Abstract
The insertion mechanism of styrene polymerization with a Cp-based ansa-matallocene catalyst (Cp = η5-C5H5) was investigated by the density functional theory (DFT). The metallocene catalyst adopted in this study, Si(CH3)2Cp 2Ti(CH3)2, is experimentally known as a highly syndiospecific catalyst for styrene polymerization. A cationic species, SiH 2Cp2Ti+-CH3, is used as an activated form of the catalyst for modeling the initiation of styrene polymerization when one calculates the first insertion of a styrene monomer into the cationic species. Calculations for the second insertion of styrene monomer into the product of the first insertion were also performed. The results of the second insertion of styrene monomer suggest that the frontside insertion of the second styrene leads to a Hβ-transfer reaction, while the backside insertion, which is favored over the frontside insertion, produces a highly syndiotactic product without the Hβ-transfer reaction. This is in agreement with the experimental result. In the backside styrene insertion, the transition state is characterized by a β-agostic interaction than an α-agostic interaction because the α-agostic interaction has the repulsive interactions between catalytic ligands and substituents bonded to Cα of growing polymer chain. The stereoselectivity of the backside insertion is rationalized by the chain-end-control mechanism, and this mechanism also rationalizes higher insertion steps of styrene monomers.
| Original language | English |
|---|---|
| Pages (from-to) | 5741-5751 |
| Number of pages | 11 |
| Journal | Macromolecules |
| Volume | 37 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - 2004 Jul 27 |
| Externally published | Yes |
Fingerprint
ASJC Scopus subject areas
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry
Cite this
A density functional study on the stereoselectivity of styrene polymerization with ansa-metallocene catalyst. / Yang, Sung Hoon; Huh, June; Yang, Jae Shick; Jo, Won Ho.
In: Macromolecules, Vol. 37, No. 15, 27.07.2004, p. 5741-5751.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - A density functional study on the stereoselectivity of styrene polymerization with ansa-metallocene catalyst
AU - Yang, Sung Hoon
AU - Huh, June
AU - Yang, Jae Shick
AU - Jo, Won Ho
PY - 2004/7/27
Y1 - 2004/7/27
N2 - The insertion mechanism of styrene polymerization with a Cp-based ansa-matallocene catalyst (Cp = η5-C5H5) was investigated by the density functional theory (DFT). The metallocene catalyst adopted in this study, Si(CH3)2Cp 2Ti(CH3)2, is experimentally known as a highly syndiospecific catalyst for styrene polymerization. A cationic species, SiH 2Cp2Ti+-CH3, is used as an activated form of the catalyst for modeling the initiation of styrene polymerization when one calculates the first insertion of a styrene monomer into the cationic species. Calculations for the second insertion of styrene monomer into the product of the first insertion were also performed. The results of the second insertion of styrene monomer suggest that the frontside insertion of the second styrene leads to a Hβ-transfer reaction, while the backside insertion, which is favored over the frontside insertion, produces a highly syndiotactic product without the Hβ-transfer reaction. This is in agreement with the experimental result. In the backside styrene insertion, the transition state is characterized by a β-agostic interaction than an α-agostic interaction because the α-agostic interaction has the repulsive interactions between catalytic ligands and substituents bonded to Cα of growing polymer chain. The stereoselectivity of the backside insertion is rationalized by the chain-end-control mechanism, and this mechanism also rationalizes higher insertion steps of styrene monomers.
AB - The insertion mechanism of styrene polymerization with a Cp-based ansa-matallocene catalyst (Cp = η5-C5H5) was investigated by the density functional theory (DFT). The metallocene catalyst adopted in this study, Si(CH3)2Cp 2Ti(CH3)2, is experimentally known as a highly syndiospecific catalyst for styrene polymerization. A cationic species, SiH 2Cp2Ti+-CH3, is used as an activated form of the catalyst for modeling the initiation of styrene polymerization when one calculates the first insertion of a styrene monomer into the cationic species. Calculations for the second insertion of styrene monomer into the product of the first insertion were also performed. The results of the second insertion of styrene monomer suggest that the frontside insertion of the second styrene leads to a Hβ-transfer reaction, while the backside insertion, which is favored over the frontside insertion, produces a highly syndiotactic product without the Hβ-transfer reaction. This is in agreement with the experimental result. In the backside styrene insertion, the transition state is characterized by a β-agostic interaction than an α-agostic interaction because the α-agostic interaction has the repulsive interactions between catalytic ligands and substituents bonded to Cα of growing polymer chain. The stereoselectivity of the backside insertion is rationalized by the chain-end-control mechanism, and this mechanism also rationalizes higher insertion steps of styrene monomers.
UR - http://www.scopus.com/inward/record.url?scp=3943074454&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=3943074454&partnerID=8YFLogxK
U2 - 10.1021/ma0497815
DO - 10.1021/ma0497815
M3 - Article
AN - SCOPUS:3943074454
VL - 37
SP - 5741
EP - 5751
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 15
ER -