Continuous-Flow Production of Succinic Anhydrides via Catalytic β-Lactone Carbonylation by Co(CO)4?Cr-MIL-101

Article abstract of DOI:10.1021/jacs.8b05948

Industrial synthesis of succinic acid relies on hydrocarbon oxidation or biomass fermentation routes that suffer from energy-costly separation processes. Here we demonstrate an alternate route to succinic anhydrides via β-lactone carbonylation by heterogeneous bimetallic ion-pair catalysis in Co(CO)₄^--incorporated Cr-MIL-101 (Co(CO)₄Cr-MIL-101, Cr-MIL-101 = Cr₃O(BDC)₃F, H₂BDC = 1,4-benzenedicarboxylic acid). Postsynthetically introduced Co(CO)₄^- facilitates CO insertion to β-lactone substrates activated by the Lewis acidic Cr(III) centers of the metal-organic framework (MOF), leading to catalytic carbonylation with activity and selectivity profiles that compare favorably to those reported for homogeneous ion-pair catalysts. Moreover, the heterogeneous nature of the MOF catalyst enables continuous production of succinic anhydride through a packed bed reactor, with room temperature β-propiolactone carbonylation activity of 1300 mol_Anhydride·mol_Co^-1 over 6 h on stream. Simple evaporation of the fully converted product stream yields the desired anhydride as isolated solids, highlighting the unique processing advantages conferred by this first example of heterogeneous β-lactone carbonylation pathway.

Full text of DOI:10.1021/jacs.8b05948

Subscriber access provided by UNIV OF THE WESTERN CAPE
Communication
Continuous-flow Production of Succinic Anhydrides via
Catalytic #-Lactone Carbonylation by Co(CO)4#Cr-MIL-101
Hoyoung D. Park, Mircea Dinca, and Yuriy Roman-Leshkov
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b05948 • Publication Date (Web): 10 Aug 2018
Downloaded from http://pubs.acs.org on August 11, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 6
Journal of the American Chemical Society
1
2
3
4
5
6
7
Continuous-flow Production of Succinic Anhydrides via
8
9
Catalytic β-Lactone Carbonylation by Co(CO)4⊂Cr-MIL-101
Hoyoung D. Park†, Mircea Dincă‡,*, and Yuriy RománꢀLeshkov†,*
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
†Department of Chemical Engineering and ‡Department of Chemistry, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, United States
Supporting Information Placeholder
ringꢀexpanding carbonylation to succinic anhydrides under condiꢀ
ABSTRACT: Industrial synthesis of succinic acid relies on hyꢀ
drocarbon oxidation or biomass fermentation routes that suffer
from energyꢀcostly separation processes. Here we demonstrate an
tions much milder than those of the hydrocarbon oxidation proꢀ
cess.12 Facile recovery of the carbonylated product from the solid
catalyst and solvent avoids energyꢀintensive separations from the
fermentation broth required in fermentative processes. In addition,
ready availability of βꢀlactone substrates from industrially accesꢀ
sible epoxides further underscores the intrinsic advantages of the
heterogeneous βꢀlactone carbonylation strategy.13
alternate route to succinic anhydrides via βꢀlactone carbonylation
by heterogeneous bimetallic ionꢀpair catalysis in Co(CO)4 ꢀ
incorporated CrꢀMILꢀ101 (Co(CO)4⊂CrꢀMILꢀ101, CrꢀMILꢀ101 =
–
Cr3O(BDC)3F, H2BDC = 1,4ꢀbenzenedicarboxylic acid). Postsynꢀ
–
thetically introduced Co(CO)4 facilitates CO insertion to βꢀ
–
lactone substrates activated by the Lewis acidic Cr(III) centers of
the metal−organic framework (MOF), leading to catalytic carꢀ
bonylation with activity and selectivity profiles that compare faꢀ
vorably to those reported for homogeneous ionꢀpair catalysts.
Moreover, the heterogeneous nature of the MOF catalyst enables
continuous production of succinic anhydride through a packed
bed reactor, with room temperature βꢀpropiolactone carbonylation
Herein, we report Co(CO)4 ꢀincorporated CrꢀMILꢀ101
(Co(CO)4⊂CrꢀMILꢀ101, CrꢀMILꢀ101 = Cr3O(BDC)3F, H2BDC =
1,4ꢀbenzenedicarboxylic acid) as the first heterogeneous catalyst
for the selective ringꢀexpansion carbonylation of βꢀlactones to
succinic anhydrides. Competitive activity and selectivity profiles
under mild conditions, along with ease of continuousꢀflow operaꢀ
tion and product separations showcase the unique advantages of
Co(CO)4⊂CrꢀMILꢀ101. More importantly, these results stand to
illustrate the potential of the heterogeneous βꢀlactone carbonylaꢀ
tion pathway as a viable route to largeꢀscale production of succinꢀ
ic anhydrides.
