3L complexes both exhibit a distorted octahedral geometry, while the Co(II)Cl2L complex has a trigonal bipyramidal conformation. Four complexes have been examined in regioselective polymerization of butadiene in combination with MAO in toluene at room temperature. The trans-1,4, cis-1,4 enchainment of resultant polybutadiene are controlled by the metal center. Activated by MAO, complex Cr(III)Cl3L produces high level of trans-1,4 selectivity (trans-1,4 up to 93.3%) with moderate polymer yield, complexes Fe(III)Cl3L and Fe(II)Cl2L both show equal cis-1,4 and trans-1,4 with minor 1,2 selectivity (<10%), and Co(II)Cl2L catalyst displays predominated cis-1,4 selectivity, which can be shifted to 1,2 selectivity by adding PPh3 as an additive. Thus, tuning of the cis-1,4, trans-1,4 and 1,2 selectivity in full range via central metal and additive chosen by these 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine supported catalysts has been achieved.