This article is licensed under CC-BY 4.

pubs.acs.org/orginorgau Article

Biomimetic Frustrated Lewis Pair Catalysts for Hydrogenation of CO

to Methanol at Low Temperatures
Jiejing Zhang, Longfei Li,* Xiaofeng Xie, Xue-Qing Song,* and Henry F. Schaefer, III*
Cite This: https://doi.org/10.1021/acsorginorgau.3c00064 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: The industrial production of methanol through CO hydro-

Downloaded via INDIAN INST OF TECH PALAKKAD on February 10, 2024 at 12:52:14 (UTC).

genation using the Cu/ZnO/Al2O3 catalyst requires harsh conditions, and the
development of new catalysts with low operating temperatures is highly
desirable. In this study, organic biomimetic FLP catalysts with good tolerance
to CO poison are theoretically designed. The base-free catalytic reaction
contains the 1,1-addition of CO into a formic acid intermediate and the
hydrogenation of the formic acid intermediate into methanol. Low-energy
spans (25.6, 22.1, and 20.6 kcal/mol) are achieved, indicating that CO can be
hydrogenated into methanol at low temperatures. The new extended
aromatization−dearomatization effect involving multiple rings is proposed
to effectively facilitate the rate-determining CO 1,1-addition step, and a new
CO activation model is proposed for organic catalysts.
KEYWORDS: CO hydrogenation, biomimetic FLP catalysts, density functional theory, 1,1-addition, base-free

1. INTRODUCTION to methanol catalyzed by various transition-metal carbonyls

Alternative energy sources have received great attention due to has been reported, but the problem of extreme reaction
the limited supply and increasing cost of fossil fuel resources.1,2 conditions was not solved.14−20 In general, CO is a high-field
Methanol is an excellent fuel in its own right and can also ligand, and its migratory insertion into a metal−hydride bond
produce energy in electrochemical cells or other energy vectors is highly endothermic, which is responsible for the harsh
such as hydrogen.3−5 Besides, methanol is a key feedstock for reaction conditions.21,22 Instead, avoiding this highly endo-
the production of small-chain hydrocarbons.6,7 Olah and co- thermic CO insertion step could allow mild reaction
conditions for the synthesis of methanol.23
workers previously advocated “methanol economy” as a way
Recently, bifunctional metal catalysts have been reported to
toward the sustainable economy, in which petroleum-based
catalyze the hydrogenolysis of esters, amides, and their
fuels and chemicals are replaced with methanol.8 However,
derivatives to produce alcohols.24−29 Those research studies
methanol is industrially produced from CO hydrogenation
inspired the design of bifunctional metal catalysts for the
using Cu/ZnO/Al2O3 heterogeneous catalysts at elevated
indirect hydrogenation of CO to methanol via ester or amide
pressures (50−100 bar) and temperatures (200−300 °C).9,10
intermediates. In 2019, Prakash and co-workers found that
Since the hydrogenation of CO to methanol is an exothermic
electron-withdrawing phenyl groups could render the Ru−
reversible reaction, CO conversion in current processes is
Macho−BH complex resistant to CO poisoning and achieved
thermodynamically limited to around 30% at such high
the Ru−Macho−BH catalyzed indirect hydrogenation of CO
operating temperatures.11 Therefore, the development of
to methanol at 145 °C with a turnover number (TON) of 539
homogeneous catalysts for CO hydrogenation at low temper-
(Scheme 2a).12 Prakash also proposed that CO was first
atures would be a significant progress toward increasing the
anchored onto the amine as a formamide and then hydro-
energy efficiency and CO conversions.12 The main challenges
genated in situ to methanol. In the same year, Beller and co-
are the high endothermic migratory insertion process of CO
workers investigated a series of metal complexes for the
into metal hydride bonds and the poisons of CO to metal
indirect hydrogenation of CO to methanol through N-
catalysts (Scheme 1).
The reported homogeneous CO hydrogenations rely on
metal catalysts, and the mechanisms can be broadly divided Received: November 27, 2023
into direct and indirect mechanisms. In the early 1950s, Revised: January 12, 2024
DuPont Company first reported the direct hydrogenation of Accepted: January 16, 2024
CO to methanol catalyzed by cobalt carbonyl complexes, but
the reaction required ultrahigh pressures (1500−5000 atm).13
In the following three decades, the direct hydrogenation of CO
© XXXX The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsorginorgau.3c00064
A ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au
Scheme 1. Catalysts for the Hydrogenation of CO to Methanol
Scheme 2. Reported Bifunctional Metal Catalysts for the Indirect Hydrogenation of CO to Methanol
formylazole intermediates, and the manganese pincer complex
exhibited the best tolerance to CO and gave the optimal TON
(3170) at 120−150 °C (Scheme 2b).30 In 2021, Leitner and
co-workers reported an alcohol-assisted indirect hydrogenation
of CO to methanol catalyzed by a manganese pincer complex
with a catalytic amount of base at 150 °C (Scheme 2c).31 They
found that the increased pressure of CO could inhibit
methanol formation. These remarkable bifunctional metal
catalysts facilitate indirect CO hydrogenation but are still
limited by high reaction temperatures and low yields, which
could be associated with the deactivation of transition-metal
catalysts in the presence of CO.32
Main-group element catalysts are desirable alternatives to
transition-metal catalysts because of their natural abundance
and low cost.33,34 More importantly, main-group element
catalysts have low binding affinity to CO, owing to the lack of
B https://doi.org/10.1021/acsorginorgau.3c00064
pubs.acs.org/orginorgau Article
suitable π-back-bonding orbitals.35 This implies good tolerance
to CO and inspires us to explore main-group element catalysts
for the indirect hydrogenation of CO to methanol. Frustrated
Lewis pairs (FLPs) introduced by Stephan and co-workers are
now an important branch of main-group element chemis-
try36,37 and have been applied in the catalytic hydrogenation of
various unsaturated compounds including CO2,38 olefins,39
alkynes,40 ketones,41 and imines.42 Particularly, the FLP-
catalyzed hydrogenation of amides43 and esters44,45 to provide
alcohols was also reported recently. However, FLP-catalyzed
CO hydrogenation has not been reported yet. How can we
endow FLP catalysts with high activities toward CO hydro-
genations?