–1
activity of 1,300 molAnhydride·molCo over 6 h on stream. Simple
evaporation of the fully converted product stream yields the deꢀ
sired anhydride as isolated solids, highlighting the unique proꢀ
cessing advantages conferred by this first example of heterogeneꢀ
ous βꢀlactone carbonylation pathway.
Our initial discovery of βꢀlactone carbonylation by
Co(CO)4⊂CrꢀMILꢀ101 was guided by mechanistic studies on
heterocycle carbonylation by homogeneous [Lewis acꢀ
id]+[Co(CO)4]– ionꢀpair catalysts. It has been proposed that βꢀ
lactone carbonylation by [Lewis acid]+[Co(CO)4]– follows a
mechanism analogous to that of epoxide carbonylation: (1) subꢀ
As a representative fourꢀcarbon diacid, succinic acid is finding
increasingly wide use as a precursor to highꢀvalue products in
polymer,1 food,2 agriculture,3 and pharmaceutical4 industries. Its
production, however, has traditionally depended on the energyꢀ
intensive benzene or nꢀbutane oxidation pathway that features
high operating temperatures,5 limited yields of ~60% due to side
oxidation reactions,6 and incineration of waste gases owing to
difficult separation of unreacted substrates.7 To address this issue,
the United States Department of Energy named succinic acid as
the first chemical on its list of twelve “Top Value Added Chemiꢀ
cals From Biomass” and fostered the development of milder ferꢀ
mentative routes to succinic acids.8 There has since been signifiꢀ
cant progress in the development of commercialꢀscale fermentaꢀ
tion processes to succinates, giving rise to numerous processes
with kilotonneꢀscale annual capacities.9 Nonetheless, microbial
fermentation processes present their own challenges, namely,
undesired metabolic flux to byproducts10 and costly product sepaꢀ
ration and purification from the fermentation broth that can acꢀ
count for up to 60−70% of the total production cost.11
strate activation by [Lewis acid]+, (2) ring opening by Co(CO)4 ,
–
(3) CO insertion, and (4) product extrusion (Figure 1A).14 Based
on this mechanistic similarity, we hypothesized that our previousꢀ
ly reported Co(CO)4⊂CrꢀMILꢀ101, a metal−organic framework
(MOF)ꢀbased epoxide carbonylation catalyst featuring Lewis
acidic Cr(III) secondary building units ionꢀpaired with postsynꢀ
thetically exchanged Co(CO)4– (Figure 1B), would also be able to
carbonylate βꢀlactones to succinic anhydrides.15 We reasoned that
the structural properties of CrꢀMILꢀ101 found favorable for epoxꢀ
ide carbonylation would also be advantageous for βꢀlactone carꢀ
bonylation: high surface area, large pore openings (12 Å and 16
Å) and pore diameters (29 Å and 34 Å) for low diffusional barrier
to active sites, and high
Heterogeneous βꢀlactone carbonylation is a process that can poꢀ
tentially circumvent current limitations in hydrocarbon oxidation
and microbial fermentation pathways. Due to their inherent ring
strain, the fourꢀmembered βꢀlactone cycles undergo selective
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 6
pressure was increased to promote CO insertion, and (3) reaction
1
2
3
4
temperature was lowered to favor carbonylation featuring a preꢀ
sumably lower activation barrier (Figure 2).14,18 These manipulaꢀ
tions combined to promote a clear preference for the carbonylaꢀ
tion pathway, with the selectivity for anhydride reaching ~87%
under optimized conditions (Figures 2 and S6).
