Development of Improved Amidoquinoline Polyolefin Catalysts with Ultrahigh Molecular Weight Capacity

Article abstract of DOI:10.1021/acs.organomet.5b00053

A new synthetic route to amidoquinoline olefin polymerization catalysts has been developed involving significantly less expensive and more readily available starting materials. The new methodology was used to prepare N-mesityl-2-methylquinolin-8-amine, which in turn was converted into trialkyl complexes of Hf, Zr, and Ti. The new complexes were characterized by elemental analysis, 1D and 2D NMR spectroscopy, and X-ray crystallography. A batch reactor ethylene/1-octene copolymerization evaluation at 140 C showed that the new Hf congener outperformed a series of previously reported molecular olefin polymerization catalysts. In particular, the new Hf catalyst exhibits excellent activity and a remarkable capacity to produce ultrahigh molecular weight copolymers at elevated reaction temperatures. (Chemical Presented).

Full text of DOI:10.1021/acs.organomet.5b00053

Article
pubs.acs.org/Organometallics
Development of Improved Amidoquinoline Polyolefin Catalysts with
Ultrahigh Molecular Weight Capacity
Philip P. Fontaine* and Steve Ueligger
Performance Plastics R&D, The Dow Chemical Company, Freeport, Texas 77541, United States
Jerzy Klosin, Amaruka Hazari, Joe Daller, and Jianbo Hou
Corporate R&D, The Dow Chemical Company, 1776 Building, Midland, Michigan 48674, United States
*
S Supporting Information
ABSTRACT: A new synthetic route to amidoquinoline olefin
polymerization catalysts has been developed involving significantly
less expensive and more readily available starting materials. The
new methodology was used to prepare N-mesityl-2-methylquino-
lin-8-amine, which in turn was converted into trialkyl complexes of
Hf, Zr, and Ti. The new complexes were characterized by
elemental analysis, 1D and 2D NMR spectroscopy, and X-ray
crystallography. A batch reactor ethylene/1-octene copolymeriza-
tion evaluation at 140 °C showed that the new Hf congener outperformed a series of previously reported molecular olefin
polymerization catalysts. In particular, the new Hf catalyst exhibits excellent activity and a remarkable capacity to produce
ultrahigh molecular weight copolymers at elevated reaction temperatures.
INTRODUCTION
comparative study. Finally, the new complexes were evaluated in
a series of batch reactor ethylene/1-octene copolymerization
reactions.
■
1
Polyolefin catalyst families that are inexpensive, easily prepared,
highly active, and composed of modular frameworks have
potential industrial utility. Recently, we discovered a promising
2
−4
RESULTS AND DISCUSSION
new class of catalysts supported by amidoquinoline ligands,
which are a subset of a larger class of imino-amido-type
■
New Synthetic Route to Ligand. The previously reported
route to the representative ligand precursor is shown in Scheme
1, along with the catalogue costs and sale quantities of the raw
materials. The preparation involves coupling of 8-bromo-2,4-
dimethylquinoline (1) with 2,6-dimethylaniline (2), to afford the
desired aminoquinoline 3 in moderate yield. A subsequent
5
,6
catalysts that have been extensively studied in our laboratory.
Such catalysts have been used to access novel and industrially
6f
relevant polyolefin structures such as olefin block copolymers.
For the Hf amidoquinoline catalysts, excellent activities were
observed at elevated reaction temperatures, along with the
capacity to produce extremely high molecular weight ethylene/1-
octene copolymers. The thermal and chemical stability of the
amidoquinoline ligands and precatalysts was another advantage,
as some previously reported imino-amido catalysts were seen to
be prone to isomerization, the result of which was a loss of several
desirable catalyst attributes.
reaction of 3 with HfBn in turn provided the precatalyst 3-
4
HfBn (Scheme 2). The major problem is the high cost and
3
limited availability of 1, for which only a single vendor was
identified. Note that the unsubstituted analogue (i.e., 8-
bromoquinoline) is also prohibitively expensive and similarly
limited in its availability. Moreover, the resulting Hf-based
polyolefin catalyst derived from 8-bromoquinoline was less
efficient, displayed lower molecular weight capacity, and
One drawback of the previously reported amidoquinoline
2
complexes, however, was that while the reported synthesis was
produced a copolymer with a broader compositional distribution,
relatively simple and required only two preparative steps, the raw
material cost was prohibitively high for large-scale operations.
Given the promising results from the initial evaluation, we sought
to develop a cost-effective route to these catalysts from materials
that are readily commercially available. Important structural
attributes of the previously reported ligands were identified and
preserved in the design of a new ligand that can be prepared via a
synthetic approach that greatly reduces the material cost and
maintains relative synthetic ease. Additionally, with larger
quantities of the ligand precursor in hand, in addition to the
Hf complex we were able to prepare Zr and Ti analogues for a
2
relative to that derived from 3-HfBn3.
We hypothesized that the observed differences between 3-
HfBn and the analogous catalyst derived from the unsubstituted
3
quinoline were due to the methyl substitution at the 2 position,
which is in close proximity to the active site and might serve to
suppress any adverse reactivity at the more activated carbon ortho
7
to the quinolino nitrogen. Specifically, since the polymer
Received: January 26, 2015
Published: March 31, 2015
©
2015 American Chemical Society
1354
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
2
Scheme 1. Previously Reported Route to the Aminoquinoline Ligand, Including Material Costs and Quantities
2
Scheme 2. Previously Reported Preparation of 3-HfBn3
final ligand, which we deemed to be important based on the
previous study. The coupling proceeded smoothly, affording the
2
desired ligand N-mesityl-2-methylquinolin-8-amine (7) as a
bright yellow solid in 79% yield after column chromatography.
While this new route necessitates an additional synthetic step,
this is easily offset by the much lower cost and higher availability
of the starting materials. For example, 4 is over 400 times less
expensive than 1. It is worth noting that 5 is also commercially
available, albeit at a significantly higher cost than 4.
As with the previously prepared aminoquinoline ligands, 7
showed appreciable solubility in hydrocarbon solvents and could
be recrystallized if desired. Single crystals of 7 suitable for X-ray
diffraction were obtained by slow evaporation of a toluene
solution. The solid-state structure shows a planar quinolino core
with an orthogonal 2,6-dimethylaniline group (Figure 1). Bond
produced by 3-HfBn had a narrower compositional distribution,
3
we postulated that substitution at the 2-position inhibited, to
some extent, the formation of a second active species. With this in
mind, we looked for a less expensive starting material that
retained an analogous substitution pattern. Fortunately, such a
material exists, along with a literature report of its transformation
to a precursor of our desired ligand target (Scheme 3). The
2
,9
angles and distances for 7 are similar to those of 3.
previous report describes the conversion of 8-hydroxyquinaldine
8
(
4) in high yields to 8-aminoquinaldine (5). Indeed, we found
that this route is practical and amenable to large-scale
preparations. We isolated 5 in 45% yield on the first attempt
via column chromatography as a pale yellow solid that has
moderate solubility in aliphatic hydrocarbons and excellent
solubility in aromatic hydrocarbons. The reaction was very clean,
and the only byproduct observed was unreacted starting material,
so we believe that the yield could be easily improved (the
reported literature yield is 97%, for example). With several grams
of 5 in hand, however, we moved on to the next step of the
synthesis without further optimization of this reaction.