The design of novel bioinspired catalysts mimicking the
mechanism of biocatalysts is an important strategy to obtain
high catalytic activity, yield, and selectivity.46−49 The nucleic
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au
Scheme 3. Nucleic Acid Bases and Bioinspired FLP Catalysts
acid bases (Scheme 3) with resonance stabilization effects can
undergo protonation or tautomerization50−53 and play an
important role in the reproduction and transmission of genetic
information.54 Can the Lewis basic nucleic acid bases form
novel FLP catalysts with borane counterparts and achieve new
chemical reactivities? The theoretical design plays a more and
more important role in discovering new chemistry, and many
achievements have been made to solve important problems in
chemistry.55−60 Inspired by our and other groups’ silico
reaction discoveries,61−67 we theoretically design bioinspired
FLP catalysts based on nucleic acid bases and compare their
catalytic activities in the CO hydrogenation reaction to
methanol with the traditional FLP catalysts.
2. COMPUTATIONAL METHODS
In accord with our previous theoretical studies,68−70 this research was
carried out with the DFT ωB97X-D71 method using the Gaussian 09
program.72 Geometries were optimized in a dichloromethane solvent
using the 6-311G(d,p)73 basis sets. The single-point energy
refinements were further performed with the 6-311++G(2d,p) basis
sets. The refined energies were then corrected to Gibbs energies at
298.15 K and 1 atm by using the ωB97X-D/6-311G(d,p) harmonic
frequencies. Solvent effects were evaluated using the SMD (solution
model based on density) solvation model.74,75 All transition states
were demonstrated to exhibit only one imaginary vibrational
frequency. Intrinsic reaction coordinate (IRC) analyses were
performed to confirm that all transition states connect the two
minima in question.76 Natural bond orbital (NBO) analyses were
performed using the NBO-7.0 program.77 The Cartesian coordinates
of all optimized structures are presented in the Supporting
Information.
3. RESULTS AND DISCUSSION
The bioinspired FLP A1 featuring a nucleic acid base-fused π-
conjugated linker is designed, and the corresponding structure
is shown in Figure 1. The distance between the Lewis acidic B
atom and the Lewis basic carbonylic O atom is large (5.34 Å),
which provides a suitable pocket for the synchronous
activation of two substrate molecules (e.g., water and CO).
The A1-catalyzed CO hydrogenation to methanol is designed
and is composed of two stages: (1) the 1,1-addition of CO into
formic acid and (2) the hydrogenation of formic acid into
methanol.
C https://doi.org/10.1021/acsorginorgau.3c00064
pubs.acs.org/orginorgau Article
Figure 1. Structure of bioinspired FLP A1 and the catalyzed
hydrogenation of CO to methanol.
3.1. 1,1-Addition of CO to the Formic Acid Intermediate
The bioinspired FLP A1 features good tolerance to CO, and
the coordination of CO to A1 will afford a thermodynamically
unstable intermediate A1_CO, being endergonic by 5.2 kcal/
mol as shown in Figure 2. The dimerization of A1 through
forming a Lewis adduct is thermodynamically disfavored, being
endergonic by 2.4 kcal/mol (Figure S2), suggesting that the
monomer of A1 is the major species in solution. The B atom of
A1 is Lewis acidic with an NBO charge of 0.94 and can bind a
H 2 O molecule through the O → B donor−acceptor
interaction, being endergonic by 4.3 kcal/mol. Through the
transition state TSA2−3, the O−H bond of the coordinated
H2O molecule is cleaved, and the hydroxy proton H(2) moves
to the adjacent carbonylic O atom with an energy barrier of 8.5
kcal/mol. Subsequently, the zwitterionic proton−hydroxo
intermediate A3 is formed, in which the C(1)−N(1) and
C(1)−N(2) bonds are significantly shortened compared with
those in A1. The nucleus-independent chemical shift (NICS)
method is widely utilized for determining aromaticity.78 The
NICS value of the pyrimidinol ring in A3 (ring 1; −6.49 ppm)
is much more negative than that of the pyrimidinone ring in
A1 (ring 1; −2.80 ppm), suggesting that the pyrimidinol ring
in A3 has become aromatized. As for ring 2 and ring 4 in A3,
the NICS values become more negative by 1.54 and 1.20 ppm,
respectively; therefore, the protonation of the carbonylic O
atom also renders the remote ring 2 and ring 4 more aromatic.
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au pubs.acs.org/orginorgau Article

Figure 2. Gibbs energy profile for the 1,1-addition of CO to a formic acid intermediate catalyzed by the bioinspired FLP A1. The relative Gibbs
energies (ΔG) and potential energies (ΔE) are in kcal/mol.

Figure 3. Atomic charges, bond lengths, and the nucleus-independent chemical shift (NICS) values of the rings in A1, A3, and A7. The −tBu and
−C6F5 groups are drawn in a wireframe for simplicity.

The NICS value of ring 3 in A3 increases a bit (0.27 ppm)
(Figure 3). The extended aromatization−dearomatization
effect involving multiple rings was not reported previously.
The proton and hydroxy moieties in zwitterionic A3 can be
added to CO through an unusual 1,1-addition process. The
H(2)...O(2) distance in A3 is 3.81 Å, and the O(2) atom is
nucleophilic with an NBO charge of −0.95. After the transition
state TSA3−4, proton H(2) and hydroxo transfer to the
D https://doi.org/10.1021/acsorginorgau.3c00064
carbonylic C atom of CO, simultaneously. The 1,1-addition of
CO also involves the extended aromatization−dearomatization
effect, and intermediate A4 with a dearomatized pyrimidinone
ring is formed. The following dissociation of the formic acid
molecule from A4 will regenerate catalyst A1, and the stage of
CO 1,1-addition is achieved. Including the energy profile of
Stage 2 included in Section 3.2, the 1,1-addition of CO via
TSA3−4 is the rate-determining step of the overall catalytic
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au pubs.acs.org/orginorgau Article

Figure 4. Comparisons between the typical traditional FLP catalysts and the new bioinspired FLP catalysts via the Gibbs energy barriers (ΔG‡) of
the rate-determining CO 1,1-addition.

