TY - JOUR
T1 - β-Diketiminate complexes of Group 4
T2 - Active complexes for the isomerization of α-olefins and the polymerization of propylene towards elastomeric polypropylene
AU - Shaviv, Ella
AU - Botoshansky, Mark
AU - Eisen, Moris S.
N1 - Funding Information:
This research was supported by German Israel Foundation under contract I-621-27.5/1999 and by the Fund for the Promotion of Research at the Technion.
PY - 2003/10/7
Y1 - 2003/10/7
N2 - The β-diketiminate lithium ligand [{N(SiMe3)C(Ph)} 2CH][Li] reacted with Group 4 metal salts (Ti and Zr) to yield the complexes [{N(SiMe3)C(Ph)}2CH] 2TiCl2 (5) and [{N(SiMe3)C(Ph)} 2CH][N(SiMe3)C(Ph)NC(Ph)CH(SiMe3)] ZrCl2 (6). The crystal structure of 6 shows that one of the two ketamidinate ligands undergoes an isomerization to the corresponding substituted benzamidinate. A mechanism for the catalyzed isomerization of the β-diketiminate ligand is presented. Complex 5 was found to be active in the polymerization of propylene, producing remarkably high-molecular weight (>100,000 g mol-1) elastomeric polymer, whereas the zirconium complex was found inactive. Complex 5, and surprisingly complex 6, were found to be active catalysts, in the presence of MAO (methylalumoxane), for the isomerization of aliphatic olefins (1-octene, allylbenzene). Each complex catalyzed the olefins by different mechanisms. Kinetic studies for the isomerization of allylbenzene by complex 5 show that the reaction rate follows a first order in both catalyst and olefin concentrations with Δ H ‡=14.7(4) kcal mol-1 and Δ S ‡=-33(1) e.u. These findings support the epimerization mechanism of the last inserted monomer that is proposed for as the primary cause for the elastomeric properties of polypropylene produced by this complex. In addition, we show how complementary isomerization studies of α-olefins shed light on the polymerization mechanism.
AB - The β-diketiminate lithium ligand [{N(SiMe3)C(Ph)} 2CH][Li] reacted with Group 4 metal salts (Ti and Zr) to yield the complexes [{N(SiMe3)C(Ph)}2CH] 2TiCl2 (5) and [{N(SiMe3)C(Ph)} 2CH][N(SiMe3)C(Ph)NC(Ph)CH(SiMe3)] ZrCl2 (6). The crystal structure of 6 shows that one of the two ketamidinate ligands undergoes an isomerization to the corresponding substituted benzamidinate. A mechanism for the catalyzed isomerization of the β-diketiminate ligand is presented. Complex 5 was found to be active in the polymerization of propylene, producing remarkably high-molecular weight (>100,000 g mol-1) elastomeric polymer, whereas the zirconium complex was found inactive. Complex 5, and surprisingly complex 6, were found to be active catalysts, in the presence of MAO (methylalumoxane), for the isomerization of aliphatic olefins (1-octene, allylbenzene). Each complex catalyzed the olefins by different mechanisms. Kinetic studies for the isomerization of allylbenzene by complex 5 show that the reaction rate follows a first order in both catalyst and olefin concentrations with Δ H ‡=14.7(4) kcal mol-1 and Δ S ‡=-33(1) e.u. These findings support the epimerization mechanism of the last inserted monomer that is proposed for as the primary cause for the elastomeric properties of polypropylene produced by this complex. In addition, we show how complementary isomerization studies of α-olefins shed light on the polymerization mechanism.
KW - Diketiminates
KW - Elastomeric polypropylene
KW - Isomerization
KW - Polymerization
KW - Titanium
KW - X-ray structure
KW - Zirconium
UR - http://www.scopus.com/inward/record.url?scp=0141493630&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(03)00592-8
DO - 10.1016/S0022-328X(03)00592-8
M3 - 文章
AN - SCOPUS:0141493630
SN - 0022-328X
VL - 683
SP - 165
EP - 180
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -