Reactivity of amine/E(C6 F5 )3 (E = B, Al) lewis pairs toward linear and cyclic acrylic monomers: Hydrogenation vs. polymerization

Article abstract of DOI:10.3390/molecules20069575

This work reveals the contrasting reactivity of amine/E(C₆F₅)₃ (E = B, Al) Lewis pairs toward linear and cyclic acrylic monomers, methyl methacrylate (MMA) and biorenewable -methyl-α-methylene--butyrolactone (MMBL). While mixing of 2,2,6,6- tetramethylpiperidine (TMP) and B(C₆F₅)₃ leads to a frustrated Lewis pair (FLP), Et₃N reacts with B(C₆F₅)₃ to form disproportionation products, ammonium hydridoborate ionic pair and iminium zwitterion. On the other hand, the stoichiometric reaction of either TMP or Et₃N with Al(C₆F₅)₃ leads to clean formation of a classic Lewis adduct (CLA). Neither TMP nor Et₃N, when paired with E(C₆F₅)₃, polymerizes MMA, but the Et₃N/2B(C₆F₅)₃ pair promotes transfer hydrogenation of MMA to form methyl isobutyrate. In contrast, the amine/E(C₆F₅)₃ pairs promote rapid polymerization of MMBL carrying the more reactive exocyclic methylene moiety, achieving full conversion in less than ₃ min even at a low catalyst loading of 0.0625 mol %. TMP is more effective than Et₃N for the polymerization when paired with either the borane or the alane, while the alane exhibits higher polymerization activity than the borane when paired with Et₃N. Overall, the TMP/Al(C₆F₅)₃ system exhibits the highest polymerization activity, achieving a maximum turn-over frequency of 96,000 h-1at 0.125 mol % of catalyst loading, producing high molecular weight PMMBL with Mn = 1.29 [[amp]]times; 105 g?mol-1 .

Full text of DOI:10.3390/molecules20069575

Molecules 2015, 20, 9575-9590; doi:10.3390/molecules20069575
OPEN ACCESS
molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Reactivity of Amine/E(C6F5)3 (E = B, Al) Lewis Pairs toward
Linear and Cyclic Acrylic Monomers: Hydrogenation
vs. Polymerization
Jiawei Chen and Eugene X.-Y. Chen *
Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, USA
* Author to whom correspondence should be addressed; E-Mail: eugene.chen@colostate.edu;
Tel.: +1-970-491-5609; Fax: +1-970-491-1801.
Academic Editor: James D. Hoefelmeyer
Received: 29 April 2015 / Accepted: 21 May 2015 / Published: 26 May 2015
Abstract: This work reveals the contrasting reactivity of amine/E(C6F5)3 (E = B, Al)
Lewis pairs toward linear and cyclic acrylic monomers, methyl methacrylate (MMA) and
biorenewable γ-methyl-α-methylene-γ-butyrolactone (γMMBL). While mixing of 2,2,6,6-
tetramethylpiperidine (TMP) and B(C6F5)3 leads to a frustrated Lewis pair (FLP), Et3N
reacts with B(C6F5)3 to form disproportionation products, ammonium hydridoborate ionic
pair and iminium zwitterion. On the other hand, the stoichiometric reaction of either TMP
or Et3N with Al(C6F5)3 leads to clean formation of a classic Lewis adduct (CLA). Neither
TMP nor Et3N, when paired with E(C6F5)3, polymerizes MMA, but the Et3N/2B(C6F5)3
pair promotes transfer hydrogenation of MMA to form methyl isobutyrate. In contrast, the
amine/E(C6F5)3 pairs promote rapid polymerization of MMBL carrying the more reactive
γ
exocyclic methylene moiety, achieving full conversion in less than 3 min even at a low
catalyst loading of 0.0625 mol %. TMP is more effective than Et3N for the polymerization
when paired with either the borane or the alane, while the alane exhibits higher polymerization
activity than the borane when paired with Et3N. Overall, the TMP/Al(C6F5)3 system exhibits
the highest polymerization activity, achieving a maximum turn-over frequency of 96,000 h−1
at 0.125 mol % of catalyst loading, producing high molecular weight PγMMBL with
Mn = 1.29 × 105 g·mol−1.