Figure 5. (a) Dewar−Chatt−Duncanson model for CO activation based on metal catalysts; (b) dynamic natural localized molecular orbital
(NLMO) analysis for the unusual CO 1,1-addition process; and (c) new CO activation model based on organic catalysts.

reaction with an energy span of 25.6 kcal/mol. Other The acceleration effects of the extended aromatization−
promoters are also considered for the 1,1-addition of CO in dearomatization of our designed bioinspired FLP catalysts are
Figure S3 in SI, and the methanol promoter under catalyst A1 studied. The typical traditional catalysts and the designed
is predicted to own a high-energy barrier of 28.1 kcal/mol. bioinspired FLP catalysts are compared to the Gibbs energy
E https://doi.org/10.1021/acsorginorgau.3c00064
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au
Figure 6. Hydrogen shuttle mechanism for hydrogen activation by bioinspired FLP A1. The relative Gibbs energies (ΔG) and potential energies
(ΔE) are in kcal/mol.
barriers (ΔG‡) of the rate-determining CO 1,1-addition steps
via TSA3−4. The corresponding whole catalytic pathways are
shown in Figures S6−S17 in the SI. The typical traditional FLP
catalysts including intermolecular and intramolecular systems
are predicted to involve high-energy barriers (34−46 kcal/mol;
Figure 4a). It is worth noting that the traditional FLPs H1 and
I1 have the similar linker structure with the designed
bioinspired FLP A1, and the distances of Lewis acid−base
sites are almost the same for H1, I1, and A1 (ca. 5.3 Å).
Differently, H1 and I1 cannot exhibit the extended
aromatization−dearomatization effect. Consequently, the
energy barriers of H1 and I1 catalysts (38.3 and 34.5 kcal/
mol) are predicted to be much higher than that of the
bioinspired FLP A1 catalysts (25.6 kcal/mol), suggesting that
the extended aromatization−dearomatization in A1 could play
an important role in facilitating the CO 1,1-addition step.
Further, the activities of the bioinspired FLP catalysts can be
controlled. As shown in Figure 4b, the intermolecular catalyst
J1 has a higher energy barrier of the rate-determining CO 1,1-
addition steps than the intramolecular ones, which could be
associated with the entropy penalty. The intramolecular
bioinspired FLP catalyst K1 with −Ph groups is predicted to
own an energy barrier (31.8 kcal/mol) higher than that of A1
with −B(C6F5)2 groups (25.6 kcal/mol), suggesting that the
higher Lewis acidity of B atom will result in lower energy
barriers. Pursuing this idea, we introduced more F substituents
on the linkers, and the modified FLP catalysts L1 and M1 are
predicted to yield even lower energy barriers (22.1 and 20.6
kcal/mol), which can allow for low operating temperatures.
The activation of CO by metal complexes is a highly
important field in chemistry, and it has been explained in terms
of the Dewar−Chatt−Duncanson model, which involves the σ-
donation and dπ-back-donation interactions (Figure 5a).79 In
F https://doi.org/10.1021/acsorginorgau.3c00064
pubs.acs.org/orginorgau Article
contrast, the CO activation by organic catalysts does not
involve dπ-back-donation, and it is still unclear. In order to
unveil the reasons for CO activation by the bioinspired FLP,
the unusual 1,1-addition of CO was simulated. This was
accomplished via performing the intrinsic reaction coordinate
(IRC) computation on the transition state TSA3−4. The
natural localized molecular orbital (NLMO) analysis was
applied to five frames of the IRC trajectory, as shown in Figure
5b. When the CO molecule approaches A3, the lone pair of the
carbonyl carbon atom is delocalized to the σ*O−H antibonding
orbital, and the lone pair electron of the O(2) atom is
delocalized to the π*C�O orbital. According to our dynamic
NLMO analysis, a new CO activation model involving the σ-
donation and σ-back-donation interactions is proposed, as
illustrated in Figure 5c. This, hopefully, will guide the
development of organic catalysts for CO hydrogenations.
3.2. Hydrogenation of Formic Acid Intermediate into
Methanol
The Lewis basic O and acidic B atoms in A1 cannot form the
effective orbital overlap with the hydrogen molecule due to the
long O...B distance (5.34 Å) and make the common hydrogen
activation pathway difficult. As shown in Figure 6, the
hydrogen molecule cleaves across the B and O atoms of A1
with a high energy barrier (39.1 kcal/mol), due to the high
strain of the hydrogen-transfer transition state TSA1−7,
indicating that this pathway is not available. Instead, a
hydrogen shuttle mechanism becomes available for the
bioinspired FLP-facilitated hydrogen activation. The water
and hydrogen molecules can approach A1 to form the complex
A5, and this step is endothermic by 23.7 kcal/mol due to the
entropy penalty. Through transition state TSA5−6, the H(3)
atom moves from the hydrogen moiety to the nearby O(2)
atom of the water moiety, which is accompanied by the H(2)
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au
Figure 7. Gibbs energy profile for the hydrogenation of formic acid to methanol catalyzed by the bioinspired FLP. The relative Gibbs energies
(ΔG) and potential energies (ΔE) are given in kcal/mol.
atom transfer from the water moiety to the carbonylic O(1)
atom. Actually, the water molecule serves as a hydrogen shuttle
and decreases the energy barrier of the hydrogen activation to
23.3 kcal/mol. Note that although the Gibbs energy of TSA5−
6 (21.0 kcal/mol) appears to be lower than that of A5 (21.4
kcal/mol), the potential energy of TSA5−6 (−15.0 kcal/mol)
is higher than that of A5 (−15.7 kcal/mol). In the following,
the intermediate A6 is generated and can release a water
molecule to form the hydrogenated intermediate A7. As shown
in Figure 3, the bond lengths and NICS values of A7 are
almost the same with those in A3, suggesting that the hydrogen
activation also experiences the extended aromatization−
dearomatization process.
