Communication

Cite This: J. Am. Chem. Soc. 2017, 139, 17747−17750 pubs.acs.org/JACS

Molecular Iridium Complexes in Metal−Organic Frameworks

Catalyze CO2 Hydrogenation via Concerted Proton and Hydride
Transfer
Bing An,†,§ Lingzhen Zeng,†,§ Mei Jia,†,§ Zhe Li,† Zekai Lin,‡ Yang Song,‡ Yang Zhou,† Jun Cheng,*,†
Cheng Wang,*,† and Wenbin Lin*,†,‡
†
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces,
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China
‡
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Department of Chemistry, University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, United States
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*
S Supporting Information

Scheme 1. Schematic Showing a Soxhlet-Type Reflux-

ABSTRACT: Molecular iridium catalysts immobilized in Condensing System To Place MOF Catalysts at a Dynamic
metal−organic frameworks (MOFs) were positioned in Triphasic Interface of CO2/H2−H2O-Catalyst for CO2
the condensing chamber of a Soxhlet extractor for efficient Hydrogenation to Formate
CO2 hydrogenation. Droplets of hot water seeped through
the MOF catalyst to create dynamic gas/liquid interfaces
which maximize the contact of CO2, H2, H2O, and the
catalyst to achieve a high turnover frequency of 410 h−1
under atmospheric pressure and at 85 °C. H/D kinetic
isotope effect measurements and density functional theory
calculations revealed concerted proton−hydride transfer in
the rate-determining step of CO2 hydrogenation, which
was difficult to unravel in homogeneous reactions due to
base-catalyzed H/D exchange.

H ydrogenation of CO2 to formic acid (HCO2H) is of great

interest, not only as an attractive path to convert CO2 to
platform chemicals, but also as a key step in hydrogen storage
using HCO2H as a chemical carrier.1 However, low solubility of
hydrogen in water has limited the catalytic turnover frequency
(TOF).2 Herein, we report the design of metal−organic
framework (MOF) catalysts for efficient CO2 hydrogenation in
a Soxhlet-type reflux-condensing system. Solid MOF catalysts
were packed in a plate that was located below the condenser.
Droplets of hot condensed water passed through the catalyst bed
intermittently, creating a dynamic gas/liquid/solid interface to
maximize the contact among CO2, H2, H2O, and the catalyst to
produce formic acid (Scheme 1). The generated formic acid in
the aqueous solution was then siphoned to the refluxing flask and
neutralized by sodium bicarbonate to formate, pushing the
chemical equilibrium of H2(g) + CO2(g) ⇄ HCO2H(aq) to the
right.
Key to this reaction design is the construction of solid MOF
catalysts3 based on molecular functionalities.4 A number of Ru,5
Rh,6 Ir,7 Co,8 Re,9 and Fe10 complexes have been reported to be
highly active in CO 2 hydrogenation, among which Ir-
polypyridine-based complexes form a versatile category.11 We
incorporated Ir complexes into UiO-type MOFs using 2,2′-
bipyridine-5,5′-dicarboxylate ligands with or without −OH
substitution on the 6-position (bpydcOH or bpydc) to provide
isolated anchoring sites for Ir. After activation, the Ir complexes
immobilized in MOFs exhibit high activity to hydrogenate CO2
to formate in the reflux-condensing setup.
Importantly, performing the reactions with D2 and/or D2O in
place of H2 and/or H2O under neutral pH revealed ultralarge H/
D kinetic isotope effects (KIEs) which were previously masked
by base-catalyzed H/D exchange in homogeneous systems. The
ultralarge KIEs for CO2 hydrogenation suggest concerted
proton−hydride transfer via quantum tunneling in the rate-
determining step (RDS), which was further supported by density
functional theory (DFT) calculations.
H2bpydcOH was prepared from H2bpydc in four steps in a
22% overall yield (see Supporting Information [SI] for details,
Figures S1−S11). The hydroxyl group in bpydcOH serves as an
electron-donating group and a hydrogen-bonding site, which has
been reported to facilitate CO2 hydrogenation in homogeneous
Ir complexes.11 Less sterically demanding 4,4′-biphenyl-
dicarboxylic acid (H2bpdc) was mixed with H2bpydcOH or
H2bpydc in MOF synthesis to preserve open channels in
metalated MOFs. The reaction between the ligand mixture and
ZrCl4 in dimethylformamide (DMF) at 120 °C yielded
Received: October 13, 2017
Published: November 28, 2017