The conversion of 5 into the desired aminoquinoline ligand 7
required a Pd-catalyzed coupling with an aryl bromide. Note that
in this case the functionality of the substrates was the reverse of
the previous route, which coupled an aniline derivative with a
bromoquinoline. For the new reaction 2-bromomesitylene (6)
was selected, as it was among the least expensive of the available
aryl halides that would lead to 2,6-dimethyl substitution in the
Figure 1. Molecular structure of 7. Hydrogen atoms, except H1, are
omitted for clarity. Thermal ellipsoids are shown at the 50% probability
level. Selected bond lengths (Å) and angle (deg): C1−N1 = 1.3915(15),
C6−N2 = 1.3652(15), C1−C6 = 1.4367(16), C1−N1−C10
120.14(19).
Scheme 3. New Route to Aminoquinoline Ligand, Including Material Costs and Quantities
1
355
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
Preparation of Metal Complexes. The ligand precursor 7
was reacted with group IV metal tetrabenzyl (MBn , M = Hf, Zr,
4
Ti) compounds to furnish, in the cases of Hf and Zr, the
respective amidoquinoline tribenzyl species 7-HfBn and 7-
3
ZrBn (Scheme 4). The analogous chemistry did not proceed for
3
Scheme 4. Preparation of Hf and Zr Amidoquinoline
Complexes
TiBn ; no reaction occurred even after several days at ambient
4
temperature, and the thermal instability of TiBn precluded
performing this reaction at elevated temperatures. Both 7-HfBn3
4
Figure 3. Molecular structure of 7-HfBn . Hydrogen atoms are omitted
3
for clarity. Thermal ellipsoids are shown at the 50% probability level.
Selected bond lengths (Å) and angle (deg): Hf−N1 = 2.090(2), Hf−
N2= 2.344(2), N1−C1 = 1.396(3), N2−C6 = 1.377(4), Hf−C20 =
2.247(3), Hf−C21 = 2.277(3), Hf−C22 =2.258(3), N1−Hf−N2 =
and 7-ZrBn were isolated in high yields as deep red crystalline
3
solids that have limited solubility in hexane and excellent
1
solubility in aromatic hydrocarbons. H NMR spectroscopy
7
2.76(9).
revealed fluxional behavior for both, in keeping with prior
2
observations for amidoquinoline complexes. Specifically, an
exchange process that renders the three benzyl groups equivalent
occurs on the NMR time scale at ambient temperature. This is
evidenced by substantially broadened resonances corresponding
to the protons of the benzyl groups (Figure 2). It appears that the
occupying the equatorial plane. The nitrogen donors of the
anionic Hf−N bonds are notably shorter in both cases, by about
0
.25 Å, than the neutral quinoline nitrogen donors.
A synthetic route to 7-TiMe3 was devised using well-
10
barrier to this process is slightly lower for 7-ZrBn , since the
3
established literature protocols (Scheme 5). Treatment of a
resonances of the benzyl groups are noticeably sharper relative to
those for 7-HfBn3.
concentrated solution of 7 with Ti(NMe ) at 50 °C led to the
2
4
formation of 7-Ti(NMe ) . Recrystallization of the crude
2 3
The molecular structure of 7-HfBn3 (Figure 3) was
determined by single crystal X-ray analysis, and is similar to
product from hexane at −30 °C afforded orange crystals of 7-
1
Ti(NMe ) in 75% isolated yield. The H NMR spectrum of 7-
2
3
that of 3-HfBn . Both adopt distorted trigonal bipyramidal
Ti(NMe ) at ambient temperature is indicative of the dynamic
3
2 3
geometries, with the anilino donor and two of the benzyl ligands
behavior of the complex in solution (Figure 4). Three separate
1
Figure 2. H NMR spectra of 7-HfBn and 7-ZrBn at ambient temperature (in C D ).
3
3
6
6
1
356
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
Scheme 5. Preparation of Ti Amidoquinoline Complexes
Figure 5. Molecular structure of complex 7-Ti(NMe ) . Complex 7-
2
3
Ti(NMe ) crystallizes with four independent molecules in the unit cell.
2
3
Hydrogen atoms are omitted for clarity. Thermal ellipsoids are shown at
5
2
1
0% probability. Selected bond lengths (Å) and angle (deg): Ti−N1=
.0272(10), Ti−N2 = 2.3049(10), N1−C1 = 1.3800(15), N2−C6 =
.3712(16), Ti−N3 = 1.9174(11), Ti−N4 = 1.9168(11), Ti−N5
=
1.9333(11), N1−Ti−N2 = 74.42(4).
resonances corresponding to NMe groups are observed at 3.40,
2
2
.85, and 2.65 ppm; two of the resonances (3.40 and 2.65 ppm)
result of hindered rotation along the Ti−N3 and Ti−N4 bonds,
giving rise at ambient temperature to two broad resonances
corresponding to C20/C22 and C21/C23 methyl groups. The
sharp resonance at 2.85 ppm corresponds to the homotopic
methyl groups C24 and C25. It should be stated that this
exchange process is fundamentally different than the afore-
are very broad, while the third resonance (2.85 ppm) remains
sharp. At 75 °C, the broad resonances at 3.40 and 2.65 ppm
coalesced into a single, broad peak at 3.1 ppm as a result of fast
chemical exchange, while the signal at 2.85 ppm remains
unchanged. The solid-state molecular structure of 7-Ti(NMe2)3
(
Figure 5) shows two distinctly different NMe groups. The
mentioned fluxional behavior exhibited by 7-HfBn and 7-
2
3
NMe group in the axial position of the trigonal bipyramid has a
ZrBn , in which all three benzyl groups undergo chemical
2
3
nitrogen atom (N5) in the plane of the Ti-amidoquinoline
framework with Me groups (C24/C25) (chemically equivalent)
positioned above and below the ligand plane. The other two
NMe groups are in the equatorial positions of the trigonal
2
bipyramid and are chemically equivalent; however, each contains
two chemically inequivalent methyl groups. Thus, C20 is
different from C21 and C22 is different from C23, while C21
and C23 (belonging to two different NMe2 groups) are
equivalent, as are C20 and C22. On the basis of these
observations, we believe that the observed fluxional process is a
that the barrier for such an exchange is higher for 7-Ti(NMe2)3
due to the comparative bulk of the NMe groups relative to Bn
2
groups, and hence at ambient temperature NMe interconver-
2
sion is in the slow exchange regime of the NMR time scale.
Treatment of 7-Ti(NMe ) with an excess of SiMe Cl in
2
3
2
2
toluene led to the precipitation of the trichloride complex 7-
1
Figure 4. Portion of the H NMR spectrum (in C D ) for 7-Ti(NMe ) , at 25 °C (bottom) and 75 °C (top).
6
6
2
3
1
357
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
1
TiCl as a black, crystalline solid. In the H NMR spectrum of 7-
Ti complexes display distorted trigonal bipyramidal geometry in
the solid state in which the quinoline nitrogen and one of the
3
TiCl , the chemical shifts of the aromatic protons on the
3
quinoline framework vary from those of the other complexes of
the ligand 7 reported here. In particular, the proton ortho (H2) to
the anilide nitrogen is significantly shifted upfield to 5.85 ppm,
suggestive of increased anisotropic shielding resulting from the
proximity of the arene ring coordinated to the anilide nitrogen.