As shown in Figure 7, the H(2)...H(4) distance in the
structure of A7 is 3.84 Å, and the NBO charges for H(2) and
H(4) atoms are 0.52 and −0.02, respectively. Through the
transition state TSA7, the H(2) and H(4) atoms can transfer
to the C�O bond of formic acid in a concerted manner with
an energy barrier of 16.5 kcal/mol. As a result, methane diol
and the catalyst A1 are formed, being exoenergic by 5.0 kcal/
mol. In the following, FLP A1 can facilitate the decomposition
of methane diol to form formaldehyde. Through the H...O
hydrogen-bonding and O→B coordinative interactions, A1 can
bind methane diol to afford the intermediate A8. Over the
transition state TSA8, the methane diol moiety in A8 can be
decomposed with the cleavage of C(3)−O(2) and O(3)−
H(2) bonds, and the corresponding energy barrier is only 6.0
kcal/mol. After that, formaldehyde is released. The generated
intermediate A3 will release a water molecule through the
water activation pathway in Figure 2 (A3 → TSA2−3 → A2
→ A1). The bioinspired FLP A1 then undergoes hydrogen
activation (see pathway in Figure 6) and the C�O bond
hydrogenation process and forms the final methanol product.
In brief, the reaction heat of the whole reaction is −18.2
kcal/mol, and the 1,1-addition of CO via the transition state
TSA3−4 (stage 1) is the rate-determining step with an energy
span of 25.6 kcal/mol for the bioinspired FLP A1. Moreover,
the pathways created by the modified bioinspired FLPs L1 and
M1 are shown in Figures S16 and S17 in SI and predicted to
G https://doi.org/10.1021/acsorginorgau.3c00064
pubs.acs.org/orginorgau Article
own even lower energy spans (22.1 and 20.6 kcal/mol),
suggesting that the designed CO hydrogenation to methanol
could be achieved at room temperatures according to both
reported theoretical studies80−84 and Eyring equation that
correlates the activation energy (ΔG‡) and the rate constant
(k) of the rate-determining step.85
4. CONCLUSIONS
The organic bioinspired FLP A1 featuring a nucleic acid base
fused π-conjugated linker is theoretically designed and can
provide a suitable pocket for the synchronous activation of two
substrate molecules. The computations suggest that the
biomimetic FLP catalyst can exhibit good tolerance to CO
poison. The base-free water-assisted indirect CO hydro-
genation to methanol catalyzed by the bioinspired FLP
catalysts contains two stages: the 1,1-addition of CO into the
formic acid intermediate and the hydrogenation of the formic
acid intermediate into methanol. The 1,1-addition of CO via
the transition state TSA3−4 is the rate-determining step with
an energy span of 25.6 kcal/mol. Furthermore, the activities of
the bioinspired FLP catalysts can be controlled through
changing the Lewis acidity of the B atom, and the modified
catalysts L1 and M1 yield lower energy spans (22.1 and 20.6
kcal/mol). These low-energy spans suggest that CO can be
hydrogenated into methanol at low operating temperatures.
The comparisons between the typical traditional catalysts
and the designed bioinspired FLP catalysts unveil that the new
extended aromatization−dearomatization effect involving
multiple rings of bioinspired FLP catalysts is an effective
strategy to facilitate the rate-determining CO 1,1-addition step.
According to the dynamic NLMO analysis, a new model
involving σ-donation and σ-back-donation interactions is
proposed for CO activation and should guide the development
of organic catalysts for CO hydrogenations. The present study
will pave the way to a new method for the hydrogenation of
CO to methanol with good stability, low cost, environmental
friendliness, and low temperatures.
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au
■ ASSOCIATED CONTENT
Data Availability Statement
The data underlying this study are available in the published
article and its Supporting Information.
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsorginorgau.3c00064.
Optimized geometries and energies of all stationary
points along the reaction pathways and the imaginary
vibrational frequencies of transition states (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Longfei Li − College of Pharmacy, Key Laboratory of
Pharmaceutical Quality Control of Hebei Province, Key
Laboratory of Medicinal Chemistry and Molecular Diagnosis
of Ministry of Education, Hebei University, Baoding 071002
Hebei, P. R. China; orcid.org/0000-0001-8435-4006;
Email: lilongfei@hbu.edu.cn
Xue-Qing Song − College of Pharmacy, Key Laboratory of
Pharmaceutical Quality Control of Hebei Province, Key
Laboratory of Medicinal Chemistry and Molecular Diagnosis
of Ministry of Education, Hebei University, Baoding 071002
Hebei, P. R. China; orcid.org/0000-0001-5527-5261;
Email: sxqing@hbu.edu.cn
Henry F. Schaefer, III − Center for Computational Quantum
Chemistry, University of Georgia, Athens, Georgia 30602,
United States; orcid.org/0000-0003-0252-2083;
Email: ccq@uga.edu
Authors
Jiejing Zhang − College of Pharmacy, Key Laboratory of
Pharmaceutical Quality Control of Hebei Province, Key
Laboratory of Medicinal Chemistry and Molecular Diagnosis
of Ministry of Education, Hebei University, Baoding 071002
Hebei, P. R. China
Xiaofeng Xie − College of Pharmacy, Key Laboratory of
Pharmaceutical Quality Control of Hebei Province, Key
Laboratory of Medicinal Chemistry and Molecular Diagnosis
of Ministry of Education, Hebei University, Baoding 071002
Hebei, P. R. China; orcid.org/0000-0002-8113-4064
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsorginorgau.3c00064
Author Contributions
CRediT: Jiejing Zhang data curation, investigation, method-
ology, software, writing-original draft; Longfei Li conceptual-
ization, funding acquisition, methodology, project adminis-
tration, supervision, writing-original draft, writing-review &
editing; Xiaofeng Xie data curation, investigation, method-
ology, visualization, writing-original draft; Xue-Qing Song
formal analysis, investigation, validation, writing-review &
editing; Henry F. Schaefer conceptualization, funding
acquisition, methodology, resources, supervision, writing-
review & editing.
