Bisiminopyridine Ferrous Complex Catalyst in Olefin Polymerization Kaidi

Bis(imino)pyridine Ferrous Complex Catalyst in Olefin Polymerization Kaidi Yang 1

Background and Significance Polyolefin Polyethylene: 141. 8 million tons in 2015 n. R-CH=CH-R’ Catalyst [CH-CH]n R R’ 2

Background and Significance Aluminum alkyls + 1960 s + water Methylaluminoxane (MAO) 1970 s Kaminsky Ziegler-Natta catalyst Transition metal complexes + Transition metal complexes Ziegler-Natta type catalyst 2010: 100 million tones of polymer 3

Problem 4

Problem Bis(imino)pyridine Ferrous Complex Possible structure of MAO (Active Compound) 5

Preliminary Result Singlet structures of AC at the Level of B 3 LYP/ 6 -31 G* 6

Preliminary Result Spin Geometry of Ph Total Energy Hartree Final Enthalpy (Hartree) Free Energy (Hartree) Singlet Cs, disrot. , I -2620. 952644 -2620. 632920 -2620. 703848 Singlet Cs, disrot. , II -2620. 946946 -2620. 627754 -2620. 701338 Singlet C 2, conrot. , III -2620. 951697 -2620. 632164 -2620. 702859 Triplet Cs, disrot. , I -2620. 988753 -2620. 669572 -2620. 741818 Triplet Cs, disrot. , II -2620. 992046 -2620. 673029 -2620. 745117 Energy Table of AC at the Level of B 3 LYP/ 6 -31 G* 7

Preliminary Result Spin density surface of the triplet AC II with MAO compounds from two different versions at the level of B 3 LYP/ 6 -31 G* 8

Specific Aim 1 �Determine the best structure of the bis(imino)pyridine ferrous complex. �Singlet, Triplet… Quintet? Stability: Triplet>Singlet. 9

Specific Aim 1 �Determine the best structure of the bis(imino)pyridine ferrous complex. �I, III? Stability: I>II…. . Singlet II>I…………Triplet ? . . . . Quintet 10

Specific Aim 2 �Understand the process of aggregation of AC and MAO compounds. �Determine the best structure of AC-MAO. Singlet? Triplet? I, III? 11

Specific Aim 2 �Understand the process of aggregation of AC and MAO compounds. �Determine the transition state. 12

Specific Aim 3 �Understand the catalysis mechanism of AC in the process of ethylene polymerization. �Ethylene: the simplest olefin. 13

Summary Step One: Step Two: Step Three: 14