Conversely, the protons para to the anilide nitrogen and meta to
the quinoline nitrogen are significantly shifted upfield (to 7.50
and 7.61 ppm, respectively) relative to the other complexes of 7,
indicative of the different electronic nature of the aromatic ring
three X-type ligands (Cl, Me, or NMe ) occupy the axial
2
positions, while the anilide nitrogen and remaining two X-type
ligands occupy the equatorial positions. Throughout the series,
relatively little variation is observed between the structures in
terms of bond distances and angles.
Polymerization Evaluation. A series of ethylene/1-octene
copolymerization runs were carried out in a 2 L batch reactor at
140 °C with a 2:1 molar ratio of 1-octene to ethylene, using
[HNMe(C H ) ][B(C F ) ] as the activator. In addition to the
18
37 2
6 5 4
system for this complex. Alkylation of 7-TiCl with three
3
new amidoquinoline complexes, 3-HfBn , several previously
3
equivalents of MeMgBr afforded complex 7-TiMe as a red,
3
reported imino-enamido and imino-amido catalysts, and a
constrained geometry catalyst (CGC) were also tested for
comparative purposes (Figure 8).
1
crystalline solid. The H NMR spectrum collected at ambient
temperature showed a single, slightly broad resonance at 1.81
ppm, corresponding to the three Ti-Me groups. The equivalence
of the three Me groups and the broadness apparent in the
resonance point to an exchange process that is analogous to that
which occurs for 7-HfBn and 7-ZrBn . Crystals suitable for X-
3
3
ray diffraction were obtained from hexane at −30 °C. Molecular
structures for complexes 7-Ti(NMe ) , 7-TiCl , and 7-TiMe , as
2
3
3
3
well as selected bond lengths and angles, are shown in Figures 5,
, and 7, respectively. As with the Zr and Hf complexes, all three
6
Figure 6. Molecular structure of complex 7-TiCl . Thermal ellipsoids
3
are shown at 50% probability. Selected bond lengths (Å) and angle
(
1
2
deg): Ti−N1= 1.9178(11), Ti−N2 = 2.2187(11), N2−C6 =
.3725(16), N1−C1 = 1.4053(16), Ti−Cl1 = 2.2477(4), Ti−Cl2 =
.2490(4), Ti−Cl3 =2.2527(4), N1−Ti−N2 = 77.89(4).
Figure 8. Complexes evaluated in polymerization reactions.
The results are shown in Table 1. A comparison of the data
obtained using 3-HfBn and 7-HfBn reveals the similarity
3
3
between the two catalysts, with the latter showing slight
improvements in activity, polymer molecular weight capacity,
and 1-octene incorporation. The zirconium congener 7-ZrBn3
resulted in a significantly poorer catalyst in terms of both activity
and molecular weight building capacity, while the titanium
analogue 7-TiMe3 was completely inactive under these
conditions. The trends observed for the Hf and Zr congeners
are similar to what has been observed previously for imino-
5
Figure 7. Molecular structure of complex 7-TiMe . Thermal ellipsoids
are shown at 50% probability. Selected bond lengths (Å) and angle
enamido and imino-amido systems. Notably, 7-HfBn3
3
produced the copolymer with the highest molecular weight
M = 460 474 g/mol at 140 °C) among all the catalysts tested,
an impressive feature of the new catalyst. Additionally, 7-HfBn3
(
deg): Ti−N1= 1.9755(14), Ti−N2 = 2.3072(14), N1−C1 = 1.393(2),
(
w
N2−C6 = 1.373(2), Ti−C20 = 2.1082(18), Ti−C21 = 2.0988(19), Ti−
C22 = 2.0995(19), N1−Ti−N2 = 75.69(5).
exhibited the highest propensity, along with 8-HfBn , to
3
incorporate 1-octene (13.3 mol %) among the imino-amido-
type catalysts.
1
358
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
a
Table 1. Ethylene/1-Octene Copolymerization Data at 140 °C
b
c
catalyst (μmol)
poly. yield (g)
activity
TM (°C)
M (g/mol)
w
M /Mn
w
octene incorp. (mol %)
3
7
7
8
8
9
9
-HfBn (0.6)
28.6
33.6
18.3
39.9
20.6
14.3
16.1
36.1
39 722
46 667
6100
49
45
400 180
460 474
285 188
237 090
233 176
64 607
3.18
3.38
3.68
2.44
7.06
2.04
8.43
2.54
12.0
13.3
10.4
13.3
9.8
3
-HfBn (0.6)
3
-ZrBn (2.5)
63
3
-HfBn (0.6)
55 417
8583
49, 97
65, 102
88
3
-ZrBn (2.0)
3
-HfBn (0.5)
23 833
19 167
100 278
7.4
3
-ZrBn (0.7)
100
7
113 667
23 277
4.8
3
CGC (0.3)
25.3
a
Polymerization conditions: 140 °C, 605 g of Isopar E, 300 g of 1-octene, and 288 psi of ethylene (∼42 g), precatalyst:activator = 1:1.2; activator
b
[
HNMe(C H ) ][B(C F ) ]; precatalyst: MMAO = 1:10; reaction time 10 min. Activity reported in units of grams polymer/mmol catalyst.
18 37 2 6 5 4
c
1
Octene content determined by H NMR spectroscopy.
1
Figure 9. Fragments of H NMR spectra of selected copolymers showing olefin region. Asterisk denotes impurity peaks resulting from polymer
degradation after prolonged heating at high temperature needed for polymer dissolution.
Table 2. Mole Fractions (in ppm) of Unsaturated Groups in the Copolymers
catalyst
vinylene (Internal, Vy3)
trisubst’d (Internal, T)
vinyl (V)
vinylene (Vy1 + Vy2)
vinylidene (Vd)
total terminal unsat’n
3
-HfBn3
-HfBn3
-ZrBn3
-HfBn3
-ZrBn3
-HfBn3
-ZrBn3
0
0
12
17
24
3
49
33
88
76
57
41
194
150
7
7
8
8
9
9
0
111
113
291
129
583
290
186
163
254
610
437
574
82
379
0
59
335
0
23
0
99
644
0
167
261
552
906
0
31
529
1281
1416
CGC
935
The capacity of 7-HfBn to produce ultrahigh polymer
amount of chain end unsaturation is directly related to the
catalyst molecular weight building capacity. Additionally, the
type of (terminal) unsaturation is determined by the specifics of
the termination mechanism; for example, termination after an
ethylene insertion results in a vinyl end group, whereas
termination after an α-olefin insertion leads to a vinlyene
(following a 2,1-insertion) or a vinylidene (following a 1,2-
insertion). The types and various amounts of these unsaturations
can directly impact the resulting polymer architecture and
properties; for example, the influence of vinyl groups’
concentration on long-chain branching formation is well
3
molecular weights at elevated temperatures, and with good
catalytic activity, is an attractive feature of this new catalyst.
Generally speaking, molecular weight building capacity is a very
valuable characteristic of molecular polyolefin catalysis, especially
at elevated temperatures. In order to gain a more detailed
understanding of this promising new catalyst, we carried out end
group analyses on the copolymers obtained in this study. Such
analysis can provide detailed information about the catalyst
11
behavior, specifically with regard to the termination events. For
polymerization runs conducted without hydrogen as a molecular
weight control agent, chain termination results in terminal
unsaturation for every polymer chain, and, as such, the total
12
established. For the copolymers generated in this study, a
striking detail is the variation in the amount of total terminal
1
359
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
unsaturations, which as expected trended with copolymer
molecular weight determined by GPC. The copolymer with
resulting mixture was heated to 170 °C for 2 days, at which point the
contents were drained out, rinsing with water (100 mL). This mixture
was extracted with CH Cl (3 × 50 mL), and the combined organic
the lowest molecular weight (M = 23 277 g/mol made by CGC)
2
2
w
extracts were dried over MgSO . NMR analysis showed partial
4
showed the highest number of terminal unsaturations (1416
conversion to the desired material and unreacted starting material.