5
Selective carbonylation activity observed with the βꢀ
butyrolactone substrate led us to conduct subsequent studies using
βꢀpropiolactone to examine the applicability of Co(CO)4⊂Crꢀ
MILꢀ101 for the synthesis of the commerciallyꢀdesirable unsubstiꢀ
tuted succinic anhydride. Remarkably, when Co(CO)4⊂CrꢀMILꢀ
101 loaded at 0.3 Co mol % with respect to the substrate was
charged with a 1.8 M solution of βꢀpropiolactone in toluene and
15 bar of CO for 18 h at room temperature, succinic anhydride
was obtained as the sole reaction product in 92% yield without the
poly(3ꢀhydroxypropionate) byproduct (Table 1, entry 2 and Figꢀ
ure S7). This corresponds to an overall site time yield of 16 h–1, an
improvement over the value of 12 h–1 reported for the homogeneꢀ
ous [(salph)Al(THF)2][Co(CO)4] under analogous conditions
(Table 1, entry 1).
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
To probe the catalytic cooperativity between the framework
–
Cr(III) sites and the postsynthetically introduced Co(CO)4 in
Co(CO)4⊂CrꢀMILꢀ101, CrꢀMILꢀ101 and Na[Co(CO)4] were testꢀ
ed individually for βꢀpropiolactone carbonylation activity (Table
1, entries
3 and 4). Expectedly, both CrꢀMILꢀ101 and
Na[Co(CO)4] produced much lower yields, likely due to the abꢀ
–
sence of Co(CO)4 needed for CO insertion and lack of strong
Lewis acids needed for substrate activation, respectively. Altꢀ
hough using an equimolar mixture of CrꢀMILꢀ101 and
Na[Co(CO)4] as a catalyst led to significantly higher yields
Figure 1. (A) Proposed catalytic cycle for the ringꢀexpansion
carbonylation of βꢀlactones by [Lewis acid]+[Co(CO)4]–.14 (B)
Illustration of the metal cluster structure of Co(CO)4⊂CrꢀMILꢀ
101 with coordinated tetrahydrofuran molecules.15
chemical and thermal stability for robust catalysis.16 Synthetic
accessibility of the catalyst through relatively inexpensive chroꢀ
mium, cobalt, and terephthalic acid precursors also distinguished
Co(CO)4⊂CrꢀMILꢀ101 as an attractive candidate for use in the
industriallyꢀrelevant βꢀlactone carbonylation.
Co(CO)4⊂CrꢀMILꢀ101 was prepared as previously reported
(Figures S1−S5 and Table S1) and subjected to batchꢀwise carꢀ
bonylation reactions with βꢀbutyrolactone as a model substrate.
When Co(CO)4⊂CrꢀMILꢀ101 loaded at 0.5 Co mol % with reꢀ
spect to the substrate was exposed to a 1.8 M solution of βꢀ
butyrolactone in toluene and 15 bar of CO at 80 °C for 24 h, full
conversion of the substrate was observed, in line with what was
reported
for
the
homogenous
catalyst
[(salph)Al(THF)2][Co(CO)4] (salph = N,N’ꢀoꢀphenylenebis(3,5ꢀ
diꢀtertꢀbutylsalicylideneimine), THF = tetrahydrofuran).17 Howꢀ
ever, the product solution contained not only the desired meꢀ
thylsuccinic anhydride, but also poly(3ꢀhydroxybutyrate) as a
major side product (Figure S6). Mixed formation of both the anꢀ
hydride and the poly(lactone) has been reported for a number of
[Lewis acid]+[Co(CO)4]– catalysts. It is the result of a competitive
reaction where subsequent to substrate ringꢀopening, CO insertion
leads to the desired carbonylation cycle while the alternative βꢀ
lactone insertion propagates the polymerization reaction (Figure
1A).14 Given the competitive nature of the two parallel pathways,
we sought to increase selectivity to the desired anhydride product
by exploiting the differences in the reaction kinetics of the carꢀ
bonylation and polymerization pathways. To this effect, reaction
conditions were altered as follows: (1) substrate concentration
was lowered to suppress βꢀlactone monomer propagation, (2) CO
Figure 2. Selectivity to succinic anhydride as a function of the
reaction conditions for batch carbonylation of βꢀbutyrolactone by
Co(CO)4⊂CrꢀMILꢀ101. Catalyst loaded at 0.5 Co mol % to the
substrate in toluene and allowed to react for >75% conversion of
the substrate under all conditions tested.
Table 1. Batch Carbonylation of β-Propiolactone.