Notes
The authors declare no competing financial interest.
H https://doi.org/10.1021/acsorginorgau.3c00064
pubs.acs.org/orginorgau Article
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (No. 22373030), the Natural Science
Interdisciplinary Research Program of Hebei University (No.
DXK202013), the Jointed Key Pharmaceutical and Drug
Project of Hebei Province (B2022208057), and the Innovation
Capacity Improvement Plan of Hebei Province (20567605H).
The authors thank the High Performance Computer Center of
Hebei University for providing computational resources. HFS
was supported by the U.S. Department of Energy, under
contract No. DE-SC0018412.
■ REFERENCES
(1) Turner, J. M. The matter of a clean energy future. Science 2022,
376, 1361.
(2) Slameršak, A.; Kallis, G.; O’Neill, D. W. Energy requirements
and carbon emissions for a low-carbon energy transition. Nat.
Commun. 2022, 13, 6932.
(3) Sen, R.; Goeppert, A.; Kar, S.; Prakash, G. K. S. Hydroxide Based
Integrated CO2 Capture from Air and Conversion to Methanol. J. Am.
Chem. Soc. 2020, 142, 4544−4549.
(4) Zhang, Z.; Mao, C.; Meira, D. M.; Duchesne, P. N.; Tountas, A.
A.; Li, Z.; Qiu, C.; Tang, S.; Song, R.; Ding, X.; Sun, J.; Yu, J.; Howe,
J. Y.; Tu, W.; Wang, L.; Ozin, G. A. New black indium oxide-tandem
photothermal CO2-H2 methanol selective catalyst. Nat. Commun.
2022, 13, 1512.
(5) Amann, P.; Klötzer, B.; Degerman, D.; Köpfle, N.; Götsch, T.;
Lömker, P.; Rameshan, C.; Ploner, K.; Bikaljevic, D.; Wang, H. Y.;
Soldemo, M.; Shipilin, M.; Goodwin, C. M.; Gladh, J.; Halldin
Stenlid, J.; Börner, M.; Schlueter, C.; Nilsson, A. The state of zinc in
methanol synthesis over a Zn/ZnO/Cu(211) model catalyst. Science
2022, 376, 603−608.
(6) Zhang, F.; Chen, K.; Jiang, Q.; He, S.; Chen, Q.; Liu, Z.; Kang,
J.; Zhang, Q.; Wang, Y. Selective Transformation of Methanol to
Ethanol in the Presence of Syngas over Composite Catalysts. ACS
Catal. 2022, 12, 8451−8461.
(7) Wang, C.; Yang, L.; Gao, M.; Shao, X.; Dai, W.; Wu, G.; Guan,
N.; Xu, Z.; Ye, M.; Li, L. Directional Construction of Active
Naphthalenic Species within SAPO-34 Crystals toward More Efficient
Methanol-to-Olefin Conversion. J. Am. Chem. Soc. 2022, 144, 21408−
21416.
(8) Olah, G. A. Beyond Oil and Gas: The Methanol Economy.
Angew. Chem., Int. Ed. 2005, 44, 2636−2639.
(9) Behrens, M.; Studt, F.; Kasatkin, I.; Kühl, S.; Hävecker, M.;
Abild-Pedersen, F.; Zander, S.; Girgsdies, F.; Kurr, P.; Kniep, B. L.;
Tovar, M.; Fischer, R. W.; No̷ rskov, J. K.; Schlögl, R. The active site of
methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science
2012, 336, 893−897.
(10) Laudenschleger, D.; Ruland, H.; Muhler, M. Identifying the
nature of the active sites in methanol synthesis over Cu/ZnO/Al2O3
catalysts. Nat. Commun. 2020, 11, 3898.
(11) Sen, R.; Goeppert, A.; Surya Prakash, G. K. Homogeneous
Hydrogenation of CO2 and CO to Methanol: The Renaissance of
Low-Temperature Catalysis in the Context of the Methanol
Economy. Angew. Chem., Int. Ed. 2022, 61, No. e202207278.
(12) Kar, S.; Goeppert, A.; Prakash, G. K. S. Catalytic Homogeneous
Hydrogenation of CO to Methanol via Formamide. J. Am. Chem. Soc.
2019, 141, 12518−12521.
(13) Walter, R. Iron catalysts for carbon monoxide hydrogenation
precipitated from ferrous sulfate solutions. U.S. Patent 2534018, 1950.
(14) Gresham, W. F. Preparation of polyfunctional compounds. U.S.
Patent 2636046, 1953.
(15) Rathke, J. W.; Feder, H. M. Catalysis of carbon monoxide
hydrogenation by soluble mononuclear complexes. J. Am. Chem. Soc.
1978, 100, 3623−3625.
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au
(16) Bradley, J. S. Homogeneous carbon monoxide hydrogenation
to methanol catalyzed by soluble ruthenium complexes. J. Am. Chem.
Soc. 1979, 101, 7419−7421.
(17) Dombek, B. D. Hydrogenation of carbon monoxide to
methanol and ethylene glycol by homogeneous ruthenium catalysts.
J. Am. Chem. Soc. 1980, 102, 6855−6857.
(18) Fahey, D. R. Rational mechanism for homogeneous hydro-
genation of carbon monoxide to alcohols, polyols, and esters. J. Am.
Chem. Soc. 1981, 103, 136−141.
(19) Dombek, B. D. Roles of metal carbonyl complexes in the
homogeneous hydrogenation of carbon monoxide. J. Organomet.
Chem. 1989, 372, 151−161.
(20) Marko, L. C2 compounds directly from synthesis gas via
organometallic catalysts. Transition Met. Chem. 1992, 17, 474−480.
(21) Berke, H.; Hoffmann, R. Organometallic migration reactions. J.
Am. Chem. Soc. 1978, 100, 7224−7236.
(22) West, N. M.; Miller, A. J. M.; Labinger, J. A.; Bercaw, J. E.
