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D. “Catalytic Formation of Acrylate from Carbon Dioxide and Ethene.” Chem.
To explore removal of the carboxylate from the coordination sphere
of the iron, several conditions were evaluated with the goal of complet-
ing a synthetic cycle. While treatment of 1-O2CC2H5 with metallic zinc
produced no reaction, addition of magnesium butadiene generated a
mixture of 1-N2 and (iPrPDI)Fe(C4H6) along with magnesium propio-
Eur. J. 2014, 20, 12037–12040. (c) Plessow, P. N.; Schäfer, A.; Limbach, M.;
Hofmann P. “Acrylate Formation from CO2 and Ethylene Mediated by Nickel
Complexes: A Theoretical Study.” Organometallics, 2014, 33, 3657−3668; (d)
Lejkowski, M. L.; Lindner, R.; Kageyama, T.; Bódizs, G. É.; Plessow, P. N.;
Müller, I. B.; Schäfer, A.; Rominger, F.; Hofmann, P.; Futter, C.; Schunk, S. A.;
Limbach, M. “The First Catalytic Synthesis of an Acrylate from CO2 and an
Alkene—A Rational Approach.” Chem. Eur. J. 2012, 18, 14017–14025.
(5) Stieber, S. C. E.; Huguet, N.; Kageyama, T.; Jevtovikj, I.; Ariyananda, P.;
Gordillo, A.; Schunk, S. A.; Rominger, F.; Hofmann, P.; Limbach, M. “Acrylate
formation from CO2 and ethylene: catalysis with palladium and mechanistic
insight.” Chem. Commun. 2015, 51, 10907–10909.
1
nate, which was identified by H and 13C NMR spectroscopies and by
comparison to an authentic sample.
In summary, an iron-mediated coupling of CO2 and ethylene to
produce a homologous series of iron carboxylates has been developed.
The composition of the carboxylate can be tuned using an appropriate
CO2 to ethylene ratio and eviden ce was provided for chain lengths of
≤21. These studies provide a new outlook for the synthesis of carbox-
ylic acids from abundant carbon sources and demonstrate the ability of
metallacyclic intermediates to control reaction outcome.
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(6) Hoberg, H.; Peres, Y.; Krüger, C.; Tsay, Y.-H. “A 1‐Oxa‐2‐nickela‐5‐
cyclopentanone from Ethene and Carbon Dioxide: Preparation, Structure, and
Reactivity.” Angew. Chem. Int. Ed. Engl. 1987, 26, 771–773.
(7) (a) Alvarez, R.; Carmona, E.; Galindo, A.; Gutierrez, E.; Marin, J. M.;
Monge, A.; Poveda, M. L.; Ruiz, C.; Savariault, J. M. “Formation of carboxylate
complexes from the reactions of carbon dioxide with ethylene complexes of
molybdenum and tungsten. X-ray and neutron diffraction studies.” Organome-
tallics 1989, 8, 2430–2439. (b) Alvarez, R.; Carmona, E.; Cole-Hamilton, D. J.;
Galindo, A.; Gutierrez-Puebla, E.; Monge, A.; Poveda, M. L.; Ruiz, C. “For-
mation of acrylic acid derivatives from the reaction of carbon dioxide with
ethylene complexes of molybdenum and tungsten.” J. Am. Chem. Soc. 1985,
107, 5529–5531.
ASSOCIATED CONTENT
Supporting Information
Complete experimental procedures including general considerations
and characterization data and NMR spectra as PDF. Crystallographic
data are included as CIF. The Supporting Information is available free
of charge at pubs.acs.org.
(8) Cohen, S. A.; Bercaw, J. E. “Titanacycles Derived from Reductive Cou-
pling of Nitriles, Alkynes, Acetaldehyde, and Carbon Dioxide with
AUTHOR INFORMATION
Bis(pentamethylcyclopentadienyl)(ethylene)titanium(II)”
Organometallics
1985, 4, 1006–1014.
Corresponding Author
(9) Hessen, B.; Meetsma, A.; van Bolhuis, F.; Teuben, J. H.; Helgesson, G.;
Jagner, S. “Chemistry of Carbon Monoxide Free Cyclopentadienylvanadium(I)
Alkene and Alkyne Complexes.” Organometallics 1990, 9, 1925–1936.
(10) Alt, H. G.; Denner, C. E. “Metallacyclen des Zirkonocens.“ J. Organ-
omet. Chem. 1990, 390, 53–60.
*pchirik@princeton.edu
Notes
The authors declare no competing financial interests.
(11) Hoberg, H.; Jenni, K.; Angermund, K.; Krüger, C.; “CC‐Linkages of
Ethene with CO2 on an Iron(0) Complex—Synthesis and Crystal Structure
Analysis of [(PEt3)2Fe(C2H4)2].” Angew. Chem. Int. Ed. Engl. 1987, 26, 153–
155.
(12) Aresta, M.; Quaranta, E. “Synthesis, characterization and reactivity of
[Rh(bpy)(C2H4)Cl]. A study on the reaction with C1 molecules (CH2O, CO2)
and NaBPh4.” J. Organomet. Chem. 1993, 463, 215–221.