Keywords: frustrated Lewis pair; Lewis pair polymerization; amine; alane; borane

Molecules 2015, 20
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1. Introduction
The combination of various highly acidic Lewis acids (LAs) and sterically hindered Lewis bases
(LBs) provides opportunities to construct different types of “frustrated Lewis pairs” (FLPs) [1–9], in
which the direct LA-LB interaction is either precluded or significantly weakened due to the steric
crowdedness. More significantly, this unquenched, orthogonal reactivity allows the cooperative
activation of small molecules [10–25], catalytic hydrogenation [26–32] and new reactivity/reaction
development [33–45]. While the original FLP systems pioneered by Stephan and Erker focused mostly on
boron-based LAs and phosphine-based LBs, the scopes of the suitable candidates for the FLP chemistry
have recently been extended to other group 13 and 14 elements as LAs (e.g., organoaluminum species,
silylium cations, and borenium cations), and group 14 and 15 elements as LBs (e.g., amines, pyridines,
and carbenes). Furthermore, a considerable amount of efforts has been directed to the design of
unimolecular FLPs and chiral versions of FLPs for asymmetric transformations [46–55].
We have been interested in developing new polymerization methods enabled by Lewis pairs,
namely Lewis Pair Polymerization (LPP) [56], to synthesize different classes of polymers. In this type
of polymerization, Lewis pairs are involved in monomer substrate activation, chain initiation, as well
as chain propagation and termination/transfer steps (Scheme 1). We have demonstrated, for example,
FLPs or classic Lewis adducts (CLAs) consisting of bulky phosphine or N-heterocyclic carbene (NHC)
LBs and the highly acidic Al(C6F5)3 LA are capable of promoting rapid polymerization of conjugated
polar alkenes such as linear acrylic monomer methyl methacrylate (MMA) and cyclic biorenewable
γ-methyl-α-methylene-γ-butyrolactone (γMMBL) into high molecular weight polymers [57–59].
Such LPP system is also effective for the polymerization of monomers featuring the C=C-C=N
functionality, including 2-vinyl pyridine and 2-isopropenyl-2-oxazoline [60,61]. Controlled Ring-opening
(co)polymerization of other monomers such as lactide and lactones into cyclic polymers has been
achieved by employing Zn(C6F5)2-based Lewis pairs [62], while radical polymerization of styrene is
successfully mediated by a persistent FLP-NO aminoxyl radical generated by N,N-cycloaddition of
a cyclohexylene-linked intramolecular P/B system to nitric oxide [63]. More recently, we found that
the boron-based LA, in combination with various NHC or phosphine LBs, can be highly effective
for polymerization of MMA and MMBL: while the B/P FLP systems exhibit no or negligible
γ
polymerization reactivity, the P→B and NHC→B CLAs have been found to exhibit unexpectedly high
activity for the polymerization of MMBL [64]. This unique polymerization method has now been
γ
employed to the regio-controlled polymerization of dissymmetric divinyl polar monomers [57,65].
A search of the current array of LPP systems reveals that the combination of LAs and amines is
scarce and not well-established [58]. In contrast, the B/N system has been studied extensively in the
area of the FLP chemistry with respect to the LA-LB interaction, small molecule activation [25],
catalysis [28,44,66,67] as well as mechanistic investigations [68]. In this context, we set out to
examine the polymerization reactivity of two widely used amines, triethylamine (Et3N) and
2,2,6,6-tetramethylpiperidine (TMP), coupled with two strong organo-LAs, E(C6F5)3 (E = B, Al). We
envisioned that the introduction of such sterically encumbered amines with different structural and
electronic properties will present an opportunity to probe the polymerization activity of the
amine/E(C6F5)3 (E = B or Al) system toward two representative acrylic monomers, linear MMA and
cyclic γMMBL (Scheme 1).