Homogeneous syngas conversion. Coord. Chem. Rev. 2011, 255, 881−
898.
(23) Mahajan, D. Atom-economical reduction of carbon monoxide
to methanol catalyzed by soluble transition metal complexes at low
temperatures. Top. Catal. 2005, 32, 209−214.
(24) Zell, T.; Ben-David, Y.; Milstein, D. Unprecedented iron-
catalyzed ester hydrogenation. Mild, selective, and efficient hydro-
genation of trifluoroacetic esters to alcohols catalyzed by an iron
pincer complex. Angew. Chem., Int. Ed. 2014, 53, 4685−4689.
(25) Srimani, D.; Mukherjee, A.; Goldberg, A. F.; Leitus, G.; Diskin-
Posner, Y.; Shimon, L. J.; Ben David, Y.; Milstein, D. Cobalt-catalyzed
hydrogenation of esters to alcohols: unexpected reactivity trend
indicates ester enolate intermediacy. Angew. Chem., Int. Ed. 2015, 54,
12357−12360.
(26) Das, U. K.; Kumar, A.; Ben-David, Y.; Iron, M. A.; Milstein, D.
Manganese Catalyzed Hydrogenation of Carbamates and Urea
Derivatives. J. Am. Chem. Soc. 2019, 141, 12962−12966.
(27) Cabrero-Antonino, J. R.; Adam, R.; Papa, V.; Beller, M.
Homogeneous and heterogeneous catalytic reduction of amides and
related compounds using molecular hydrogen. Nat. Commun. 2020,
11, 3893.
(28) Gausas, L.; Kristensen, S. K.; Sun, H.; Ahrens, A.; Donslund, B.
S.; Lindhardt, A. T.; Skrydstrup, T. Catalytic Hydrogenation of
Polyurethanes to Base Chemicals: From Model Systems to
Commercial and End-of-Life Polyurethane Materials. JACS Au
2021, 1, 517−524.
(29) Liu, X.; Werner, T. Indirect reduction of CO2 and recycling of
polymers by manganese-catalyzed transfer hydrogenation of amides,
carbamates, urea derivatives, and polyurethanes. Chem. Sci. 2021, 12,
10590−10597.
(30) Ryabchuk, P.; Stier, K.; Junge, K.; Checinski, M. P.; Beller, M.
Molecularly Defined Manganese Catalyst for Low-Temperature
Hydrogenation of Carbon Monoxide to Methanol. J. Am. Chem.
Soc. 2019, 141, 16923−16929.
(31) Kaithal, A.; Werlé, C.; Leitner, W. Alcohol-Assisted Hydro-
genation of Carbon Monoxide to Methanol Using Molecular
Manganese Catalysts. JACS Au 2021, 1, 130−136.
(32) Kumar, A.; Daw, P.; Milstein, D. Homogeneous Catalysis for
Sustainable Energy: Hydrogen and Methanol Economies, Fuels from
Biomass, and Related Topics. Chem. Rev. 2022, 122, 385−441.
(33) Weetman, C.; Inoue, S. The Road Travelled: After Main-Group
Elements as Transition Metals. ChemCatChem. 2018, 10, 4213−4228.
(34) Paradies, J. Structure-Reactivity Relationships in Borane-Based
FLP-Catalyzed Hydrogenations, Dehydrogenations, and Cycloisome-
rizations. Acc. Chem. Res. 2023, 56, 821−834.
(35) Fujimori, S.; Inoue, S. Carbon Monoxide in Main-Group
Chemistry. J. Am. Chem. Soc. 2022, 144, 2034−2050.
(36) Jupp, A. R.; Stephan, D. W. New Directions for Frustrated
Lewis Pair Chemistry. Trends Chem. 2019, 1, 35−48.
(37) Stephan, D. W. Diverse Uses of the Reaction of Frustrated
Lewis Pair (FLP) with Hydrogen. J. Am. Chem. Soc. 2021, 143,
20002−20014.
I https://doi.org/10.1021/acsorginorgau.3c00064
pubs.acs.org/orginorgau Article
(38) Barrales-Martínez, C.; Durán, R.; Jaque, P. Metal-free catalytic
conversion of CO2 into methanol: local electrophilicity as a tunable
property in the design and performance of aniline-derived amino-
borane-based FLPs. Inorg. Chem. Front. 2023, 10, 2344−2358.
(39) Greb, L.; Oña-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan,
D. W.; Paradies, J. Metal-free catalytic olefin hydrogenation: low-
temperature H2 activation by frustrated Lewis pairs. Angew. Chem., Int.
Ed. 2012, 51, 10164−10168.
(40) Chernichenko, K.; Madarász, A.; Pápai, I.; Nieger, M.; Leskelä,
M.; Repo, T. A frustrated-Lewis-pair approach to catalytic reduction
of alkynes to cis-alkenes. Nat. Chem. 2013, 5, 718−723.
(41) Mahdi, T.; Stephan, D. W. Enabling catalytic ketone
hydrogenation by frustrated Lewis pairs. J. Am. Chem. Soc. 2014,
136, 15809−15812.
(42) Farrell, J. M.; Posaratnanathan, R. T.; Stephan, D. W. A family
of N-heterocyclic carbene-stabilized borenium ions for metal-free
imine hydrogenation catalysis. Chem. Sci. 2015, 6, 2010−2015.
(43) Sitte, N. A.; Bursch, M.; Grimme, S.; Paradies, J. Frustrated
Lewis Pair Catalyzed Hydrogenation of Amides: Halides as Active
Lewis Base in the Metal-Free Hydrogen Activation. J. Am. Chem. Soc.
2019, 141, 159−162.
(44) Sapsford, J. S.; Csókás, D.; Turnell-Ritson, R. C.; Parkin, L. A.;
Crawford, A. D.; Pápai, I.; Ashley, A. E. Transition Metal-Free Direct
Hydrogenation of Esters via a Frustrated Lewis Pair. ACS Catal. 2021,
11, 9143−9150.