Rather than continuing the reaction, the mixture was purified at this
point via column chromatography on silica gel, eluting with 1:1 CH Cl /
ppm), while the copolymer (M = 460 474 g/mol) made by 7-
w
HfBn had almost an order of magnitude lower level of
3
2
2
unsaturation (150 ppm). The relative distribution of unsatura-
tion types was similar among all copolymers derived from imino-
amido, imino-enamido, and amidoquinoline catalysts (Figure 9,
Table 2), with the main difference being the level of unsaturation.
hexane, affording 5 as a yellow solid (4.50 g, 45%). Spectroscopic data
8
were consistent with the published data.
For the copolymer made by 7-HfBn , the intensities of the vinyl,
3
vinylene, and vinylidene end groups were lower relative to all the
other catalysts, indicating higher termination barriers following
both ethylene and octene (1,2 and 2,1) insertions for this
catalyst. In contrast to CGC, all the imino-amido-type catalysts
produced very small amounts of internal unsaturations (Vy3, T).
Preparation of N-Mesityl-2-methylquinolin-8-amine (7). A round-
bottomed flask equipped with a reflux condenser was charged with
Pd (dba) (0.72 g, 0.79 mmol), rac-BINAP (1.08 g, 1.74 mmol), and
2
3
sodium tert-butoxide (2.13 g, 22.1 mmol) in toluene (75 mL). To the
resulting suspension were added 5 (2.50 g, 15.8 mmol) and 6 (3.73 g,
SUMMARY
■
A new synthetic route to amidoquinoline ligands has been
developed involving significantly less expensive and more readily
available starting materials. The new methodology was used to
prepare N-mesityl-2-methylquinolin-8-amine (7), which in turn
was reacted with Hf and Zr tetrabenzyl precursors, affording the
respective tribenzyl compounds 7-HfBn3 and 7-ZrBn3 in
excellent yields. The analogous trialkyl Ti complex, 7-TiMe3,
was synthesized via chlorination and subsequent alkylation of 7-
Ti(NMe ) The new complexes were characterized by NMR
1
5.8 mmol). The mixture was heated under reflux overnight and then
pumped down to dryness under vacuum. The crude residue was purified
by flash column chromatography eluting with 5% EtOAc in hexane. The
product was dried under vacuum, affording 7 as a bright yellow solid
1
3
(
8
3.45 g, 79%). H NMR (C D ): 7.76 (1H, s, NH); 7.58 (1H, d, J
=
6
6
H−H
3
3
.4 Hz, H7), 7.13 (1H, dd, J
= 8.1, 7.6 Hz, H3), 6.95 (1H, dd, J
H−H H−H
4
=
8.1 Hz, J
= 1.2 Hz, H4), 6.85 (2H, m, H12, H14); 6.80 (1H, d,
H−H
3
3
4
JH−H = 8.4 Hz, H8), 6.41 (1H, dd, J
.51 (3H, s, Me ), 2.18 (3H, s, Me ), 2.17 (6H, s, Me17,18). C{ H}
= 7.6 Hz, J
= 1.2 Hz, H2),
H−H
H−H
1
3
1
2
16 19
2
3.
NMR (C D ): 156.0, 143.7, 138.4, 137.2, 136.7, 136.6, 136.01, 129.96,
6
6
spectroscopy and X-ray crystallography.
A batch reactor ethylene/1-octene copolymerization evalua-
tion showed that 7-HfBn compared favorably to previously
1
27.8, 127.6, 122.5, 115.1, 106.6, 25.5, 21.4, 18.7. ES-HRMS (m/e):
+
calcd for C H N (M + H) 277.1705, found 277.1706.
21
24
2
3
reported amidoquinoline catalysts and outperformed many of
the previously reported imino-amido-based catalysts. The new
catalyst derived from 7-HfBn exhibited excellent activity and an
3
impressive capacity to produce ultrahigh molecular weight
copolymers. The discovery of advantaged catalysts such as 7-
HfBn that can be easily prepared in a few steps from inexpensive
3
and readily available materials is an important goal within the
industrial polyolefin community and remains a research focus in
our laboratory.
Preparation of (Mesityl(2-methylquinolin-8-yl)amino)-
tribenzylhafnium (7-HfBn ). A solution of 7 (0.285 g, 1.03 mmol) in
3
toluene (5 mL) was cooled to −30 °C, then added to a vial containing
HfBn (0.528 g, 0.973 mmol). The resulting solution turned orange
4
EXPERIMENTAL SECTION
immediately and was allowed to warm to ambient temperature and
stirred for 0.5 h. The volume of toluene was reduced to ca. 2 mL, and
hexane (ca. 8 mL) was added, at which point the solution was cooled to
−30 °C. After 1 day, the resulting orange crystals were collected and
dried under vacuum, affording the desired product in high purity (0.67 g,
■
General Considerations. All reagents and solvents were obtained
from commercial sources and used directly, unless otherwise noted.
Toluene and hexane were degassed and dried over alumina prior to use.
Air-sensitive manipulations were performed in a Vacuum Atmospheres
inert atmosphere glovebox under a dry nitrogen atmosphere or by using
standard Schlenk and vacuum line techniques. NMR spectra were
recorded on Bruker Avance-400 and Varian Mercury-400 spectrom-
95%). Anal. Calcd for C40H40HfN : C, 66.06; H, 5.54; N, 3.85. Found:
2
1
3
C, 66.16; H, 5.49; N, 3.78. H NMR (C
Hz, H7), 7.02 (1H, dd, JH−H = 8.1, 7.8 Hz, H3), 6.96 (2H, m, H12,
H14), 6.88 (6H, br, Hf-Bn), 6.70 (1H, dd, JH−H = 8.1 Hz, JH−H 3= 1.1
Hz, H4), 6.67 (3H, br, Hf-Bn), 6.56 (6H, br, Hf-Bn), 6.29 (1H, d, JH−H
= 8.4 Hz, H8), 6.20 (1H, dd, JH−H = 7.8 Hz, JH−H = 1.1 Hz, H2), 2.51
D
6
): 7.38 (1H, d, JH−H = 8.4
6
3
1
3
4
eters. H NMR data are reported as follows: chemical shift (integration,
multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p
1
3
4
=
pentet, and m = multiplet), and assignment). Chemical shifts for H
NMR data are reported in ppm downfield from internal tetramethylsi-
(6H, br, Hf-Bn), 2.23 (3H, s, Me19), 2.14 (6H, s, Me17,18), 1.98 (3H, s,
13
1
lane (TMS, δ scale) using residual protons in the deuterated solvent
Me16). C{ H} NMR (C D ): 159.6, 151.7, 147.0 (br), 144.1, 140.9,
6 6
1
3
(
C D , 7.15 ppm; toluene-d , 2.09 ppm) as references. C NMR data
139.5, 135.8, 135.3, 130.8, 129.6, 128.3 (br), 128.1, 127.9 (br), 123.8,
122.6 (br), 115.7, 111.2, 89.9 (br), 25.8, 21.4, 19.0.