© 2017 American Chemical Society 17747 DOI: 10.1021/jacs.7b10922

J. Am. Chem. Soc. 2017, 139, 17747−17750
Journal of the American Chemical Society Communication

Table 1. Hydrogenation of CO2 to Formate Using Different

Catalysts
entry catalyst Ir (wt%) TONb TOFb (h−1)
1a
mbpyOH-IrCl3-UiO 2.6 543 ± 35 36 ± 2
2a mbpy-IrCl3-UiO 3.8 23 ± 4 1.5 ± 0.2
3a mbpyOH-UiO no formate
4a mbpy-UiO no formate
5a mbpyOH-[IrIII]-UiO 2.4 6149 ± 50 410 ± 3
6a mbpy-[IrIII]-UiO 3.8 417 ± 22 28 ± 2
7a Ir-NP 100 0 0
8c mbpyOH-[IrIII]-UiO 2.4 0 0
9d bpydcOH-IrCl3(OH2) 31 13/11e/8f 0.9/0.7e/ 0.5f
10c bpydcO−-IrCp*OH 18.4 0 0
11d bpydcO−-IrCp*OH 18.4 256 ± 10 17.0 ± 0.7
a
Reaction conditions: 5 mg of catalysts in reflux-condensing system,
0.1 MPa H2/CO2 = 1, 1 M NaHCO3(aq) in bottom flask, temp = 85
°C, time = 15 h. bTON and TOF are both based on Ir. c10 mg of
catalysts, 10 mL of 1 M NaHCO3(aq) in a flask, 0.1 MPa H2/CO2 = 1,
temp = 85 °C, time = 15 h. d10 mg of catalysts, 10 mL of 1 M
NaHCO3(aq) in a bomb, 1 MPa H2/CO2 = 1, temp = 85 °C, time =
15 h. eWith NaHBEt3. fWith AgNO3.