Entry
Catalyst
t (h)
Yield (%)
ACS Paragon Plus Environment

Page 3 of 6
Journal of the American Chemical Society
–1
thylsuccinic anhydride, with an activity of 360 molAnhydride·molCo
1
2
3
4
5
[(salph)Al(THF)2][Co(CO)4]17
Co(CO)4⊂CrꢀMILꢀ101
CrꢀMILꢀ101
24
18
18
18
18
98
92a
0a
12a
43a
1
2
3
4
5
6
7
8
over 60 h on stream at 40 °C when exposed to a flow of 0.5 M βꢀ
butyrolactone in toluene at 0.02 ml/min or a WHSV of 7.1 h–1 and
an excess CO flow of 30 ml/min at 30 bar (Figures 3B and S11).
The dramatically higher activity observed with βꢀpropiolactone is
in line with the proposed SN2 attack on the βꢀcarbon of the lacꢀ
Na[Co(CO)4]
CrꢀMILꢀ101 + Na[Co(CO)4]b
–
tone by Co(CO)4 (Figure 1A), where decreased steric hindrance
on the βꢀcarbon leads to a significant increase in activity.14 Carꢀ
bonylation activity was also highly sensitive to CO pressure,
where stability of the observed activity profiles was impaired
a
1
As determined by HꢀNMR analysis against mesitylene as a
b
standard. CrꢀMILꢀ101 + Na[Co(CO)4] = equimolar mixture of
the two species.
9
compared to using either precursor individually, the equimolar
mixture was still inferior to Co(CO)4⊂CrꢀMILꢀ101 with preꢀ
installed Cr/Co sites (Table 1, entry 5). We attribute this behavior
to an incomplete in-situ formation of Cr/Co sites that leads to
fractional carbonylation activity for the mixture of CrꢀMILꢀ101
and Na[Co(CO)4]. The need for the coexistence of both the Lewis
acidic Cr(III) and Co(CO)4– for appreciable carbonylation activity
suggests Cr/Co cooperative catalysis to be active for
Co(CO)4⊂CrꢀMILꢀ101.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
When several solvents were screened for optimizing βꢀ
propiolactone carbonylation activity with Co(CO)4⊂CrꢀMILꢀ101,
the highest activities were observed with nonꢀcoordinating solꢀ
vents such as toluene and dichloromethane (DCM) (Table S2,
entries 1 and 2). Reactions in coordinating solvents greatly reꢀ
duced carbonylation activity, as exemplified by the low yields
from reactions with 1,2ꢀdimethoxyethane, tetrahydrofuran, and
acetonitrile (Table S2, entries 3−5). These results deviate from the
solvent dependence observed for epoxide carbonylation by
Co(CO)4⊂CrꢀMILꢀ101, in which mildly coordinating solvents,
such as 1,2ꢀdimethoxyethane, were found to be ideal. A similar
discrepancy has been observed for various homogeneous catalysts
of the general formula [Lewis acid]+[Co(CO)4]–, where βꢀlactone
carbonylation proceeded much faster in solvents that are less coꢀ
ordinating than those optimal for epoxide carbonylation. This
behavior has been accredited to substrate activation and ringꢀ
opening being the rate limiting step for βꢀlactone carbonylation,
where Lewis basic solvents more effectively compete for coordiꢀ
nation to the Lewis acidic metal sites and hinder substrate ringꢀ
opening by Co(CO)4– (Figure 1A).14 Observation of an analogous
solvent dependence with Co(CO)4⊂CrꢀMILꢀ101 lends credence
that a similar mechanistic explanation may be applicable to βꢀ
lactone carbonylation by Co(CO)4⊂CrꢀMILꢀ101.
In order to confirm the heterogeneous nature of catalysis by
Co(CO)4⊂CrꢀMILꢀ101, a βꢀpropiolactone carbonylation reaction
mixture at ~35% conversion was divided into two aliquots, one of
which was filtered (Figure S8). When the filtrate and the unfilꢀ
tered fraction were allowed to further react, the anhydride yield
did not increase for the filtrate whereas the unfiltered portion
resumed its carbonylation activity. The crystalline structure of
Co(CO)4⊂CrꢀMILꢀ101 was also maintained throughout all carꢀ
bonylation reactions, as verified by powder Xꢀray diffraction
analysis of spent Co(CO)4⊂CrꢀMILꢀ101 (Figure S9).