6
6
8
1
were determined with H decoupling, and the chemical shifts are
reported in ppm vs tetramethylsilane (C D , 128.1 ppm; toluene-d ,
6
6
8
20.4 ppm). Elemental analyses were performed at Midwest Microlab,
LLC. High-resolution mass spectroscopy (HRMS) analyses were
carried out using flow injection (0.5 mL of 50/50 v/v% of 0.1% formic
acid in water/THF) on an Agilent 6520 quadrupole-time-of-flight MS
system via a dual-spray electrospray interface operating in the positive
ion mode.
Preparation of 2-Methylquinolin-8-amine (5). A 100 mL Parr
reactor was charged with 4 (10.0 g, 62.8 mmol), (NH ) SO ·H O (16.9
4
2
3
2
g, 126 mmol), and aqueous ammonia solution (32%, 50 mL). The
1
360
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
3
= 7.7, 4JH−H = 1.1 Hz, H2), 3.13 (3H, s, Me ), 2.38 (3H,
Preparation of (Mesityl(2-methylquinolin-8-yl)amino)-
5.83 (dd, J
H−H
16
4
4
13
tribenzylzirconium (7-ZrBn ). A solution of 7 (0.285 g, 1.03 mmol)
d, J
= 0.7 Hz, Me ), 2.28 (6H, d, J
(126 MHz, CD Cl ): δ 160.26, 156.75, 147.72, 141.01, 139.82, 138.49,
130.07, 129.39, 128.54, 128.04, 125.70, 122.85, 108.58, 25.67, 21.17,
8.45.
= 0.7 Hz, Me17,18). C NMR
3
H−H
19
H−H
in toluene (5 mL) was cooled to −30 °C, then added to a vial containing
2 2
ZrBn (0.443 g, 0.973 mmol). The resulting solution turned deep red
4
immediately and was allowed to warm to ambient temperature and
stirred for 0.5 h. The volume of toluene was reduced to ca. 2 mL, and
hexane (ca. 8 mL) was added, at which point the solution was cooled to
1
−
30 °C. After 1 day, the resulting deep red crystals were collected and
dried under vacuum, affording the desired product in high purity (0.62 g,
8
7
8%). Anal. Calcd for C H ZrN : C, 75.07; H, 6.30; N, 4.38. Found: C,
40 40 2
1
3
4.86; H, 6.25; N, 4.49. H NMR (C D ): 7.45 (1H, d, J = 8.3 Hz,
6
6
H−H
3
H7), 7.05 (1H, dd, J
= 8.0, 7.8 Hz, H3), 6.97 (2H, m, H12, H14),
H−H
3
4
6.95 (6H, br, Hf-Bn), 6.79 (1H, dd, JH−H = 8.0 Hz, J
= 1.1 Hz, H4),
H−H
= 1.1 Hz, H2), 2.32 (6H, br,
H−H
3
6.77 (3H, br, Hf-Bn), 6.64 (6H, br, Hf-Bn), 6.36 (1H, d, J
= 8.3 Hz,
3
4
H8), 6.26 (1H, dd, J
= 7.8 Hz, J
H−H
H−H
Preparation of (Mesityl(2-methylquinolin-8-yl)amino)-
trimethyltitanium (7-TiMe ). To 7-TiCl (0.681 g, 1.59 mmol)
Hf-Bn), 2.24 (3H, s, Me ), 2.10 (6H, s, Me
), 2.03 (3H, s, Me16).
19
17,18
3
3
1
3
1
C{ H} NMR (C D ): 158.6, 152.1, 147.2 (br), 146.3, 140.5, 139.5,
6
6
dissolved in 15 mL of toluene was added 1.69 mL (5.07 mmol) of a 3
M diethyl ether solution of MeMeBr, giving a deep red solution. The
reaction mixture was stirred for 1 h at ambient temperature. The solvent
was removed from the reaction mixture under reduced pressure. To the
residue was added 40 mL of hexane. After stirring for 5 min at ambient
temperature, the suspension was filtered, giving a red filtrate that was put
into the freezer (−30 °C). The supernatant was decanted from the
chilled filtrate, affording large red crystals, which were washed with 2 mL
of cold hexane and then dried under reduced pressure to give 0.158 g of
product (first crop). NMR spectroscopy showed the clean formation
product. The supernatant was dried under reduced pressure, leaving a
red, crystalline solid. To this residue was added 8 mL of hexane, which
partly dissolved the residue. This suspension was put into the freezer
1
1
35.3, 134.7, 130.7, 129.7 (br), 129.5, 127.7 (br), 123.9, 122.8 (br),
15.4, 110.1, 77.7 (br), 26.4, 21.4, 19.3.
Preparation of (Mesityl(2-methylquinolin-8-yl)amino)tris-
(
dimethylaminato)titanium (7-Ti(NMe ) ). To a solution of 7 (2.536
2 3
(
−30 °C) for 3 days. The supernatant was decanted from a red,
g, 9.2 mmol) dissolved in 10 mL of warm (60 °C) hexane was added
crystalline solid that was washed with 1 mL of cold hexane and then
dried under reduced pressure to give 0.182 g of product (second crop).
NMR showed clean product. Combined yield: 0.340 g, 58%. Anal. Calcd
for C H N Ti: C, 71.74; H, 7.61; N, 7.61. Found: C, 71.51; H, 7.38; N,
7
7
Ti(NMe ) (2.057 g, 9.2 mmol). The reaction mixture was heated at 65
2
4
°C. Within 30 min, the solution became deep red. After stirring for 22 h
at 65 °C, the resulting hazy solution was filtered. Upon filtration, large
crystals started to form. After 1 h at ambient temperature, the vial was
put into the freezer for 5 h (−30 °C). Crystals were collected on a frit,
washed with 2 mL of cold (−30 °C) hexane, and dried under reduced
pressure to produce 3.125 g of product. Yield: 75%. Anal. Calcd for
C H N Ti: C, 65.93; H, 8.19; N, 15.38. Found: C, 66.20; H, 7.86; N,
2
2
28
2
1
3
.46. H NMR (400 MHz, C D ): δ 7.41 (1H, d, J
.07 (1H, t, J
= 8.4 Hz, H7),
= 0.7 Hz, H12,
6
6
H−H
3
4
= 7.9 Hz, H3), 7.01 (2H, h, J
H−H
H−H
3
4
H14), 6.78 (1H, dd, J
Hz, H8), 6.27 (1H, dd, J
= 8.0, J
= 1.0 Hz, H4), 6.51 (1H, d, J = 8.4
H−H
H−H
3
4
= 7.8, J
= 1.1 Hz, H2), 2.49 (3H, s,
H−H
H−H
2
5
37
5
1
3
Me ), 2.37 (6H, s, Me ), 2.25 (3H, s, Me ), 1.81 (br s, 9H, Ti-Me).