(45) Guo, X.; Unglaube, F.; Kragl, U.; Mejia, E. B(C6F5)3-Catalyzed
transfer hydrogenation of esters and organic carbonates towards
alcohols with ammonia borane. Chem. Commun. 2022, 58, 6144−
6147.
(46) Li, Z.; Wang, Z.; Chekshin, N.; Qian, S.; Qiao, J. X.; Cheng, P.
T.; Yeung, K. S.; Ewing, W. R.; Yu, J. Q. A tautomeric ligand enables
directed C-H hydroxylation with molecular oxygen. Science 2021, 372,
1452−1457.
(47) Rumo, C.; Stein, A.; Klehr, J.; Tachibana, R.; Prescimone, A.;
Häussinger, D.; Ward, T. R. An Artificial Metalloenzyme Based on a
Copper Heteroscorpionate Enables sp3 C-H Functionalization via
Intramolecular Carbene Insertion. J. Am. Chem. Soc. 2022, 144,
11676−11684.
(48) Lentz, N.; Reuge, S.; Albrecht, M. NADH-Type Hydride
Storage and Release on a Functional Ligand for Efficient and Selective
Hydrogenation Catalysis. ACS Catal. 2023, 13, 9839−9844.
(49) Chen, M.-W.; Wu, B.; Liu, Z.; Zhou, Y.-G. Biomimetic
Asymmetric Reduction Based on the Regenerable Coenzyme
NAD(P)H Models. Acc. Chem. Res. 2023, 56, 2096−2109.
(50) Podolyan, Y.; Gorb, L.; Leszczynski, J. Protonation of Nucleic
Acid Bases. A Comprehensive Post-Hartree−Fock Study of the
Energetics and Proton Affinities. J. Phys. Chem. A 2000, 104, 7346−
7352.
(51) Sanchez, R.; Giuliano, B. M.; Melandri, S.; Favero, L. B.;
Caminati, W. Gas-Phase Tautomeric Equilibrium of 4-Hydroxypyr-
imidine with Its Ketonic Forms: A Free Jet Millimeterwave
Spectroscopy Study. J. Am. Chem. Soc. 2007, 129, 6287−6290.
(52) Caminati, W. Nucleic acid bases in the gas phase. Angew. Chem.,
Int. Ed. 2009, 48, 9030−9033.
(53) Jin, L.; Lv, M.; Zhao, M.; Wang, R.; Zhao, C.; Lu, J.; Wang, L.;
Wang, W.; Wei, Y. Formic acid catalyzed isomerization of protonated
cytosine: a lower barrier reaction for tautomer production of potential
biological importance. Phys. Chem. Chem. Phys. 2017, 19, 13515−
13523.
(54) Kasende, O. E.; Muya, J. T.; Broeckaert, L.; Maes, G.;
Geerlings, P. Theoretical Study of the Regioselectivity of the
Interaction of 3-Methyl-4-pyrimidone and 1-Methyl-2-pyrimidone
with Lewis Acids. J. Phys. Chem. A 2012, 116, 8608−8614.
(55) Houk, K. N.; Cheong, P. H. Computational prediction of small-
molecule catalysts. Nature 2008, 455, 309−313.
(56) Guan, Y.; Wheeler, S. E. Automated Quantum Mechanical
Predictions of Enantioselectivity in a Rhodium-Catalyzed Asymmetric
Hydrogenation. Angew. Chem., Int. Ed. 2017, 56, 9101−9105.
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX
ACS Organic & Inorganic Au
(57) Jiang, B.; Zhang, Q.; Dang, L. Theoretical studies on bridged
frustrated Lewis pair (FLP) mediated H2 activation and CO2
hydrogenation. Org. Chem. Front. 2018, 5, 1905−1915.
(58) Kondo, M.; Tatewaki, H.; Masaoka, S. Design of molecular
water oxidation catalysts with earth-abundant metal ions. Chem. Soc.
Rev. 2021, 50, 6790−6831.
(59) Mroz, A. M.; Posligua, V.; Tarzia, A.; Wolpert, E. H.; Jelfs, K. E.
Into the Unknown: How Computation Can Help Explore Uncharted
Material Space. J. Am. Chem. Soc. 2022, 144, 18730−18743.
(60) Tu, Z.; Stuyver, T.; Coley, C. W. Predictive chemistry: machine
learning for reaction deployment, reaction development, and reaction
discovery. Chem. Sci. 2023, 14, 226−244.
(61) Li, L.; Lei, M.; Xie, Y.; Schaefer, H. F., III; Chen, B.; Hoffmann,
R. Stabilizing a different cyclooctatetraene stereoisomer. Proc. Natl.
Acad. Sci. U.S.A. 2017, 114, 9803−9808.
(62) Li, L.; Wu, Z.; Zhu, H.; Robinson, G. H.; Xie, Y.; Schaefer, H.
F. Reduction of Dinitrogen via 2,3′-Bipyridine-Mediated Tetrabora-
tion. J. Am. Chem. Soc. 2020, 142, 6244−6250.
(63) Zahrt, A. F.; Henle, J. J.; Rose, B. T.; Wang, Y.; Darrow, W. T.;
Denmark, S. E. Prediction of higher-selectivity catalysts by computer-
driven workflow and machine learning. Science 2019, 363,
No. eaau5631.
(64) Hannagan, R. T.; Giannakakis, G.; Réocreux, R.; Schumann, J.;
Finzel, J.; Wang, Y.; Michaelides, A.; Deshlahra, P.; Christopher, P.;
Flytzani-Stephanopoulos, M.; Stamatakis, M.; Sykes, E. C. H. First-
principles design of a single-atom−alloy propane dehydrogenation
catalyst. Science 2021, 372, 1444−1447.
(65) Sanchez, D. M.; Raucci, U.; Martínez, T. J. In Silico Discovery
of Multistep Chemistry Initiated by a Conical Intersection: The
Challenging Case of Donor-Acceptor Stenhouse Adducts. J. Am.
Chem. Soc. 2021, 143, 20015−20021.