Molecules 2015, 20
9577
X (O, NR)
LA = B(C6F5)3, Al(C6F5)3
LB
LA
LB
FLP
LA
+
FG
CLA
N
R
LB =
N
H
(M)
Et3N
O
TMP
O
LA
LA
X
X
M
LA
M =
n
FG
LB
LB
X
FG
O
OMe
MMA
n M
R
R
R
MMBL
FG
Scheme 1. Generalized chain initiation and propagation mechanism for polymerization
of conjugated polar alkenes carrying a functional group (FG) by Lewis pairs through
zwitterionic active species or intermediates [56], and the structure of LAs, LBs and
monomers examined in this study.
2. Results and Discussion
2.1. Reaction of Amines and E(C6F5)3 in the Absence of Monomer
A survey of the recent literatures indicates that the coordination chemistry and structural
characterizations of several amine/E(C6F5)3 pairs have been reported. Preceding the discovery of the
FLP system, earlier studies focused on systems featuring direct B-N and Al-N bond formation with less
sterically hindered amines. For instance, Lancaster and co-workers [69] reported that both the borane
and alane E(C6F5)3 form stable adducts with a variety of primary and secondary amines. In addition, in
all of the cases, the two Lewis acids show invariable reactivity towards these amines. On the other hand,
we observed markedly different polymerization activity between the borane and the alane, when used as
(co)catalysts and monomer activators for both transition-metal-catalyzed and LPP processes [59,70–73].
In general, the alane is more effective than borane due to its higher Lewis acidity, oxophilicity and
larger radius. Our recent work showed that the alane displays clear advantages over the borane in
several different types of FLP-type catalysis [74]. In this LPP work, we chose two sterically congested
amines, Et3N and TMP, as the LB to pair with E(C6F5)3 (Scheme 1).
These two amines exhibit FLP-type reactivity when coupled with the borane [25,75], but their
reaction with the alane has not yet been examined. An earlier study showed that, mixing of B(C6F5)3
and Et3N results in a disproportionation reaction of the Lewis pair to form ammonium hydridoborate
(C6F5)3B-H···H-N(C2H5)3, concomitant with equimolar iminium zwitterion (C6F5)3B-CH2-
CH=N(C2H5)2 [75] (Scheme 2). B(C6F5)3 is known to abstract a hydride from the α-position of a bulky
amine with α-hydrogens and form an FLP with the one without α-hydrogens such as TMP. The latter
system was utilized for dihydrogen activation and CO2 reduction [25,44]. We speculated that switching
from B(C6F5)3 to its congener Al(C6F5)3 could achieve different coordination reactivity. As expected,
the alane, considered possessing higher Lewis acidity and less steric hindrance, forms a dative bond
with both Et3N and TMP. In the stoichiometric reaction between Al(C6F5)3 and Et3N, the crystalline
adduct Et3N·Al(C6F5)3 was isolated in a yield of 81%. Only one set of ethyl and one set of C6F5
1
19
resonances were presented in the H- and F-NMR spectra, respectively (Figure 1). Apparently, the
direct Al-N bonding prevents other reactions such as hydride abstraction, which stands in contrast to

Molecules 2015, 20
9578
the borane. Similarly, the TMP·Al(C6F5)3 adduct was isolated as colorless crystals in a yield of 85%,
1
19
in which the complex formation was confirmed by both H- and F-NMR spectroscopy (Figure 2).
1
In the H-NMR spectrum, the N-H signal is significantly downfield shifted to 3.71 ppm (cf. 0.64 ppm
for the free TMP), as a result of the enhanced acidity after coordination to the electron-deficient alane.
This adduct is stable in solution up to 2 days, which precludes the possibility of catalyst decomposition
(e.g., protonolytic cleavage of the Al-C bond by the N-H proton) during the course of polymerization
(vide infra). In addition, an intramolecular FLP (5) [67] was also included for the LPP study.
0.5
0.5
Et2N CH CH2 B(C6F5)3
Et3N
(C6F5)3Al
NEt3
Al(C6F5)3 + Et3N
B(C6F5)3 + Et3N
H
H B(C6F5)3
N
3
1
B(C6F5)2
(C6F5)3Al
N
H
B(C6F5)3
+
HN
FLP
HN
Al(C6F5)3
+
5
2
4
Scheme 2. Different amine/E(C6F5)3 (E = B or Al) systems employed for this LPP study
and their corresponding reactivity in the absence of monomer.