Figure 3. (A) Continuousꢀflow carbonylation of βꢀpropiolactone
by Co(CO)4⊂CrꢀMILꢀ101. Reaction conditions: 0.1 ml/min of
0.1 M βꢀpropiolactone in DCM, 30 ml/min of CO at 45 bar or 15
bar, and 6.0 mg catalyst at 21 °C. (B) Continuousꢀflow carbonylaꢀ
tion of βꢀbutyrolactone by Co(CO)4⊂CrꢀMILꢀ101. Reaction conꢀ
ditions: 0.02 ml/min of 0.5 M βꢀbutyrolactone in toluene, 30
ml/min of CO at 30 bar or 15 bar, and 130 mg catalyst at 40 °C.
at lower CO pressures for both βꢀpropiolactone and βꢀ
butyrolactone substrates (Figure 3). This behavior parallels the
analogous CO pressure dependence observed in batch carbonylaꢀ
tion studies, suggesting that competing side reactions, such as βꢀ
lactone homopolymerization, may be a major cause of deactivaꢀ
tion.
Having confirmed the heterogeneous βꢀlactone carbonylation
activity by Co(CO)4⊂CrꢀMILꢀ101, we designed a laboratoryꢀ
scale packedꢀbed reactor process to study Co(CO)4⊂CrꢀMILꢀ101
under continuousꢀflow conditions (Figure S10). As a singular
example among all βꢀlactone carbonylation catalysts developed to
date, when Co(CO)4⊂CrꢀMILꢀ101 at room temperature was subꢀ
jected to a flow of 0.1 M βꢀpropiolactone in DCM at 0.1 ml/min
or a weight hourly space velocity (WHSV) of 1,200 h–1 and an
excess CO flow of 30 ml/min at 45 bar, succinic anhydride was
obtained as the sole product at 1,300 molAnhydride·molCo–1 over 6 h
on stream (Figures 3A and S11). Co(CO)4⊂CrꢀMILꢀ101 was also
able to carbonylate βꢀbutyrolactone cleanly to the respective meꢀ
A key feature of βꢀlactone carbonylation by Co(CO)4⊂CrꢀMILꢀ
101 is the ease of product recovery from the heterogeneous cataꢀ
lyst. When catalyst loading was increased to fully convert the
substrate in a continuousꢀflow βꢀpropiolactone carbonylation,
ambient evaporation of the volatile DCM from the product stream
led to isolation of the desired succinic anhydride as a crystalline
solid (Figure S12). Similar results were obtained from batchꢀwise
βꢀpropiolactone carbonylation studies, where filtration of the solid
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 6
Production. in Handbook of Maleic Anhydride Based Materials; Musa, O.
M., Ed.; Springer International Publishing Switzerland: Cham, 2016; pp
3−54.
(6) Trifirò, F.; Grasselli, R. K. How the Yield of Maleic Anhydride in
nꢀButane Oxidation, Using VPO Catalysts, was Improved Over the Years.
Top. Catal. 2014, 57, 1188−1195.
catalyst and subsequent evaporation of the fully converted product
mixture resulted in recovery of succinic anhydride crystals. These
simple operations greatly contrast the complicated separations
schemes required in hydrocarbon oxidation or microbial fermentaꢀ
tion processes (e.g., NH3/H2SO4ꢀassisted succinate precipitation,
NaOHꢀassisted electrodialysis, amineꢀassisted reactive extraction,
etc.19) and further corroborates the potential of our heterogeneous
βꢀlactone carbonylation pathway for the industrial production of
succinic anhydrides.
1
2
3
4
5
6
7
8
(7) Lohbeck, K.; Haferkorn, H.; Fuhrmann, W.; Fedtke, N. Maleic and
Fumaric Acids. in Ullmann’s Encyclopedia of Industrial Chemistry;
Elvers, B., Ed.; WileyꢀVCH: Weinheim, 2011; Vol. 22, pp 145−155.
(8) Top Value Added Chemicals from Biomass; DOE/GOꢀ102004ꢀ
1992; U.S. Department of Energy, U.S. Department of Commerce
National Technical Information Service: Alexandria, VA, 2004.
(9) Mazière, A.; Prinsen, P.; García, A.; Luque, R.; Len, C. A Review
of Progress in (Bio)catalytic Routes from/to Renewable Succinic Acid.
Biofuels, Bioprod. Bioref. 2017, 11, 908−931.
(10) Ahn, J. H.; Jang, Y. S.; Lee, S. Y. Production of Succinic Acid by
Metabolically Engineered Microorganisms. Curr. Opin. Biotechnol. 2016,
42, 54−66.