Figure 1. (a) Preparation of mbpyOH-[IrIII]-UiO and mbpy-[IrIII]-UiO

catalysts. (b) Local structure of mbpyOH-[IrIII]-UiO. (c) EXAFS
spectra of mbpyOH-[IrIII]-UiO at the Ir LIII-edge together with the
fittings in R-space, showing the magnitude (hollow squares, red) and the
real (hollow squares, blue) components. The fitting range is 1.0−3.0 Å
in R-space (within the black line).
mbpyOH-UiO and mbpy-UiO MOFs with [Zr6(μ3-O)4(μ3-
OH)4]12+ as secondary building units (SBUs) (Figure 1a,b).
The UiO-type MOF structures of mbpyOH-UiO and mbpy-
UiO were revealed by the similarity of their powder X-ray
diffraction (PXRD) patterns to that of UiO-67 (Figure S12).12
Transmission electron microscopy (TEM) showed octahedral
nanocrystals of the MOFs (Figures S13 and S14). Chemical
formulas of these MOFs were established by a combination of
thermogravimetric analyses to determine mass ratios of metal/
organics (Figures S15 and S16) and proton nuclear magnetic
resonance (1H NMR) spectra of digested MOFs in NaOD/D2O
to quantify amounts of ligands and capping formates (Figures
S17 and S18). We obtained chemical formulas of Zr6(μ3-O)4(μ3-
OH)4(bpdc)2.67(bpydcOH)2.67(HCO2)1.33 for mbpyOH-UiO
and Zr6(μ3-O)4(μ3-OH)4(bpdc)2.07(bpydc)3.10(HCO2)1.66 for
mbpy-UiO.
Postsynthetic metalation of the MOFs with IrCl3·3H2O in a
mixture of tetrahydrofuran (THF) and DMF gave metalated
MOFs mbpyOH-IrCl3-UiO and mbpy-IrCl3-UiO with bpyOH-
IrCl3(THF) and bpy-IrCl3(THF) moieties, respectively. Ir
loading levels determined by inductively coupled plasma-mass
spectrometry (ICP-MS) correspond to incorporation of 10.5
mol% of Ir on the bpyOH sites in mbpyOH-IrCl3-UiO and 13.7
mol% of Ir on the bpy sites in mbpy-IrCl3-UiO. PXRD patterns
showed that both metalated MOFs remained crystalline (Figure
S12). Nitrogen sorption experiments gave BET surface areas of
705 m2/g for mbpyOH-Ir-UiO and 843 m2/g for mbpy-Ir-UiO
(Figure S19).
Local coordination environments of Ir in MOFs were probed
by X-ray absorption spectroscopy (XAS) at the Ir LIII-edge. X-ray
absorption near edge structure (XANES) of mbpyOH-IrCl3-UiO
confirmed the oxidation state of IrIII by a rising edge similar to
that of IrCl3 (main peak at 11217 eV) (Figure S20).4e Fittings of
the extended X-ray absorption fine structure (EXAFS) regions
17748
afforded six-coordinated Ir centers with two nitrogen atoms from
bipyridine moiety, three chlorides, and one oxygen atom from a
THF molecule in the first coordination sphere (Figures S21 and
S22).
The catalytic activities of mbpyOH-IrCl3-UiO and mbpy-
IrCl3-UiO in CO2 hydrogenation were evaluated in the Soxhlet-
type reflux-condensing system. The bottom flask contained a
basic aqueous solution of 1 M NaHCO3. After a reaction of 15 h,
formate was detected in the bottom flask by 1H NMR and
quantified by high performance liquid chromatography (HPLC)
(Table 1, entries 1 and 2; Figures S28−S30). No gaseous product
was detected in the headspace by gas chromatography (Figure
S31). mbpyOH-IrCl3-UiO gave an Ir-based turnover number (Ir-
TON) of 543 ± 35 in 15 h with an average Ir-TOF of 36 ± 2 h−1
under 1 atm of H2/CO2 = 1/1, while mbpy-IrCl3-UiO afforded
an Ir-TON of 23 ± 4 and an Ir-TOF of 1.5 ± 0.2. Control
experiments with non-metalated mbpyOH-UiO or mbpy-UiO
gave no products (Table 1, entries 3 and 4), confirming the role
of Ir as the catalytic center. The temperature of the condensed
water at the catalyst bed was measured to be 85 °C.
Monitoring the Ir-TONs of mbpyOH-IrCl3-UiO over time
revealed an induction period of approximately 8 h, suggesting the
need to transform the bpyOH-IrIIICl3(solvent) species to an
active form, which possibly involves breaking Ir−Cl bonds. To
facilitate chloride removal, mbpyOH-IrCl3-UiO and mbpy-IrCl3-
UiO were treated with NaBHEt3 followed by air oxidation to
yield mbpyOH-[IrIII]-UiO and mbpy-[IrIII]-UiO (Figure 1a). A
mixture of [bpyO-IrIIICl2(OH2)2], [bpyO-IrIIICl(OH2)3]+, and
[bpyO-IrIII(OH)(OH2)3]+ were present in mbpyOH-[IrIII]-UiO
with different extents of chloride removal (Figures S23−S26). In
the following discussions, we focus on the [bpyO−-IrIII(OH)-
(OH2)3]+ species as a representative site. The degree of
deprotonation of [bpyO−-IrIII(OH)(OH2)3]+ was based on