Figure 1. 1H- and 19F- (inset) spectra (C6D6) of adduct Et3N·Al(C6F5)3.
Figure 2. 1H- and 19F- (inset) spectra (C6D6) of adduct TMP·Al(C6F5)3.

Molecules 2015, 20
9579
2.2. Stoichiometric Hydrogenation of MMA to Methyl Isobutyrate by Et3N/B(C6F5)3
We first examined the activity of the current amine/LA pairs toward polymerization of the linear
methacrylate, MMA, but found no polymerization activity under our standard polymerization conditions
for all five amine/LA systems. To gain further insight into this observation, we carried out NMR
scale reactions for the amine/LA pairs with equimolar MMA (Figure 3). Accordingly, upon mixing
stoichiometric amounts of Et3N/B(C6F5)3/MMA, only the signals of MMA and the products of the
disproportionation reaction of Et3N/B(C6F5)3 were observed, regardless of the mixing sequence.
Interestingly, addition of more B(C6F5)3 into the above mixture resulted in the consumption of MMA
and formation of a new species, which was identified as methyl isobutyrate, Me2CHC(=O)OMe, a
product of C=C double bond hydrogenation of MMA (Scheme 3). This transfer hydrogenation was fast
and clean, and all of the MMA was consumed in the presence of an additional equivalent of B(C6F5)3.
Noteworthy is the inability to generate the ammonium enolborate initiation species, which was further
supported by the presence of the geminal protons (=CH2) NMR signals derived from a 1:1:1 mixture of
TMP/B(C6F5)3/MMA (see Supporting Information). Similarly, mixing of a preformed Et3N·Al(C6F5)3
adduct with MMA only resulted in the replacement of Et3N with MMA, as indicated by the generation
of free Et3N and the remaining geminal protons (=CH2) signals. Overall, these NMR experiments
showed that the combination of Et3N or TMP with E(C6F5)3 provides insufficient activation for the
polymerization of MMA, either due to the reduction of MMA into the inactive methyl isobutyrate, or
the steric bulkiness around the amine, which impairs the effective formation of the active species
for polymerization.
1
Figure 3. H-NMR spectra (CD2Cl2) of a mixture of Et3N/B(C6F5)3/MMA in the ratio of
1:1:1 (top), 1:1.5:1 (middle) and 1:2:1 (bottom, some amount of Et3N-H···H-B(C6F5)3
remains due to a slight deficiency of MMA).

Molecules 2015, 20
9580
N
H2C
B(C6F5)3
Et2N CH CH2 B(C6F5)3
O
0.5
0.5
O
CH3
Et3N
H
H
B(C6F5)3
OMe
OMe
B(C6F5)3
Et2N CH CH2 B(C6F5)3
0.5 Et2N CH CH2 B(C6F5)3
B(C6F5)3
O
B(C6F5)3
H3C
H3C
O
0.5 Et3N
H
H
B(C6F5)3
CH
OMe
OMe
Scheme 3. Stoichiometric hydrogenation of MMA to methyl isobutyrate by Et3N/B(C6F5)3.
2.3. Characteristic of γMMBL Polymerization by Amine/E(C6F5)3
Next, we set out to investigate activity of the amine/E(C6F5)3 systems toward cyclic MMBL, the
γ
results of which were summarized in Table 1. The intramolecular FLP system 5 yielded no polymer
formation up to 24 h, under the current standard conditions and with or without another equivalent of
B(C6F5)3 (entries 17 and 18). Mixing of equimolar γMMBL and 5 in CD2Cl2 led to formation of adduct
γMMBL·5 via the Lewis acidic borane site in 5, but no active species or polymer formation. This result
implies that the inability of 5 to polymerize γMMBL is attributed to the lack of initiation by the bulky
amine site in 5. On the other hand, the intermolecular Lewis pair systems 1 to 4 initiated rapid and
quantitative polymerization of MMBL into PγMMBL. Under our current standard polymerization
γ
conditions ([γMMBL]:[LA]:[LB] = 200:2:1, 0.5 mL MMBL, 2.0 mL CH2Cl2, RT), Et3N/LA system 1
γ
(B) or 3 (Al) polymerized γMMBL with full conversion in 1 or 0.5 min, giving PγMMBL with Mn = 3.12
or 1.92 × 104 g·mol−1 (Đ = 2.31 or 2.02), thus achieving an averaged turn-over frequency (TOF) of
12,000 or 24,000 h−1 for the borane or alane, respectively (entries 1 and 3). Increasing the ratio to
800:2:1 resulted in an increase of Mn to 5.13 or 3.30 × 104 g·mol−1 for the B and Al LA, respectively,
although a significantly prolonged polymerization period of 60 or 30 min was needed to achieve full
monomer conversion (entries 2 and 4). Overall, the alane showed two-fold higher activity over the
borane when coupled with Et3N. Moreover, the reverse addition sequence, in which equimolar Et3N
and LA were premixed, followed by addition to a CH2Cl2 solution of γMMBL, was also effective, albeit
a slightly slower rate compared to the standard procedure, with or without an additional equivalent of LA.