(66) Kim, S.-T.; Strauss, M. J.; Cabré, A.; Buchwald, S. L. Room-
Temperature Cu-Catalyzed Amination of Aryl Bromides Enabled by
DFT-Guided Ligand Design. J. Am. Chem. Soc. 2023, 145, 6966−
6975.
(67) Xu, R.; Meisner, J.; Chang, A. M.; Thompson, K. C.; Martinez,
T. J. First principles reaction discovery: from the Schrodinger
equation to experimental prediction for methane pyrolysis. Chem. Sci.
2023, 14, 7447−7464.
(68) Jia, Z.; Li, L.; Zhang, X.; Yang, K.; Li, H.; Xie, Y.; Schaefer, H.
F., III Acceleration Effect of Bases on Mn Pincer Complex-Catalyzed
CO2 Hydroboration. Inorg. Chem. 2022, 61, 3970−3980.
(69) Rong, H.; Zhang, Y.; Ai, X.; Li, W.; Cao, F.; Li, L. Theoretical
Study on the Hydrogenolysis of Polyurethanes to Improve the
Catalytic Activities. Inorg. Chem. 2022, 61, 14662−14672.
(70) Ai, X.; Xie, X.; Song, X.; Li, L.; Schaefer, H. F., III Is the
polarization of the C = C bond imperative for bifunctional outer-
sphere C = C hydrogenation? Org. Chem. Front. 2023, 10, 1301−
1308.
(71) Chai, J.-D.; Head-Gordon, M. Long-Range Corrected Hybrid
Density Functionals with Damped Atom-Atom Dispersion Correc-
tions. Phys. Chem. Chem. Phys. 2008, 10, 6615−6620.
(72) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.;
Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.;
Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi,
R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar,
S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox,
J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.;
Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.;
Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.;
Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A.
D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.
Gaussian 09, revision B.01; Gaussian, Inc.: Wallingford, CT, 2009.
J https://doi.org/10.1021/acsorginorgau.3c00064
pubs.acs.org/orginorgau Article
(73) Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. Self-
consistent molecular orbital methods. XX. A basis set for correlated
wave functions. J. Chern. Phys. 1980, 72, 650−654.
(74) Tomasi, J.; Persico, M. Molecular Interactions in Solution: An
Overview of Methods Based on Continuous Distributions of the
Solvent. Chem. Rev. 1994, 94, 2027−2094.
(75) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal
Solvation Model Based on Solute Electron Density and on a
Continuum Model of the Solvent Defined by the Bulk Dielectric
Constant and Atomic Surface Tensions. J. Phys. Chem. B 2009, 113,
6378−6396.
(76) Tsutsumi, T.; Ono, Y.; Arai, Z.; Taketsugu, T. Visualization of
the Intrinsic Reaction Coordinate and Global Reaction Route Map by
Classical Multidimensional Scaling. J. Chem. Theory Comput. 2018, 14,
4263−4270.
(77) Glendening, E. D.; Landis, C. R.; Weinhold, F. NBO 7.0: New
vistas in localized and delocalized chemical bonding theory. J. Comput.
Chem. 2019, 40, 2234−2241.
(78) Chen, Z.; Wannere, C. S.; Corminboeuf, C.; Puchta, R.;
Schleyer, P. V. R. Nucleus-Independent Chemical Shifts (NICS) as an
Aromaticity Criterion. Chem. Rev. 2005, 105, 3842−3888.
(79) Qin, J.; Li, F.; Qiu, R.; Chen, L.; Luo, L.; Wang, M.; Pu, Z.;
Shuai, M. Insights into the Metal-CO Bond in O2M(η1-CO) (M = Cr,
Mo, W, Nd, and U) Complexes. Inorg. Chem. 2022, 61, 2066−2075.
(80) Zhang, S.-Q.; Taylor, B. L. H.; Ji, C.-L.; Gao, Y.; Harris, M. R.;
Hanna, L. E.; Jarvo, E. R.; Houk, K. N.; Hong, X. Mechanism and
Origins of Ligand-Controlled Stereoselectivity of Ni-Catalyzed
Suzuki-Miyaura Coupling with Benzylic Esters: A Computational
Study. J. Am. Chem. Soc. 2017, 139, 12994−13005.
(81) Chen, Y.; Zhang, X.; Liu, F.; He, G.; Zhang, J.; Houk, K. N.;
Smith, A. B., III; Liang, Y. The role of CuI in the siloxane-mediated
Pd-catalyzed cross-coupling reactions of aryl iodides with aryl lithium
reagents. Chin. Chem. Lett. 2021, 32, 441−444.
(82) Qin, C.; Koengeter, T.; Zhao, F.; Mu, Y.; Liu, F.; Houk, K. N.;
Hoveyda, A. H. Z-Trisubstituted α,β-Unsaturated Esters and Acid
Fluorides through Stereocontrolled Catalytic Cross-Metathesis. J. Am.
Chem. Soc. 2023, 145, 3748−3762.
(83) Kaasik, M.; Chen, P.-P.; Ričko, S.; Jo̷ rgensen, K. A.; Houk, K.
N. Asymmetric [4 + 2], [6 + 2], and [6 + 4] Cycloadditions of
Isomeric Formyl Cycloheptatrienes Catalyzed by a Chiral Diamine
Catalyst. J. Am. Chem. Soc. 2023, 145, 23874−23890.
(84) Galeotti, M.; Lee, W.; Sisti, S.; Casciotti, M.; Salamone, M.;
Houk, K. N.; Bietti, M. Radical and Cationic Pathways in C(sp3)-H
Bond Oxygenation by Dioxiranes of Bicyclic and Spirocyclic
Hydrocarbons Bearing Cyclopropane Moieties. J. Am. Chem. Soc.
2023, 145, 24021−24034.
(85) Ryu, H.; Park, J.; Kim, H. K.; Park, J. Y.; Kim, S.-T.; Baik, M.-H.
Pitfalls in Computational Modeling of Chemical Reactions and How
To Avoid Them. Organometallics 2018, 37, 3228−3239.
ACS Org. Inorg. Au XXXX, XXX, XXX−XXX