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Letter
Computational Transition-State Design Provides Experimentally Verified
Cr(P,N) Catalysts for Control of Ethylene Trimerization and Tetramerization
Doo-Hyun Kwon, Jack T. Fuller, Uriah Kilgore, Orson Larry Sydora, Steven M. Bischof, and Daniel H. Ess
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b04026 • Publication Date (Web): 04 Jan 2018
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Computational Transition-State Design Provides
8 Experimentally Verified Cr(P,N) Catalysts for Control of
9
10 Ethylene Trimerization and Tetramerization
11
12 Doo-Hyun Kwon,‡1 Jack T. Fuller, III,‡1 Uriah J. Kilgore,2 Orson. L. Sydora,2 Steven. M. Bischof,*2 and
13 Daniel H. Ess*1
14 1
15 Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602 (USA). 2Research and Tech-
16 nology, Chevron Phillips Chemical Company LP, 1862 Kingwood Drive, Kingwood, Texas 77339 (USA)
17
18
19 Supporting Information Placeholder
20
ABSTRACT: Computational design of molecular homogeneous density-functional theory (DFT) methods have the potential to
21
organometallic catalysts followed by experimental realization predict catalysts,13-16 there are very few cases of specific and gen-
22 uine prediction followed by experimental realization for molecu-
remains a significant challenge. Here, we report the development
23 and use of a density functional theory transition-state model that lar organometallic catalysts.14 Here, we report the development
24 provided quantitative prediction of molecular Cr catalysts for and use of a DFT transition-state model that provides quantitative
25 controllable selective ethylene trimerization and tetramerization. prediction of phosphine imine (P,N) Cr catalysts for controllable
26 This computational model identified a general class of phosphine selective ethylene trimerization and tetramerization. The DFT
correlation model is based on competitive transition states from a
27 monocyclic imine (P,N)-ligand Cr catalysts where changes in the
ligand structure control 1-hexene versus 1-octene selectivity. Ex- common chromacycloheptane catalytic cycle intermediate. This
28 model identified a new family of highly selective catalysts that
perimental ligand and catalyst synthesis, and reaction testing,
29 quantitatively confirmed predictions. through computational-based ligand design resulted in a predicta-
30 ble selectivity shift from 1-hexene to 1-octene. Subsequent exper-
31 imental ligand and catalyst synthesis, and ethylene oligomeriza-
32 tion reaction testing, realized the computational predictions.
33 Keywords SELECTIVE POLYMERIZATION TO 1-ALKENES
34 Computational predictions, transition-state design, molecular
catalysis, chromium catalysis, ethylene trimerization, ethylene Alkene Targets
35 This Work:
tetramerization. Computationally Designed
36 Cr(P,N) Catalysts
37
Linear α-olefins (LAOs, 1-alkenes) are produced from ethylene
38 oligomerization at ~3,000,000 tons/year worldwide.1,2 LAOs are
39 Scheme 1. Ethylene Oligomerization Targets.
key petrochemical precursors for the synthesis of larger polymers,
40 detergents, plasticizers, and lubricants. Several manufacturers Cr bidentate phosphine imine (Cr(P,N)) catalysts17-24 (Scheme 2)
represent a desirable class of catalysts for selective LAO produc-
41 such as Shell, Ineos, Idemitsu, SABIC, and Chevron Phillips
tion from ethylene for several reasons25-27: (1) (P,N) ligands can
42 Chemical Company LP (CPChem) use metal-catalyzed multi-step
be synthesized in a modular route that is highly flexible. (2) Meta-
43 ethylene oligomerization processes to produce LAOs. Most of
these processes generate a wide distribution of LAO carbon chain lation to Cr is straightforward, and the starting (P,N)CrIIICl3 cata-
44 lengths from C4 (1-butene) to C20 (1-eicosene).1,3 Sasol also re- lysts can be characterized. (3) Ethylene oligomerization reactions
45 covers LAOs from Fischer-Tropsch synthesis. A major ongoing are generally highly reproducible and lead to high purity LAOs
46 industrial challenge is to develop homogeneous molecular cata- without chain branching,17 which is generally challenging for
47 lysts that result in selective and tunable ethylene oligomerization other types of catalysts. In pursuit of controlling targeted C6 to C8
to only 1-hexene and 1-octene (Scheme 1),4-6 which are in de- 1-alkene selectivity with Cr(P,N) catalysts, Sydora and co-
48 workers reported LAO selectivity for several aryl and benzyl dec-
49 mand as co-monomers for polyethylene production and elasto-
mers. While CPChem was the first to commercialize a selective orated phosphine imine catalysts (Scheme 2).17,18 These catalysts