A stoichiometric reaction of Et3N/B(C6F5)3/γMMBL revealed that all of the monomer was rapidly
consumed, with generation of PγMMBL (see Supporting Information). We reasoned that ammonium
hydridoborate, formed by premixing of Et3N and B(C6F5)3, can initiate the polymerization via the
nucleophilic hydride, whereas the Et3N·Al(C6F5)3 adduct formed via premixing can dissociate in
the presence of MMBL and thus promote the subsequent initiation and bimolecular, activated
γ
monomer propagation.
As mentioned above, the combination of the alane or the borane with TMP offered more well-defined
coordination chemistry (i.e., either CLA or FLP). Hence, the TMP/LA pairs were investigated for LPP
with 6 different [monomer]:[LA]:[TMP] ratios, ranging from 50:2:1 to 1600:2:1, as well as different

Molecules 2015, 20
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addition sequences. Impressively, the polymerizations were finished within 1 min for a ratio up to of
800:2:1 (entries 5–9 and 11–15), and even under lower catalyst loading (0.0625 mol % relative to TMP)
conditions (1600:2:1), the polymerizations were completed in 3 min (entries 10 and 16). Thus,
the polymerization by the B/TMP and Al/TMP Lewis pairs was very rapid with TOF up to 96,000 h−1
(for Al), providing polymers with Mn ranging from medium 6.75 × 104 to high 2.55 × 105 g·mol−1
(Đ = 1.54 to 1.92) and medium 6.96 × 104 to high 1.38 × 105 g·mol−1 (Đ = 2.16 to 2.42) for the borane
and alane, respectively. Interestingly, under the current standard conditions, if the LAs were premixed
with TMP and added to a CH2Cl2 solution of the monomer, the polymerization proceeded rapidly as well.
This result confirmed that the TMP·Al(C6F5)3 adduct formed via premixing can rapidly dissociate in the
presence of MMBL monomer and promote the subsequent initiation and bimolecular, activated
γ
monomer propagation [58,59], while the B/TMP FLP should be active regardless of the addition sequence.
Table 1. Selected results of polymerization of γMMBL by LA/amine LPs a.
O
n
Amine/LA
O
O
(CLA or FLP)
O
MMBL
PMMBL
c
Time
(min)
1
Conv. b
TOF
(h-1)
Mn
(kg·mol−1) (Mw/Mn)
Đ d
Entry
LP
[M]/[Base]
(%)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
0
1
2
B/Et3N (1)
200
800
200
800
50
12,000
800
31.2
53.1
19.2
33.0
67.5 d
100 d
145 d
156 d
253 d
255 d
69.6
77.2
113
2.31
2.47
2.02
2.26
1.54
1.64
1.78
1.92
1.64
1.66
2.41
2.29
2.16
2.38
2.21
2.16
-
60
3
Al/Et3N (3)
B/TMP (2)
0.5
30
24,000
1600
4
5
0.5
0.5
0.5
0.5
1
6000
6
100
200
400
800
1600
50
12,000
24,000
48,000
48,000
32,000
6000
7
8
9
10
11
12
13
14
15
16
17
18 e
3
Al/TMP (4)
0.5
0.5
0.5
0.5
0.5
3
100
200
400
800
1600
200
200
12,000
24,000
48,000
96,000
32,000
-
119
129
138
B-TMP (5)
5 + B
1440
1440
-
0
-
-
-
a
b
Conditions: carried out at RT (ca. 25 C) in CH2Cl2 with 2.5 mL of the total solution; Monomer
1
c
conversion measured by H-NMR spectroscopy; Number-average molecular weight (Mn) and molecular
d
weight distribution (Đ) determined by GPC in DMF relative to PMMA standards; Bimodal distribution,
with an additional small peak (5.0% to 18.3%) on the higher molecular weight region; e Carried out with an
additional equivalent of B(C6F5)3.