(11) Morales, M.; Ataman, M.; Badr, S.; Linster, S.; Kourlimpinis, I.;
Papadokonstantakis, S.; Hatzimanikatis, V.; Hungerbühler, K.
Sustainability Assessment of Succinic Acid Production Technologies from
Biomass Using Metabolic Engineering. Energy Environ. Sci. 2016, 9,
2794−2805.
In summary, we report Co(CO)4⊂CrꢀMILꢀ101 as the first hetꢀ
erogeneous catalyst for the selective ringꢀexpanding carbonylation
of βꢀlactones to succinic anhydrides. Its facile application to a
packedꢀbed reactor process for continuous production and recovꢀ
ery of succinic anhydrides substantiates the potential efficacy of
the heterogeneous βꢀlactone carbonylation pathway. We ascribe
the favorable performance of the catalyst to the intrinsic structural
advantages of the MOF platform, which supports precise coordiꢀ
nation geometries20–22 as isolated single sites23–25 within a robust
porous scaffold26–28 for novel catalytic applications. We believe
these unique structural properties could be leveraged for the deꢀ
velopment of an improved class of heterogeneous catalysts. In
addition, identification of an optimum flow reactor configuration
through reaction kinetics studies is anticipated to further enhance
the performance of the βꢀlactone carbonylation process.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(12) Church, T. L.; Getzler, Y. D. Y. L.; Byrne, C. M.; Coates, G. W.
Carbonylation of Heterocycles by Homogeneous Catalysts. Chem.
Commun. 2007, 657−674.
(13) Allen, S. D.; Valente, R. R.; Lee, H.; Cherian, A. E.; Bunning, D.
L.; Clinton, N. A.; Fruchey, O. S.; Dombek, B. D. Process for Betaꢀ
lactone Production. U.S. 9,493,391, Nov. 15, 2016.
ASSOCIATED CONTENT
Supporting Information
(14) Rowley, J. M.; Lobkovsky, E. B.; Coates, G. W. Catalytic Double
Carbonylation of Epoxides to Succinic Anhydrides: Catalyst Discovery,
Reaction Scope, and Mechanism. J. Am. Chem. Soc. 2007, 129,
4948−4960.
The Supporting Information is available free of charge on the
ACS Publications website.
(15) Park, H. D.; Dincă, M.; RománꢀLeshkov, Y. Heterogeneous
–
Epoxide Carbonylation by Cooperative Ionꢀpair Catalysis in Co(CO)4 ꢀ
Experimental information and supplementary data
(PDF)
incorporated CrꢀMILꢀ101. ACS Cent. Sci. 2017, 3, 444−448.
(16) Hong, D. Y.; Hwang, Y. K.; Serre, C.; Férey, G.; Chang, J. S.
Porous Chromium Terephthalate MILꢀ101 with Coordinatively
Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and
Catalysis. Adv. Funct. Mater. 2009, 19, 1537−1552.
(17) Getzler, Y. D. Y. L.; Kundnani, V.; Lobkovsky, E. B.; Coates, G.
W. Catalytic Carbonylation of βꢀLactones to Succinic Anhydrides. J. Am.
Chem. Soc. 2004, 126, 6842−6843.
(18) Reichardt, R.; Vagin, S.; Reithmeier, R.; Ott, A. K.; Rieger, B.
Factors Influencing the Ringꢀopening Polymerization of Racemic βꢀ
Butyrolactone Using CrIII(salphen). Macromolecules 2010, 43,
9311−9317.
(19) Jansen, M. L. A.; van Gulik, W. M. Towards Large Scale
Fermentative Production of Succinic Acid. Curr. Opin. Biotechnol. 2014,
30, 190−197.
(20) Wang, L.; Agnew, D. W.; Yu, X.; Figueroa, J. S.; Cohen, S. M. A
Metal−Organic Framework with Exceptional Activity for C−H Bond
Amination. Angew. Chem. Int. Ed. 2018, 57, 511−515.
(21) Stubbs, A. W.; Braglia, L.; Borfecchia, E.; Meyer, R. J.; Románꢀ
Leshkov, Y.; Lamberti, C.; Dincǎ, M. Selective Catalytic Olefin
Epoxidation with MnIIꢀexchanged MOFꢀ5. ACS Catal. 2018, 8, 596−601.