DFT calculation of pKa values of protons in each coordinated
water and the hydroxyl group on the ligand (Figures S53−S55).
The activated mbpyOH-[IrIII]-UiO gave much higher catalytic
activity than the unactivated one, achieving an Ir-TON of 6149 ±
50 in 15 h and an Ir-TOF of 410 ± 3 h−1 (Table 1, entry 5, Figure
S32) with a shorter induction period of ∼3 h (Figure 2a). These
DOI: 10.1021/jacs.7b10922
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Journal of the American Chemical Society
Figure 2. Catalytic data of the Ir-based catalysts: (a) TONs as a function
of reaction time and (b) KIE values under different conditions.
TON and TOF values compare favorably with other catalysts for
CO2 hydrogenation at ambient pressure (Table S6).
mbpyOH-[IrIII]-UiO was recovered and reused for at least
three times without obvious loss of catalytic activity (Figure
S34). The recovered mbpyOH-[IrIII]-UiO after catalysis
remained crystalline, as shown by PXRD patterns (Figure
S12). The oxidation state of IrIII in mbpyOH-[IrIII]-UiO
remained unchanged based on XANES and XPS studies (Figures
S20 and S26). ICP-MS analyses of the aqueous solution in the
refluxing flask showed negligible metal leaching (0.18% of Ir and
0.05% of Zr). Importantly, a second 15 h reaction of this solution
produced no additional products, proving that the mbpyOH-
[IrIII]-UiO instead of the leached species was the active catalyst.
Control experiments using Ir nanoparticles (Ir-NP) did not give
any CO2 hydrogenation products (Table 1, entry 7; Figures S35
and S36), ruling out Ir-NPs as catalysts.
The reflux-condensing system for placing the catalysts at
liquid−gas interface greatly enhanced their TOFs compared to
catalysis with the same catalysts in solutions. For example,
mbpyOH-[IrIII]-UiO in a 1 M NaHCO3 solution generated
negligible amounts of formate at 85 °C (Table 1, entry 8), in part
due to the decomposition of the MOF in basic solutions.
Furthermore, homogeneous molecular bpydcOH-IrCl3(OH2)
complex with or without treatment with NaBHEt3 or AgNO3
gave low activities with TOFs of <1 h−1 at gas pressures of 1 MPa
(Table 1, entry 9). The homogeneous catalysts may form inactive
dimers or oligomers, which is prevented in MOFs due to active
site isolation on the framework. Consistent with this hypothesis,
introduction of a bulky pentamethylcyclopentadiene (Cp*)
group in the complex bpydcO−-IrCp*OH slowed catalyst
deactivation to afford a moderate Ir-TON of 256 ± 10 in 15 h
at a gas pressure of 1 MPa and a temperature of 85 °C (Table 1,
entry 11, Figure S37), which is still much lower than that of
mbpyOH-[IrIII]-UiO in the reflux-condensing setup at a gas
pressure of 0.1 MPa.
The enhanced activity of mbpyOH-[IrIII]-UiO over that of
mbpy-[IrIII]-UiO by 11 times (Table1, entry 6, Figure S33)
demonstrated the importance of hydroxyl group on the bpyOH
ligand.13 To further probe the mechanism, we measured solvent
KIEs (Figures 2b, S38−S40) by comparing the reaction rates
using D2O vs H2O in two separate experiments. HCO2Na but
not DCO2Na was produced with D2O in the bottom flask and H2
in the headspace for both mbpyOH-[IrIII]-UiO and mbpy-[IrIII]-
UiO as revealed by 1H NMR and 2H NMR (Figures S41 and
S42). These results suggest that hydrogen in formate comes from
H2 in the gas phase. As the heterolytic splitting of H2 generates
iridium hydride species, formates must be produced from CO2
via a hydride transfer step. Importantly, a dramatic reduction of
reaction rate was observed using D2O as the solvent with a large
KIE (H2O/H2-D2O/H2) value ([rate in H2O]/[rate in D2O]) of
140 for mbpyOH-[IrIII]-UiO. Such a large KIE value is only
17749
Communication
Figure 3. (a) Proposed mechanism for the hydrogenation of CO2 by
mbpyOH-[IrIII]-UiO with activation enthalpies (see SI). (b) Calculated
free-energy profiles for the proposed catalytic cycle for CO2 hydro-
genation to formic acid.
possible when quantum tunneling of proton is involved in the
RDS. In contrast, mbpy-[IrIII]-UiO gave a KIE (H2O/H2-D2O/
H2) value of 7.8.
On the other hand, when D2 was used in the gas phase and
H2O was used as the solvent, DCO2Na was exclusively produced