Molecules 2015, 20
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3. Experimental Section
3.1. Materials, Reagents, and Methods
All syntheses and manipulations of air- and moisture-sensitive materials were carried out in flamed
Schlenk-type glassware on a dual-manifold Schlenk line, on a high-vacuum line, or in an inert gas-filled
glovebox. NMR-scale reactions were conducted in Teflon-valve-sealed J. Young-type NMR tubes.
HPLC-grade organic solvents were first sparged extensively with nitrogen during filling 20 L solvent
reservoirs and then dried by passage through activated alumina (for Et2O, THF, and CH2Cl2) followed
by passage through Q-5 supported copper catalyst (for toluene and hexanes) stainless steel columns.
Benzene-d6 and toluene-d8 were dried over sodium/potassium alloy and vacuum-distilled or filtered,
whereas CD2Cl2 and CDCl3 were dried over activated Davison 4 Å molecular sieves. HPLC-grade
dimethyl formamide (DMF) was degassed and dried over CaH2 overnight, followed by vacuum
distillation (CaH2 was removed before distillation). NMR spectra were recorded on Varian Inova 300
1
13
19
(300 MHz, H; 75 MHz, C; 282 MHz, F) or a Varion 400 MHz spectrometer. Chemical shifts for
1H-, F- and C- spectra were referenced to internal solvent resonances and are reported as parts per
19
13
million relative to SiMe4.
Methyl methacrylate (MMA) was purchased from Sigma-Aldrich Co. (St. Louis, MO, USA), while
γ-methyl-α-methylene-γ-butyrolactone (γMMBL) was purchased from TCI America (Portland, OR,
USA). These monomers were first degassed and dried over CaH2 overnight, followed by vacuum
distillation. Further purification of MMA involved titration with neat tri(n-octyl)aluminum to a yellow
end point [76], followed by distillation under reduced pressure. All purified monomers were stored in
brown bottles and stored inside a glovebox freezer at −30 C. Amines including triethylamine and
2,2,6,6-tetramethylpiperidine (TMP) were purchased from Sigma-Aldrich Co (St. Louis, MO, USA),
distilled over CaH2, and store brown bottles in a glovebox prior to use. BHT-H was recrystallized
from hexanes prior to use. Tris(pentafluorophenyl)borane, obtained as a research gifts from Boulder
Scientific Company (Mead, CO, USA), was further purified by sublimation under vacuum.
Tris(pentafluorophenyl)alane·(toluene)0.5 [77–79] and 1-(2-[bis(pentafluorophenyl)boryl]benzyl)-
2,2,6,6-tetramethylpiperidine [67] were synthesized according to literature procedures.
3.2. Isolation of Adduct Et3N·Al(C6F5)3
Al(C6F5)3·(toluene)0.5 (135 mg, 0.235 mmol) and Et3N (32.6 μL, 0.235 mmol, 1.0 equiv) were
dissolved in toluene (1 mL) in a glovebox. The mixture was allowed to react for 10 min, then layered
with hexanes (4 mL), and placed in a freezer and recrystallized at −35 °C. The titled product was
isolated as colorless crystals. Yield: 120 mg (81%). 1H-NMR (C6D6, 23 °C): δ 2.60 (q, J = 7.2 Hz, 6H,
13
CH2CH3), 0.55 (t, 9H, CH2CH3). C-NMR (C6D6, 23 °C): δ 150.1, 141.9, 137.4 (C6F5, ipso-C6F5-Al
not observed), 47.4 (CH2), 8.8 (CH3). 19F-NMR (C6D6, 23 °C): δ −119.0 (d, 3J = 19.4 Hz, 6F, o-F), −152.0
(t, 3J = 19.9 Hz, 3F, p-F), −160.9 (m, 6F, m-F) ppm.