(22) Ji, P.; Feng, X.; Veroneau, S. S.; Song, Y.; Lin, W. Trivalent
Zirconium and Hafnium Metal−Organic Frameworks for Catalytic 1,4ꢀ
Dearomative Additions of Pyridines and Quinolines. J. Am. Chem. Soc.
2017, 139, 15600−15603.
(23) Chen, X.; Peng, Y.; Han, X.; Liu, Y.; Lin, X.; Cui, Y. Sixteen
Isostructural Phosphonate Metal−Organic Frameworks with Controlled
Lewis Acidity and Chemical Stability for Asymmetric Catalysis. Nat.
Commun. 2017, 8, 2171−2179.
(24) Ji, P.; Solomon, J. B.; Lin, Z.; Johnson, A.; Jordan, R. F.; Lin, W.
Transformation of Metal−Organic Framework Secondary Building Units
into Hexanuclear Zr−Alkyl Catalysts for Ethylene Polymerization. J. Am.
Chem. Soc. 2017, 139, 11325−11328.
AUTHOR INFORMATION
Corresponding Author
*Email: mdinca@mit.edu
*Email: yroman@mit.edu
Notes
The authors are listed as inventors on a patent pertaining to the
results herein.
ACKNOWLEDGMENT
H.D.P. gratefully acknowledges the Samsung Foundation for
support through the Samsung Scholarship program. Y.R.ꢀL.
thanks the Department of Energy for funding through the Office
of Basic Energy Sciences (DEꢀSC0016214). Studies of ion exꢀ
change and small molecule reactivity in MOFs were supported by
a CAREER grant from the National Science Foundation to M.D.
(DMRꢀ1452612). We thank Chenyue Sun for assistance with the
inductively coupled plasma mass spectrometry analysis.
REFERENCES
(1) Bechthold, I.; Bretz, K.; Kabasci, S.; Kopitzky, R.; Springer, A.
Succinic Acid: A New Platform Chemical for Biobased Polymers from
Renewable Resources. Chem. Eng. Technol. 2008, 31, 647−654.
(2) Sauer, M.; Porro, D.; Mattanovich, D.; Branduardi, P. Microbial
Production of Organic Acids: Expanding the Markets. Trends Biotechnol.
2008, 26, 100−108.
(3) Cheng, K.; Zhao, X.; Zeng, J.; Zhang, J. Biotechnological
Production of Succinic Acid: Current State and Perspectives. Biofuels,
Bioprod. Bioref. 2012, 6, 302−318.
(25) Dubey, R. J. C.; Comito, R. J.; Wu, Z.; Zhang, G.; Rieth, A. J.;
Hendon, C. H.; Miller, J. T.; Dincǎ, M. Highly Stereoselective
Heterogeneous Diene Polymerization by CoꢀMFUꢀ4l:
A Singleꢀsite
Catalyst Prepared by Cation Exchange. J. Am. Chem. Soc. 2017, 139,
12664−12669.
(26) Choi, K. M.; Kim, D.; Rungtaweevoranit, B.; Trickett, C. A.;
Barmanbek, J. T. D.; Alshammari, A. S.; Yang, P.; Yaghi, O. M. Plasmonꢀ
(4) Schultheiss, N.; Newman, A. Pharmaceutical Cocrystals and Their
Physicochemical Properties. Cryst. Growth Des. 2009, 9, 2950−2967.
(5) Hood, D. K.; Musa, O. M. Progress in Maleic Anhydride
ACS Paragon Plus Environment

Page 5 of 6
Journal of the American Chemical Society
enhanced Photocatalytic CO2 Conversion within Metal−Organic
J. Am. Chem. Soc. 2017, 139, 15251−15258.
Frameworks Under Visible Light. J. Am. Chem. Soc. 2017, 139, 356−362.
(27) Li, Z.; Peters, A. W.; PlateroꢀPrats, A. E.; Liu, J.; Kung, C. W.;
Noh, H.; DeStefano, M. R.; Schweitzer, N. M.; Chapman, K. W.; Hupp, J.
T.; Farha, O. K. Fineꢀtuning the Activity of Metal−Organic Frameworkꢀ
supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane.
(28) Yuan, S.; Qin, J.ꢀS.; Lollar, C. T.; Zhou, H.ꢀC. Stable
Metal−Organic Frameworks with Group 4 Metals: Current Status and
Trends. ACS Cent. Sci. 2018, 4, 440−450.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 6
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
TOC graphic:
6
ACS Paragon Plus Environment