for both mbpyOH-[IrIII]-UiO and mbpy-[IrIII]-UiO (Figures
S43 and S44), again confirming that the deuterium in DCO2−
originated from D2. The KIE (H2O/H2−H2O/D2) value ([rate
with H2]/[rate with D2]) was 19 for mbpyOH-[IrIII]-UiO and
5.9 for mbpy-[IrIII]-UiO. Such a KIE value over 10 for mbpyOH-
[IrIII]-UiO also indicates nuclear tunneling during the hydride
transfer to CO2.
When the reaction was carried out using a combination of D2
in the gas phase and D2O in the aqueous phase, negligible
amount of formate was produced with mbpyOH-[IrIII]-UiO
(Figures S45 and S46), affording an overall KIE (H2/H2O−D2/
D2O) value of over 3000, which is no less than the product of KIE
(H2O/H2-D2O/H2) and KIE (H2O/H2−H2O/D2). This is only
possible when proton transfer and hydride transfer to CO2 take
place in the same RDS.14 Similarly, the double deuterium
experiment for mbpy-[IrIII]-UiO gave a KIE (H2/H2O−D2/
D2O) value over 45, larger than the product of KIE (H2O/H2-
D2O/H2) and KIE (H2O/H2−H2O/D2).
Based on these experimental observations, we propose a
catalytic cycle which is supported by DFT calculations as shown
in Figure 3. The transition states of H2 heterolysis (A*) and
proton−hydride transfer (C*) gave activation energies of Ea1 =
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Journal of the American Chemical Society
0.34 kcal·mol−1 and Ea2 = 16.26 kcal·mol−1, supporting the
proton−hydride transfer to be the RDS. The corresponding
energy profiles are shown in Figure 3b. The equilibria between
B/C and D/A depend on the reaction pH and the pKa’s of B and
A (Figure S57). In addition, calculated H/D KIE value
considering only zero-point energies gave a small number of
∼2, suggesting that the quantum tunneling effect plays a key role
in the experiment. Similar concerted proton and hydride transfer
has been previously reported for the alcohol dehydrogenase and
an Os complex.15
It is worth noting that the homogeneous catalyst bpydcO−-
IrCp*OH in basic solution gave different isotope distributions in
products. With both H2O/D2 and D2O/H2, the homogeneous
catalyst produced a mixture of DCO2Na and HCO2Na with the
DCO2Na/HCO2Na ratios of 0.80 and 0.98, respectively (Figures
S47−S52). This D/H exchange likely results from base-assisted
reductive elimination of the slightly protonic Ir−H(D) bond to
produce IrI species, which can be further protonated by
D2O(H2O) to regenerate Ir-D(H). The D/H exchange masked
the KIE to give moderate apparent values of 1.1 and 1.6 with
H2O/D2 and D2O/H2, respectively.
In summary, we performed efficient catalytic CO2 hydro-
genation to form formic acid/formate by placing MOF catalysts
in a Soxhlet-type reflux-condensing system. Replacing H2 and/or
H2O by D2 and/or D2O in the reaction revealed ultralarge H/D
KIEs by preventing base-catalyzed H/D exchange in homoge-
neous reactions. The ultralarge KIEs and DFT calculations
suggest concerted proton−hydride transfer in the rate-
determining step of CO2 hydrogenation. This work highlights
opportunities to use MOFs as solid molecular catalysts in
designer reactors to improve catalytic conversions and to
uncover interesting mechanistic details.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.7b10922.
Experimental procedures; spectroscopic characterization
of precatalysts and catalysts; X-ray absorption spectro-
scopic analysis; evaluation of catalytic performances; KIEs
and quantifications of HCOOH and DCOOH; and DFT
calculations (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*chengjun@xmu.edu.cn
*wangchengxmu@xmu.edu.cn
*wenbinlin@uchicago.edu
ORCID
Cheng Wang: 0000-0002-7906-8061
Wenbin Lin: 0000-0001-7035-7759
Author Contributions
§ (14) O’Leary, M. H. Annu. Rev. Biochem. 1989, 58, 377−401.
B.A., L.Z., and M.J. contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We acknowledge funding support from the National Natural
Science Foundation and Ministry of Science and Technology of
the P. R. China (NSFC21671162, 2016YFA0200702, NSFC-
21471126, NSFC21373166, NSFC21621091), the National
17750
Communication
Thousand Talents Program of the P. R. China, Xiamen
University, and the U.S. National Science Foundation (DMR-
1308229).
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