TY - JOUR
T1 - Activation of Single-Component Nickel(II) Polyethylene Catalysts via Phase Transfer of Fluorous Phosphine Ligands
AU - Xi, Zhenxing
AU - Bazzi, Hassan S.
AU - Gladysz, John A.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/9/2
Y1 - 2015/9/2
N2 - The nickel salicylaldiminato phosphine complexes [1,2,3-C6H3(9-anthracenyl)O(CH=N(2,6-C6H3(iPr)2)]Ni(Me)[P(4-C6H4R)3] (4; R = a, (CH2)2Rf8; b, (CH2)3Rf8; c, H (Rf8 = (CF2)7CF3)) are prepared from the corresponding phosphines 3a-c and nickel NCMe adduct (46-68%). These are applied as catalysts for ethylene polymerization in toluene and fluorous/toluene liquid/liquid biphasic mixtures. Under the latter conditions, the fluorous phosphines 3a,b that must dissociate to generate the active catalyst migrate to the fluorous phase (partition coefficients 97.5:2.5 and 66.6:33.4 vs <0.5:>99.5 for 4a,b). Catalysts 4a,b show marked accelerations under biphasic conditions, but 4c (which has a lipophilic phosphine ligand) does not. Under all conditions, 4a,b are faster catalysts than the Ni(Ph)(PPh3) analogue, a previously reported benchmark.
AB - The nickel salicylaldiminato phosphine complexes [1,2,3-C6H3(9-anthracenyl)O(CH=N(2,6-C6H3(iPr)2)]Ni(Me)[P(4-C6H4R)3] (4; R = a, (CH2)2Rf8; b, (CH2)3Rf8; c, H (Rf8 = (CF2)7CF3)) are prepared from the corresponding phosphines 3a-c and nickel NCMe adduct (46-68%). These are applied as catalysts for ethylene polymerization in toluene and fluorous/toluene liquid/liquid biphasic mixtures. Under the latter conditions, the fluorous phosphines 3a,b that must dissociate to generate the active catalyst migrate to the fluorous phase (partition coefficients 97.5:2.5 and 66.6:33.4 vs <0.5:>99.5 for 4a,b). Catalysts 4a,b show marked accelerations under biphasic conditions, but 4c (which has a lipophilic phosphine ligand) does not. Under all conditions, 4a,b are faster catalysts than the Ni(Ph)(PPh3) analogue, a previously reported benchmark.
UR - http://www.scopus.com/inward/record.url?scp=84940979081&partnerID=8YFLogxK
U2 - 10.1021/jacs.5b06562
DO - 10.1021/jacs.5b06562
M3 - Article
AN - SCOPUS:84940979081
SN - 0002-7863
VL - 137
SP - 10930
EP - 10933
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 34
ER -