50 showed moderate oligomerization activity with high purity LAO
catalyst system for 1-hexene,7 Wass/BP, and Sasol have devel-
51 oped technology for selective ethylene trimerization and tetramer- production and trace polymer production. Product purity typically
52 ization.8-12 However, despite all of these efforts there is no clear exceeded >98% 1-olefin in the C6 and C8 fractions. It was through
53 empirical approach to the design of molecular homogeneous Cr- time consuming (several years) experimental screening that cata-
lyst 1a was identified that results in >90 weight % yield of C6 (at
54 based catalysts that increase LAO selectivity towards 1-octene
>99% 1-hexene purity). Unfortunately, changes to the 1a (P,N)
55 Computational molecular catalyst design has the potential to sig- ligand structure resulted in no more than ~30 weight % of C8, and
56 nificantly impact selective ethylene oligomerization, if new metal- no systematic empirical approach was identified to further in-
57 ligand catalysts can be identified that have predictable control of crease the LAO selectivity towards 1-octene. Therefore, we un-
ethylene trimerization versus tetramerization. While accurate
58 dertook the task of computational design of new Cr(P,N) catalysts
59
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with the goal of predictable control of 1-hexene and 1-octene Scheme 3. Mechanism for Homogeneous Cr-Catalyzed Ethylene
1 selectivity. Trimerization and Tetramerization. (Black arrows represent com-
2 mon reaction steps. Blue arrows represent 1-hexene pathway. Red
3 arrows represent 1-octene pathway.)
4 Previous computational studies28-29 established that the M06L38-39
5 density functional is accurate for treating the multiple spin states
and oxidation and reduction steps involved in Cr catalytic cycles
6 similar to that shown in Scheme 3. Therefore, we used unrestrict-
7 ed UM06L/def2-TZVP//UM06L/6-31G(d,p)(LANL2DZ) theo-
8 ry40-43 combined with the SMD44 continuum solvent model for
9 cyclohexane to estimate free energies for intermediates and transi-
10 tion states. With the adoption of the mechanism shown in Scheme
11 3, we commenced examining transition-state structures for Cr
catalysts in Scheme 2 to accurately replicate the C6 to C8 weight
12
% relative selectivity. We found that the lowest-energy transition-
13 state structures arise from the low-valent high-spin quartet cation-
14 ic (P,N)CrIII(C6H12) chromacycloheptane intermediate (intermedi-
15 ate D).45-46 As stated above, the key transition states that control
16 selectivity in this mechanism are β-hydrogen transfer (TS1) and
Scheme 2. Reported Ethylene Trimerization/Tetramerization
17 Catalysts and Relative Mass % of C6 and C8.17 [Selectivity %] =
ethylene migratory insertion (TS2). The top structures in Figure
147 show the lowest-energy structures from the ensembles of TS1
18 % of 1-Alkene Relative to Total Alkenes. and TS2 for catalyst 1a. In this case, the TS1 ensemble is com-
19 prised of up to 25 unique transition-state conformations and the
20 To build a predictive DFT transition-state selectivity model, we TS2 ensemble has up to 40 unique structures (see SI for details).
21 undertook quantitative modeling of 1a-1e LAO selectivity. This The large number of conformations in each transition-state en-
22 required identification of a catalytic mechanism and comparison semble results from the flexibility of the chromacycloheptane ring
23 of calculated 1-hexene:1-octene ratio selectivity to experiment. and aryl ligand groups. For the relative energies of TS1 and TS2
24 Previous computational studies by Britovsek and McGunniess,28- to control selectivity, intermediates leading to these transition
29
Cheong,30 Liu,31-33 and others34-36 explored possible mecha- states need to be in equilibrium (i.e. Curtin-Hammett type condi-
25 tions). Consistent with this assumption, ethylene coordination to
nisms for ethylene oligomerization by related Sasol and Phillips
26 Cr-type catalysts. Combined with experimental studies,37 and our the chromacycloheptane intermediate is endergonic by ~3
27 own calculations (see Supporting Information (SI)), Scheme 3 kcal/mol. For catalyst 1a, the ∆G(TS1-TS2) of ~3 kcal/mol, and is
28 shows the most plausible catalytic mechanism that has emerged quantitatively in accord with the 94%:1% C6:C8 relative weight
29 for ethylene trimerization and tetramerization. Pre-catalyst activa- ratio.
30 tion generates a low-valent Cr species A with ethylene coordina-
31 tion. Oxidative C-C bond coupling forms chromacyclopentane B.
Another ethylene coordination gives intermediate C and migrato-
32
ry insertion leads to the key chromacycloheptane intermediate D.