16 17,18 19
C NMR (101 MHz, C D ): δ 156.84, 151.90, 146.85, 139.22, 138.90,
6 6
1
5.01. H NMR (500 MHz, C D ): δ 7.59 (1H, d, J
.14 (1H, t, J
JH−H = 7.9, J
dd, dd, J
= 8.3 Hz, H7),
6
6
H−H
13
3
7
= 7.9 Hz, H3), 7.05 (2H, m, H12, H14), 6.85 (1H, dd,
= 1.1 Hz, H4), 6.76 (1H, d, J = 8.3 Hz, H8), 6.18 (1H,
H−H
3
4
134.96, 133.71, 130.01, 129.08, 127.65, 123.43, 115.00, 107.61, 70.21
(br), 24.38, 21.12, 18.68.
H−H
= 7.9, J
3
4
= 1.1 Hz, H2), 3.60−3.20 (6H, br s, Ti-
H−H
H−H
Structure Determination. X-ray intensity data were collected on a
Bruker SMART diffractometer using Mo Kα radiation (λ = 0.710 73 Å)
and an APEXII CCD area detector. Raw data frames were read by the
N (CH )) 2.86 (6H, s, Ti-N (CH ) ), 2.80−2.50 (6H, br s, Ti-
eq
3
ax
3 2
N (CH )), 2.30 (3H, s, Me ), 2.27 (3H, s, Me ), 2.25 (6H, s, Me ).
eq
3
19
16
17,18
1
3
C NMR (126 MHz, C D ): δ 156.33, 153.64, 146.92, 139.77, 138.10,
6
6
13
SAINT program and integrated using 3D profiling algorithms. The
1
4
33.01, 132.34, 129.33, 129.19, 127.91, 123.15, 113.06, 106.55, 48.03,
5.37 (br), 22.01, 21.08, 21.06, 18.66.
resulting data were reduced to produce hkl reflections and their
intensities and estimated standard deviations. The data were corrected
for Lorentz and polarization effects, and numerical absorption
corrections were applied based on indexed and measured faces. The
structures were solved and refined in SHELXTL6.1, using full-matrix
least-squares refinement. The non-H atoms were refined with
anisotropic thermal parameters, and all of the H atoms were calculated
in idealized positions and refined riding on their parent atoms. The
2
refinement was carried out using F rather than F values. R is calculated
1
to provide a reference to the conventional R value, but its function is not
Preparation of (Mesityl(2-methylquinolin-8-yl)amino)-
minimized.
trichlorotitanium (7-TiCl ). To complex 7-Ti(NMe ) (2.976 g, 6.5
Structure 7. C H N , M = 276.37, triclinic, P1 (0.210 × 0.160 ×
̅
3
2
3
19 20 2 w
3
mmol) dissolved in 8 mL of toluene was added SiMe Cl (3.373 g, 26.1
0.130 mm ), a = 7.1032(2) Å, b = 8.6182(2) Å, c = 12.4141(4) Å, a =
98.911(2)°, β = 90.099(2)°, γ = 91.834(2)°, temp = 100(2) K, Z = 2, V =
2
2
mmol), resulting in a sudden color change of the solution from orange-
red to brown. After 10 min of stirring at ambient temperature, highly
crystalline product (brown-black) appeared. After stirring for 3 h at
ambient temperature, 10 mL of hexane was added and the suspension
was placed in the freezer for 3 h. A crystalline solid was collected on a frit,
and it was washed with cold hexane (2 × 3 mL) and dried under reduced
pressure to give 2.716 g of product. Yield: 97%. Anal. Calcd for
C H N Ti: C, 53.12; H, 4.46; N, 6.52. Found: C, 52.82; H, 4.53; N,
3
750.38(4) Å , R1 = 0.0431, 0.0544, wR2 = 0.1154, 0.1226 (I > 2σ(I), all
data), GOF = 1.070.
Structure 7-HfBn . C H Hf N , M = 1449.42, monoclinic, P2 /c
3
80 75
2
4
w
1
3
(0.160 × 0.130 × 0.090 mm ), a = 20.9081(3) Å, b = 18.6828(3) Å, c =
18.2982(3) Å, β = 112.6890(10)°, temp = 100(2) K, Z = 4, V =
3
6594.53(18) Å , R1 = 0.0262, 0.0400, wR2 = 0.0533, 0.0575 (I > 2σ(I),
all data), GOF = 1.029.
Structure 7-Ti(NMe ) . C100H148N Ti , 1821.98, triclinic, P1 (0.420
× 0.260 × 0.240 mm ), a = 13.9968(2) Å, b = 1814.0744(2) Å, c =
26.3453(5) Å, a = 91.5480(10)°, β = 96.0730(10)°, γ = 101.1860(10)°,
1
9
19
2
1
3
6
7
.24. H NMR (500 MHz, CD Cl ): δ 8.40 (1H, d, J
.61 (1H, d, J
= 8.4 Hz, H7),
̅
2
2
H−H
2 3 20 4
3
3
4
3
= 8.4 Hz, H8), 7.50 (1H, dd, J
= 8.0, J = 1.1
H−H
H−H
H−H
Hz, H4), 7.36 (1H, t, J = 7.9 Hz, H3), 7.08−7.03 (2H, m, H12, H14),
1
361
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
3
temp = 100(2) K, Z = 8, V = 5056.75(14) Å , R1 = 0.0334, 0.0401, wR2
0.0906, 0.0956 (I > 2σ(I), all data), GOF = 1.05.
Structure 7-TiCl . C H Cl N Ti, 507.72, triclinic, P1
two Polymer Laboratories PL gel 10 μm MIXED-B columns (300 mm ×
10 mm) at a flow rate of 2.0 mL/min at 150 °C. Sample detection was
performed using a PolyChar IR4 detector in concentration mode. A
conventional calibration of narrow polystyrene (PS) standards was
utilized, with apparent units adjusted to homopolyethylene (PE) using
known Mark−Houwink coefficients for PS and PE in TCB at this
temperature. To determine octene incorporation, polymer samples were
dissolved at a concentration of 30 mg/mL in 1,2,4-trichlorobenzene at
160 °C for 1 h while shaking. A 100 μL aliquot of each polymer/TCB
solution was deposited into individual cells on a custom silicon wafer at
160 °C under inert nitrogen atmosphere. The wafer was held at 160 °C
for 45 min and then pulled from the heat and allowed to cool to ambient
temperature. The wafer was then analyzed using a Nicolet Nexus 670
FT-IR ESP infrared spectrometer. Octene incorporation was
determined by 1H NMR spectroscopy. Typically, 0.055 g of the
respective copolymer sample was cut into pieces and transferred into an
8 mm NMR tube, followed by adding approximately 1.6 mL of 1,1,2,2-
=
3
25 25
3
2
̅
(0.350 ×
3
0
.280 × 0.240 mm ), a = 10.1358(2) Å, b = 11.3270(3) Å, c =
1.8363(3) Å, a = 69.3490(10)°, β = 75.1330(10)°, γ = 80.5650(10)°,
temp = 100(2) K, Z = 2, V = 1224.96(5) Å , R1 = 0.0251, 0.0286, wR2 =
.0634, 0.066 (I > 2σ(I), all data), GOF = 1.045.
Structure 7-TiMe . C H N Ti, 368.36, triclinic, P1
0.090 mm ), a = 11.7159(2) Å, b = 12.8671(2) Å, c = 14.0049(2) Å, a
1
3
0
̅
(0.270 × 0.140
3
22 28
2
3
×
=
104.0544(11)°, β = 96.1202(11)°, γ = 97.9432(11)°, temp = 100(2)
K, Z = 4, V = 2006.68(6) Å , R1 = 0.0391, 0.0597, wR2 = 0.0933, 0.1025
3
(I > 2σ(I), all data), GOF = 1.029.