Molecules 2015, 20
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3.3. Isolation of Adduct TMP·Al(C6F5)3
Al(C6F5)3·(toluene)0.5 (141 mg, 0.246 mmol) and TMP (42 μL, 0.246 mmol, 1.0 equiv) were
dissolved in toluene (1 mL) in a glovebox. The mixture was allowed to react for 10 min, then layered
with hexanes (3 mL), and placed in a freezer and recrystallized at −35 °C. The titled product was
isolated as colorless crystals and kept in the freezer to avoid decomposition. Yield: 140 mg (85%).
1H-NMR (C6D6, 23 °C): δ 3.72 (br, 1H, NH), 1.09 (br, 6H, CH3), 0.93 (br, 6H, CH3), 0.90 (br, 4H, CH2),
0.75 (m, 2H, CH2). 13C-NMR (C6D6, 23 °C): δ 150.2, 142.1, 137.5 (C6F5, ipso-C6F5-Al not observed),
3
60.4, 40.6, 32.7, 24.7, 16.2 (TMP). 19F-NMR (C6D6, 23 °C): δ −119.1 (d, J = 16.1 Hz, 6F, o-F),
−151.7 (t, 3J = 20.3 Hz, 3F, p-F), −161.2 (pst, 3J = 18.3 Hz, 6F, m-F) ppm.
3.4. Stoichiometric Hydrogenation of MMA by Et3N/2B(C6F5)3 to Methyl Isobutyrate
A CD2Cl2 (0.7 mL) solution of MMA (5.0 L, 0.0469 mmol) in a J. Young NMR tube was added
B(C6F5)3 (24 mg, 0.0469 mmol), followed by addition of Et3N (6.54 L, 0.0469 mmol). The mixture was
1
allowed to react for 10 min before H-NMR measurement, which indicated formation of ammonium
hydridoborate (C6F5)3B-H···H-N(C2H5)3 and iminium zwitterion (C6F5)3B-CH2-CH=N(C2H5)2 but
without consuming any MMA (Scheme 3, Figure 3). In the next step, a second equivalent of B(C6F5)3
1
was transferred to the same NMR tube and the reaction progress was monitored by H-NMR. The
transfer hydrogenation went to completion yielding methyl isobutyrate.
3.5. Typical Procedure for the NMR Scale Reactions (TMP/B(C6F5)3/MMA as an Example)
A CD2Cl2 (0.7 mL) solution of MMA (5.0 L, 0.0469 mmol) in a J. Young NMR tube was added
B(C6F5)3 (24 mg, 0.0469 mmol), followed by addition of TMP (7.98 L, 0.0469 mmol). The mixture
1
was allowed to react for 10 min before H-NMR measurement, which indicated the retention of the
geminal protons of MMA.
In the case of the alane, a different addition sequence was adopted, in which the preformed
amine/Al adduct was transferred to the corresponding monomer in specific deuterated solvents as the
solvent will decompose the alane upon mixing directly.