33 The catalytic cycle diverges into two pathways at this chromacy-
34 cloheptane intermediate. In one pathway, β-hydrogen transfer,
35 which can be considered a one-step β-hydrogen elimina-
36 tion/reductive elimination process, results in formation of 1-
37 hexene and Cr catalyst reduction (blue arrows). In a second path-
way, ethylene coordination by intermediate E and migratory in-
38
sertion leads to the chromacyclononane intermediate F that leads
39 to 1-octene (red arrows). Therefore, selectivity can result from
40 competitive β-hydrogen transfer and ethylene migratory insertion
41 from intermediate D.
42
43
44
45
46
47
48
49
50
51 Figure 1. Top: TS1 and TS2 transition-state structures for cata-
52 lyst 1a. Bottom: Predictive linear correlation plot between ∆G(TS1-
53 TS2) and natural log of 1-hexene:1-octene weight ratio.
54
55 While accurate prediction for individual catalysts is important, it
56 is potentially more powerful to correlate48 ∆G(TS1-TS2) values and
57 the relative % weight of 1-hexene to 1-octene. This type of ap-
58
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proach has the advantage of reducing errors in predicting selectiv- TS2 for L1 and L2. Inspection of these structures shows that the
1 ity for some experimental parameters not directly included in this 2-methyl group of L1 resides close to the Cr catalytic pocket and
2 DFT transition-state model, but it may have the disadvantage of intrudes in the ethylene migratory insertion transition state. Re-
3 being less accurate for ligands that have large electronic or struc- moval of this alkyl group lowers the energy of TS2 and results in
tural changes to the (P,N) core scaffold. Therefore, we explored significantly greater 1-octene production. Importantly, the pre-
4
all reasonable transition-state conformations for catalysts 1a-1e. dicted 44:56 % weight of 1-hexene:1-octene is significantly high-
5 The bottom of Figure 1 plots the energy difference between the er in 1-octene content than any of the catalysts 1a-1e previously
6 lowest energy structures for TS1 and TS2 (∆G(TS1-TS2)) for cata- tested. Subsequent synthesis of the (L2)CrIII(Cl)3(THF) complex
7 lysts 1a-1e versus their experimental relative weight % of alkenes and ethylene oligomerization reaction testing under standard con-
8 by ln(C6/C8). This direct correlation approach gives a high degree ditions resulted in a quantitative confirmation of this prediction
9 of linear correlation with a slope of 1.08 (y = 1.079x + 2.076) and with a C6:C8 weight % ratio of 43:57 (Scheme 4), and confirms
10 an R2 value of 0.97. the controllable shift from C6 selectivity towards C8 selectivity
through modification of the backbone monocyclic imine group.
11 With the correlation curve in Figure 1 complete, we began the
The (L2)CrIII catalyst complex was confirmed with an X-ray
12 design of new classes of phosphine imine Cr catalysts for predict-
able control of the 1-hexene to 1-octene ratio. Our calculations structure of the [Li(THF)2]+[(L2)CrIIICl4]- complex (bottom right-
13 quickly converged on phosphine monocyclic imine catalysts hand corner of Scheme 4).
14 (Scheme 4 shows the Cr (P,N) ligands). Phosphine monocyclic
15 imines retain the (P,N) ligand core, but provide a significantly
16 new steric and electronic environment with several ligand posi-
17 tions that can be readily modified. We first calculated TS1 and
18 TS2 for 2-methyl-3,4-dihydro-2H-pyrrol-5-amine phosphine (L1,
Scheme 4 and Figure 2). This 2-substituted monocyclic imine was
19 chosen first because it was assumed based on previous experi-
20 mental results that substitution at or near the imine functional
21 group will result in high LAO purity and potential selectivity for
22 1-octene.17-18 However, the calculated selectivity suggested a
23 94:06 relative % weight of 1-hexene:1-octene, which is a ratio
24 similar to that observed for catalysts 1a and 1b. Subsequent syn-
thesis of the (L1)CrIII(Cl)3(THF) complex and testing of ethylene
25
oligomerization under standard conditions confirmed the predic-
26 tion of C6 selectivity with an experimental C6:C8 ratio of 85:15. In
27 this case, and in some cases, C6 selectivity is slightly overestimat-
28 ed. However, this overestimation of C6 selectivity is advantageous
29 in our DFT transition-state model since the goal is to increase
30 selectivity towards C8 production
31 Computational Design of (P,N) Ligands and Catalysts

32
NH NH
33 Me NH N NH N N
N Me
P P
P P Figure 2. TS1 and TS2 transition-state structures for cationic
34
(L1)CrIII(C6H12) and (L2)CrIII(C6H12).