Batch Reactor Ethylene/1-Octene Copolymerizations. Poly-
merization reactions were carried out at 140 °C. While the reactor was
reaching polymerization temperature, 10 μmol of MMAO was added to
the reactor as a scavenger for trace O and water. A 2 L Parr reactor was
2
used in the polymerizations. All feeds were passed through columns of
alumina and Q-5 catalyst (available from Engelhard Chemicals Inc.)
prior to introduction into the reactor. Precatalyst and activator
tetrachloroethane-d (TCE) containing 1 mM Cr(acac) . The sample
2
3
tube was then purged with nitrogen, sealed with a piece of Teflon tape,
and heated at 110 °C using a heating block. The tube was vortexed
repeatedly to ensure sample homogeneity prior to any NMR
(
[HNMe(C H ) ][B(C F ) ], obtained from Boulder Scientific
18 37 2 6 5 4
Co.) solutions were handled in a nitrogen-filled glovebox. A stirred 2
L reactor was charged with approximately 605 g of mixed alkanes solvent
and 300 g of 1-octene comonomer. Once at temperature, the reactor was
saturated with ethylene at 288 psig (1.99 MPa). Precatalysts were mixed
with the activator, as dilute solutions in toluene, and transferred to a
catalyst addition tank and injected into the reactor. The polymerization
conditions were maintained for 10 min with ethylene added on demand.
Heat was continuously removed from the reaction vessel through an
internal cooling coil. The resulting solution was removed from the
reactor, quenched with isopropyl alcohol, and stabilized by addition of
1
measurement. Subsequent H NMR experiments were performed on
a Bruker AVANCE 600 MHz spectrometer equipped with a 10 mm
probe. For each sample, two types of experiments were conducted. A
1
standard single-pulse H experiment was performed first to quantify the
peak ratio of polymer to solvent. The second experiment employed the
1
H presaturation sequence using a continuous wave to suppress the
polymer backbone peak. The level of octane was quantified by
referencing the unsaturated CH signal to the same solvent peak. All
3
measurements were performed at 110 °C with no sample spinning using
the following parameters: 90° pulse of 26.5 μs, 2.7 s acquisition time, 2 s
presaturation time (pw = 0.24 mW), 15 s total repetition time, 16 scans
for standard spectra, and 128−256 scans for presaturated spectra. The
spectra were centered at 1.296 ppm with a spectrum width of 20 ppm.
1
0 mL of a toluene solution containing approximately 67 mg of a
hindered phenol antioxidant (Irganox 1010 from Ciba Geigy
Corporation) and 133 mg of a phosphorus stabilizer (Irgafos 168
from Ciba Geigy Corporation). Between polymerization runs, a wash
cycle was conducted in which 850 g of mixed alkanes was added to the
reactor, and the reactor was heated to 160 °C. The reactor was then
emptied of the heated solvent immediately before beginning a new
polymerization run. Polymers were recovered by drying for about 12 h in
a temperature-ramped vacuum oven with a final set point of 140 °C.
Note that the catalyst activities were determined using the resulting
polymer yields, relative to the amount of precatalyst injected. The
amount of catalyst, in turn, was varied in accord with its activity.
Specifically, it was necessary to add enough of each precatalyst to obtain
sufficient quantities of the copolymer products for analytical measure-
ments. Conversely, it was also desired to maintain temperature control
of the exothermic polymerization reactions (the polymerization
exotherms were kept to less than 5 °C for all runs), and so it was not
feasible to inject an arbitrary amount of the precatalysts. Additionally,
catalyst activity can be significantly impacted by the presence of
impurities; therefore, comparison of the catalyst control (CGC) to
historical data was used to ensure the proper performance of the reactor.
The data presented herein correspond to single runs with the indicated
catalysts. From the historical data with CGC, we estimate the variation
in catalyst activity on a given day is ±10%. Likewise, the variation in the
resulting polymer molecular weight and octene incorporation data is
typically ±10%, while the variation in the polymer melting temperatures
is ±2 °C.
1
The obtained H spectra were referenced to the TCE solvent peak at 6.0
ppm (residual protonated solvent).
ASSOCIATED CONTENT
Supporting Information
■
*
S
NMR spectra (1D and 2D) and X-ray data (including CIF files)
for all new compounds and tabulated NMR data for polymer
analyses are included. This material is available free of charge via
the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
E-mail: PFontaine@dow.com.
■
*
Notes
The authors declare no competing financial interest.
REFERENCES
■
(1) For reviews on postmetallocene molecular polyolefin catalyst
familes, see: (a) Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. Angew.
Chem., Int. Ed. 1999, 38, 428−447. (b) Gibson, V. C.; Spitzmesser, S. K.
Chem. Rev. 2003, 103, 283−316. (c) Lamberti, M.; Mazzeo, M.;
Pappalardo, D.; Zambelli, A.; Pellecchia, C. Macromol. Symp. 2004, 213,
235−252. (d) Busico, V. Macromol. Chem. Phys. 2007, 208, 26−29.
(e) Baier, M. C.; Zuideveld, M. A.; Mecking, S. Angew. Chem., Int. Ed.
2014, 53, 2−25.
Polymer Characterization. Melting (T ) temperatures of
m
polymers were measured by differential scanning calorimetry (Q2000
DSC, TA Instruments, Inc.). Samples were first heated from ambient
temperature to 200 °C using the “Jump To” feature. After being held at
this temperature for 4 min, the samples were cooled to −90 °C at 10 °C/
min, held for 4 min, and then heated again to 200 °C. Molecular weight
distribution (M , M ) information was determined by analysis on a
(2) Fontaine, P. P.; Klosin, J.; McDougal, N. Organometallics 2012, 31,
6244−6251.
w
n
custom Dow-built robotic-assisted dilution high-temperature gel
permeation chromatographer (RAD-GPC). Polymer samples were
dissolved for 90 min at 160 °C at a concentration of 5−7 mg/mL in
(3) For selected examples of metal complexes ligated by aminoquino-
line ligands, see: (a) Lee, J. C.; Muller, B.; Pregosin, P.; Yap, G. P. A.;
Rheingold, A. L.; Crabtree, R. H. Inorg. Chem. 1995, 34, 6295−6301.
(b) Peters, J. C.; Harkins, S. B.; Brown, S. D.; Day, M. W. Inorg. Chem.
2001, 40, 5083−5091. (c) Pi, C.; Zhang, Z.; Pang, Z.; Zhang, J.; Luo, J.;
Chen, Z.; Weng, L.; Zhou, X. Organometallics 2007, 26, 1934−1946.
1
,2,4-trichlorobenzene (TCB) stabilized by 300 ppm of BHT in capped
vials while stirring. They were then diluted to 1 mg/mL immediately
before a 400 μL aliquot of the sample was injected. The GPC utilized
1
362
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363

Organometallics
Article
(
1
d) Betley, T. A.; Qian, B. A.; Peters, J. C. Inorg. Chem. 2008, 47, 11570−
(12) (a) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98,
2587−2598. (b) Wang, W.-J.; Yan, D.; Zhu, S.; Hamielec, A. E.
Macromolecules 1998, 31, 8677−8683. (c) Wang, W.-J.; Kolodka, E.;
Zhu, S.; Hamielec, A. E. J. Polym. Sci. A Polym. 1999, 37, 2949−2957.
