Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: A Tool for Molecular Mass Prediction

被引：86
作者：
Falivene, Laura [1 ]
Cavallo, Luigi [1 ]
Talarico, Giovanni [2 ]
机构：
[1] King Abdullah Univ Sci & Technol, Kaust Catalysis Ctr, Phys Sci & Engn Div, Thuwal 239556900, Saudi Arabia
[2] Univ Naples Federico II, Dipartimento Sci Chim, I-80126 Naples, Italy
来源：
ACS CATALYSIS | 2015年 / 5卷 / 11期
关键词：
propene polymerization catalysis; buried volume; metallocene and postmetallocene systems; chain transfer to the monomer; GAUSSIAN-BASIS SETS; HETEROCYCLIC CARBENES NHC; ZETA-VALENCE QUALITY; CHAIN-TRANSFER; OLEFIN POLYMERIZATION; PROPYLENE POLYMERIZATIONS; STEREOCHEMICAL CONTROL; CONSTRAINED GEOMETRY; TITANIUM COMPLEXES; AB-INITIO;
D O I：
10.1021/acscatal.5b01363
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%V-Bur) as molecular descriptor is reported. The %V-Bur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by density functional theory (DFT) methods is found for Group 4 metal catalysts. The "master curves" derived for Ti, Zr, and Hf confirm not only that the % V-Bur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.
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收藏
页码：6815 / 6822
页数：8
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