35 Prediction Prediction Prediction Prediction
To test if L2 is a general class of ligand with the capability of 1-
36 L1 L2 L3 L4
octene selectivity based on transition states, we computationally
37
94:06 44:56 99:01 49:51

Experiment Experiment Experiment

predicted and then experimentally examined the selectivity for the
38
Experiment
L1 L2 L3 L4 corresponding six-membered and seven-membered monocyclic
39 85:15 43:57 93:07 47:53
imine ligands with and without the α-methyl imine group. Indeed,
40 tetrahydropyridin-2-amine L3 and tetrahydro-2H-azepin-7-amine
41 Me
N NH N NH L5 were predicted to give complete selectivity for 1-hexene while
42
P P L4 and L6 were predicted to have 49:51 and 62:38 % weight
ratios, respectively (Scheme 4). Experimental testing of these
43 catalysts confirmed the quantitative predictions of the C6 selective
Prediction
44
Prediction
L5 L6 catalysts with L3 and L5 ligands. Experiments also confirmed a
45 99:01 62:38
very close prediction for the catalysts with ligand L4 for C8 selec-
46 Experiment
L5
Experiment
L6
tivity. The prediction for catalysis with ligand L6 underestimated
47 NA 52:48 the C8 production by ~10%.
48 Scheme 4. Predicted 1-Hexene:1-Octene Weight % Ratio for Cr- This combined computational-experimental study demonstrates
49 catalyzed Ethylene Oligomerization with Phosphine Monocyclic the successful use of a practical DFT transition-state model for
50 Imine Ligands. Experimental Weight % Ratios are Normalized for quantitative prediction and experimental realization of designing
C6+C8 Fractions and Include All C6 or C8 Components. (Bottom new classes of Cr phosphine imine catalysts for control of eth-
51 ylene trimerization/tetramerization selectivity. This begins our
Right-Hand Corner: X-ray Structure for
52 efforts to identify new classes of Cr catalysts and ligands by using
[Li(THF)2]+[(L2)CrIIICl4]-. NA = Catalyst Not Synthesized.)
53 computational design to predict catalyst selectivity and activity.
Our calculations identified that removal of the 2-methyl group in
54 L1 could lead to a dramatic shift in increased C8 production. Cal-
55 culation of TS1 and TS2 for the 3,4-dihydro-2H-pyrrol-5-amine
56 phosphine ligand L2 gave a prediction of 44%:56% weight C6:C8 ASSOCIATED CONTENT
57 ratio. Figure 2 shows the transition-state structures for TS1 and
58
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AUTHOR INFORMATION (14) For organometallic examples see: (a) Wang, Y.; Wang, J.; Su, J.;
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(38) Zhao, Y.; Truhlar, D., Theor. Chem. Acc. 2008, 120, 215−241. changes made no significant difference in predicted 1-hexene/1-
1 (39) Zhao, Y.; Truhlar, D. G., Acc. Chem. Res. 2008, 41, 157−167 octene selectivity.
(40) (a) DFT calculations were carried out in Gaussian 09. (b) Frisch, (46) van Rensburg, W. J.; van den Berg, J-A.; Steynberg, P. J. Organ-
2 M. J. et al. Gaussian 09, Revision B.01, Gaussian, Inc.: ometallics 2007, 26, 1000−1013.
3 Wallingford, CT, USA, 2009. (47) (a) 3D strucutres were rendered suing CYLview. (b) Legault, C. Y.
4 (41) Def2-TZVP basis sets were downloaded from CYLview, 1.0b, Université de Sherbrooke: 2009.
https://bse.pnl.gov/bse/portal (01/01/2015). (48) (a) QSAR-DFT methods have been used to examine bisphosphine
5
(42) Weigend, F.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2005, 7, amine (PNP) type ligands for LAO selectivity. Tang, S.; Liu, Z.;
6 3297−3305. Zhan, X.; Cheng, R.; He, X.; Liu, B. J. Mol. Model. 2014, 20,
7 (43) Andrae, D.; Haeussermann, U.; Dolg, M.; Stoll, H.; Preuss, H. 2129. (b) For a general QSAR review see: Karelson, M.;
8 Theor. Chim. Acta. 1990, 77, 123−141. Lobanov, V. S.; Katritzky, A. R. Chem. Rev. 1996, 96,
(44) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G., J. Phys. Chem. B. 1027−1043
9 2009, 113, 6378−6396.
10 (45) We also examined changes to the (P,N) ligand structure due to
11 NH activation by alkylaluminums, such as R2’N-AlR2, but these
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