(d) Dekmezian, A. H.; Soares, J. B. P.; Jiang, P. J.; Garcia-Franco, C. A.;
Weng, W. Q.; Fruitwala, H.; Sun, T.; Sarzotti, D. M. Macromolecules
1782. (e) Deraeve, C.; Maraval, A.; Vendier, L.; Faugeroux, V.; Pitie,
M.; Meunier, B. Eur. J. Inorg. Chem. 2008, 36, 5622−5631. (f) Betley, T.
A.; Qian, B. A.; Peters, J. C. Inorg. Chem. 2008, 47, 11570−11582.
(
g) Malassa, A.; Koch, C.; Stein-Schaller, B.; Gorls, H.; Friedrich, M.;
Westerhausen, M. Inorg. Chim. Acta 2008, 361, 1405−1414. (h) O’Neill,
M. K.; Trappey, F. A.; Battle, P.; Boswell, C. L.; Blauch, D. N. Dalton
Trans. 2009, 3391−3394. (i) Liu, D.; Cui, D. Dalton Trans. 2011, 40,
7
2
2
002, 35, 9586−9594.
13) Sheldrick, G. M. SHELXTL6.1, Crystallographic Software Package;
Bruker AXS, Inc.: Madison, WI, USA, 2008.
(
755−7761. (j) Liu, D.; Luo, Y.; Gao, W.; Cui, D. Organometallics 2010,
9, 1916−1923.
(
4) For examples of polymerization catalysts utilizing quinoline-based
ligands, see: (a) Nagy, S.; Krishnamurti, R.; Tyrell, J. A.; Cribbs, L. V.;
Cocoman, M. (Occidental Chemical Corporation, USA) Appl.-
WO9633202, 1996. (b) Fontaine, P. P.; Kuhlman, R. L. (Dow Global
Technologies) Appl. WO2011102990, 2011. (c) Nagy, S.; Winslow, L.
N.; Mihan, S.; Chevalier, R.; Lukesova L.; Nifant’ev, I. E.; Ivchenko, P. V.
(
Equistar Chemicals) Appl. WO2011011040, 2011. (d) Nagy, S.;
Winslow, L. N.; Mihan, S.; Chevalier, R.; Lukesova L.; Nifant’ev, I. E.;
Ivchenko, P. V.; Lynch, M. W. (EquistarChemicals) Appl.
WO2011011041, 2011. (e) Lamberti, M.; Bortoluzzi, M.; Paolucci,
G.; Pellecchia, C. J. Mol. Catal. A: Chem. 2011, 351, 112−119. (f) Nagy,
S.; Winslow, L. N.; Mihan, S.; Lukesova, L.; Nifant’ev, I. E.; Ivchenko, P.
V.; Bagrov, V. V. (Basell Polyolefine GmbH, Germany) Appl.
US20120016092, 2012. (g) Song, S.; Xiao, T.; Wang, L.; Redshaw, C.;
Wang, F.; Sun, W.-H. J. Organomet. Chem. 2012, 699, 8−25.
(
5) (a) De Waele, P.; Jazdzewski, B. A.; Klosin, J.; Murray, R. E.;
Petersen, J. L.; Theriault, C. N.; Vosejpka, P. C. Organometallics 2007,
2
6, 3896−3899. (b) Mashima, K.; Ohnishi, R.; Yamagata, T.; Tsurugi,
H. Chem. Lett. 2007, 36, 1420−1421. (c) Tsurugi, H.; Ohnishi, R.;
Kaneko, H.; Panda, T. K.; Mashima, K. Organometallics 2009, 28, 680−
687. (d) Kaneko, H.; Tsurugi, H.; Panda, T. K.; Mashima, K.
Organometallics 2010, 29, 3463−3466. (e) Froese, R. D.; Jazdzewski,
B. A.; Klosin, J.; Kuhlman, R. L.; Theriault, C. N.; Welsh, D. M.; Abboud,
K. A. Organometallics 2011, 30, 251−262. (f) Figueroa, R.; Froese, R. D.;
He, Y.; Klosin, J.; Theriault, C. N.; Abboud, K. A. Organometallics 2011,
3
0, 1695−1709. (g) Fontaine, P. P.; Figueroa, R.; McCann, S. D.; Mort,
D.; Klosin, J. Organometallics 2013, 32, 2963−2972. (h) Klosin, J.;
Fontaine, P. P.; Figueroa, R.; McCann, S. D.; Mort, D. Organometallics
2
(
1
2
013, 32, 6488−6499.
6) (a) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100,
169−1203. (b) Tian, J.; Hustad, P. D.; Coates, G. W. J. Am. Chem. Soc.
001, 123, 5134−5135. (c) Bollmann, A.; Blann, K.; Dixon, J. T.; Hess,
F. M.; Killian, E.; Maumela, H.; McGuinness, D. S.; Morgan, D. H.;
Neveling, A.; Otto, S.; Overett, M.; Slawin, A. M. Z.; Wasserscheid, P.;
Kuhlmann, S. J. Am. Chem. Soc. 2004, 126, 14712−14713. (d) Boussie,
T. R.; Diamond, G. M.; Goh, C.; Hall, K. A.; LaPointe, A. M.; Leclerc, M.
K.; Murphy, V.; Shoemaker, J. A. W.; Turner, H.; Rosen, R. K.; Stevens,
J. C.; Alfano, F.; Busico, V.; Cipullo, R.; Talarico, G. Angew. Chem., Int.
Ed. 2006, 45, 3278−3283. (e) Arriola, D. J.; Carnahan, E. M.; Hustad, P.
D.; Kuhlman, R. L.; Wenzel, T. T. Science 2006, 312, 714−719.
(
f) Kuhlman, R. L.; Klosin, J. Macromolecules 2010, 43, 7903−7904.
7) For selected examples of organometallic additions to quinolines,
see: (a) Gilman, H.; Eisch, J.; Soddy, T. S. J. Am. Chem. Soc. 1959, 81,
(
4000−4003. (b) Goldstein, S. W.; Dambek, P. J. Synthesis 1989, 3, 221−
222. (c) Rezgui, F.; Mangeney, P.; Alexakis, A. Tetrahedron Lett. 1999,
40, 6241−6244. (d) Wang, Z.-X.; Li, Y.-X. Organometallics 2003, 22,
4900−4904. (e) Amiot, F.; Cointeaux, L.; Silve, E. J.; Alexakis, A.
Tetrahedron 2004, 60, 8221−8231.
8) Belser, P.; Bernhard, S.; Guerig, U. Tetrahedron 1996, 52, 2937−
944.
9) Full experimental details are provided in the Supporting
Information section.
10) (a) Parssinen, A.; Luhtanen, T.; Klinga, M.; Pakkanen, T.; Leskela,
M.; Repo, T. Eur. J. Inorg. Chem. 2005, 2100−2109. (b) Parssinen, A.;
Luhtanen, T.; Klinga, M.; Pakkanen, T.; Leskela, M.; Repo, T.
Organometallics 2007, 26, 3690−3698.
11) He, Y.; Qiu, X.; Klosin, J.; Cong, R.; Roof, G.; Redwine, D.
Macromolecules 2014, 47, 3782−3790.
(
2
(
(
̈
̈
̈
̈
(
1
363
DOI: 10.1021/acs.organomet.5b00053
Organometallics 2015, 34, 1354−1363