3.6. General Polymerization Procedures
Polymerizations were performed either in 25 mL flame-dried Schlenk flasks interfaced to the
dual-manifold Schlenk line for runs using external temperature bath, or in 20 mL glass reactors inside
the glovebox for ambient temperature (ca. 25 °C) runs. In a typical polymerization procedure, a
predetermined amount of B(C6F5)3 or Al(C6F5)3 was first dissolved in a monomer (0.5 mL of MMA or
γMMBL, 200 equiv relative to the LB) and 2.0 mL of solvent (CH2Cl2) inside a glovebox. The
polymerization was started by rapid addition of a solution of a LB (1 equiv of an amine) in 0.5 mL of
CH2Cl2 via a gastight syringe to the above mixture containing the LA and monomer under vigorous
stirring. The amount of the monomer was fixed for the varied [M]/[LB] ratio runs. In a second
procedure of polymerization, the premixed LA/LB system (or the intramolecular Lewis pair) was
dissolved in 0.5 mL of toluene (for the alane system since the alane is known to decompose in CH2Cl2
in the absence of a monomer) or CH2Cl2 (for the borane system), followed by addition to a CH2Cl2

Molecules 2015, 20
9584
(2.0 mL) solution of monomer (0.5 mL) to initiate the polymerization. After the measured time interval,
a 0.2 mL aliquot was taken from the reaction mixture via syringe and quickly quenched into a 4-mL
vial containing 0.6 mL of undried “wet” CDCl3 stabilized by 250 ppm of BHT-H; the quenched
1
aliquots were later analyzed by H-NMR to obtain the percent monomer conversion data. After the
polymerization was stirred for the stated reaction time and then the polymer was immediately
precipitated into 200 mL of methanol, stirred for 1 h, filtered, washed with methanol, and dried in a
vacuum oven at 50 C overnight to a constant weight.
3.7. Polymer Characterizations
Polymer number-average molecular weights (Mn) and molecular weight distributions (Đ = Mw/Mn)
were measured by gel permeation chromatography (GPC) analyses carried out at 40 °C and a flow rate
of 1.0 mL·min−1, with DMF as the eluent, on a Waters University 1500 GPC instrument equipped with
one PLgel 5 μm guard and three PLgel 5 μm mixed-C columns (Polymer Laboratories; linear range of
molecular weight = 200–2,000,000). The instrument was calibrated with 10 PMMA standards, and
chromatograms were processed with Waters Empower software (version 2002).
4. Conclusions
In summary, Lewis pairs consisting of bulky amine Et3N and TMP as LBs and bulky E(C6F5)3 as
strong organo-LAs were employed for investigation into their reactivity toward two acrylic monomers,
including linear MMA and cyclic MMBL. While TMP and B(C6F5)3 form an FLP, Et3N reacts with
γ
B(C6F5)3 to form disproportionation products ammonium hydridoborate ionic pair and iminium
zwitterion. On the other hand, the stoichiometric reaction of Et3N and TMP with Al(C6F5)3 leads to
clean formation CLAs.
In the case of linear MMA, the Et3N/2B(C6F5)3 pair promotes transfer hydrogenation of MMA to
form methyl isobutyrate. The TMP/B(C6F5)3 FLP is also incapable of polymerizing MMA, attributable
to the steric hindrance and low nucleophilicity at N in TMP, which resulted in no formation of the
active propagating species. In contrast, the amine/LA pairs promote rapid polymerization of MMBL
γ
carrying the more reactive exocyclic methylene moiety, achieving full conversion in less than 3 min
even at a low catalyst loading of 0.0625 mol %. The Al/Et3N pair displays higher activity when
compared with the B/Et3N pair. Meanwhile, TMP is more efficient than Et3N when paired with either
the borane or the alane. Of the four LA/LB pairs investigated in this study, the TMP/Al(C6F5)3 pair
exhibits the highest activity, achieving a maximum TOF of 96,000 h−1 at 0.125 mol % of catalyst
loading or 32,000 h−1 at 0.0625 mol %, producing high molecular weight PγMMBL with Mn = 1.29 × 105
or 1.38 × 105 g·mol−1, respectively. As compared with the previous LBs employed for LPP, such as
phosphines and NHCs, the current LPP system utilizing the inexpensive, readily available and more
stable and environmentally friendly amine LBs will provide a greener alternative approach toward
bio-renewable polymers based on γMMBL and other monomers.
Supplementary Materials
Supplementary materials can be accessed at: http://www.mdpi.com/1420-3049/20/06/9575/s1.

Molecules 2015, 20
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Acknowledgments
This work was supported by the National Science Foundation (NSF-1150792 and NSF-1507702).
We thank Boulder Scientific Co. for the research gift of B(C6F5)3.
Author Contributions
J.C. and E.Y.-X.C. formulated the research idea and participated in the design of the experiments
and preparation of the manuscript. J.C. carried out the actual experiments and interpreted the data. All
authors have read and approved the final manuscript.
Conflicts of Interest
The authors declare no conflict of interest.
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