(13) Fischer, R.; Langer, J.; Malassa, A.; Walther, D.; Görls, H.; Vaughan; G. “A key
step in the formation of acrylic acid from CO2 and ethylene: the transformation of a
nickelalactone into a nickel-acrylate complex.” Chem. Commun. 2006, 2510–2512.
(14) (a) Jin, D.; Williard, P. G.; Hazari, N.; Bernskoetter, W. H. “Effect of
Sodium Cation on Metallacycle β-Hydride Elimination in CO2–Ethylene
Coupling to Acrylates.” Chem. Eur. J. 2014, 20, 3205–3211. (b) Jin, D.;
Schmeier, T. J.; Williard, P. G.; Hazari, N.; Bernskoetter, W. H. “Lewis Acid
Induced β-Elimination from a Nickelalactone: Efforts toward Acrylate Produc-
tion from CO2 and Ethylene.” Organometallics, 2013, 32, 2152–2159.
(15) Price, C. J.; Reich, B. J. E.; Miller, S. A. “Thermodynamic and kinetic
considerations in the copolymerization of ethylene and carbon dioxide.” Mac-
romolecules 2006, 39, 2751-2756.
(16) Tortajada, A,; Juliá-Hernández, F.; Börjesson, M.; Moragas, T.; Martin,
R. “Transition metal‐catalyzed carboxylation reactions with carbon dioxide.”
Angew. Chem. Int. Ed. 10.1002/anie.201803186.
(17) Hoberg, H.; Peres, Y.; Milchereit, A. “C–C-Verknüpfung von Alkenen
mit CO2 an Nickel(0); n-Pentensäuren aus Ethen.“ J. Organomet. Chem. 1986,
307, C41–C43.
(18) Karsh, H. H. “Funktionelle Trimethylphosphinderivate, III. Ambivalen-
tes Verhalten von Tetrakis(trimethylphosphin)eisen: Reaktion mit CO2”
Chem. Ber. 1977, 110, 2213.
(19) (a) Hoyt, J. M.; Schmidt, V. A.; Tondreau, A. M.; Chirik, P. J. “Iron-
catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes.” Science
2015, 349, 960–963 (b) Russell, S. K.; Lobkovsky, E.; Chirik, P. J. “Iron-
Catalyzed Intermolecular [2π + 2π] Cycloaddition.” J. Am. Chem. Soc. 2011,
133, 8858–8861.
ACKNOWLEDGMENT
We thank SABIC for financial support.
REFERENCES
(1) (a) Aresta, M.; Dibenedetto, A.; Angelini, A. “Catalysis for the Valoriza-
tion of Exhaust Carbon: from CO2 to Chemicals, Materials, and Fuels. Techno-
logical Use of CO2.” Chem. Rev. 2014, 114, 1709−1742. (b) Huang, K.; Sunwa,
C.-L.; Shi, Z.-J. “Transition-metal-catalyzed C–C bond formation through the fixation
of carbon dioxide.” Chem. Soc. Rev. 2011, 40, 2435–2452. (c) Cokoja, M.; Bruck-
meier, C.; Rieger, B.; Herrmann, W. A.; Kühn, F. E. “Transformation of Carbon
Dioxide with Homogeneous Transition‐Metal Catalysts: A Molecular Solution
to a Global Challenge?” Angew. Chem. Int. Ed. 2011, 50, 8510–8537. (d)
Mikkelsen, M.; Jørgensen, M.; Krebs, F. C. “The teraton challenge. A review of fixation
and transformation of carbon dioxide”. Energy Environ. Sci. 2010, 3, 43–81. (e) Aresta,
M. “Carbon Dioxide as Chemical Feedstock.” WILEY-VCH Gmbh & Co.
KGaA: Weinheim, 2010.
(2) (a) Short-Term Outlook for Hydrocarbon Gas Liquids; U.S. Energy In-
formation Administration, U.S. Department of Energy: Washington, D.C.,
March
2016;
supplements/2016/hgl/pdf/2016_sp_01.pdf. (b) Short Term Energy Out-
look; U.S. Energy Information Administration, U.S. Department of Energy:
Washington,
D.C.,
April
2017;
outlooks/steo/pdf/steo_full.pdf. (c) U. S. E. I. Administration U.S. Crude Oil
and Natural Gas Proved Reserves 2011; pp 1−49 (2013). (d) George, D. L.;
Bowles, E. B., Jr. Pipeline Gas J. 2011, 238, 38−41.
(3) (a) Wang, X.; Wang, H.; Sun, Y. “Synthesis of Acrylic Acid Derivatives
from CO2 and Ethylene.” Chem 2017, 3, 211–228. (b) Kraus, S.; Rieger, B. “Ni-
Catalyzed Synthesis of Acrylic Acid Derivatives from CO2 and Ethylene.” Top.
Organomet. Chem. 2016, 53, 199–223.
(4) (a) Huguet, N.; Jevtovikj, I.; Gordillo, A.; Lejkowski, M. L.; Lindner, R.;
Bru, M.; Khalimon, A. Y.; Rominger, F.; Schunk, S. A.; Hofmann, P.; Limbach,
M. “Nickel‐Catalyzed Direct Carboxylation of Olefins with CO2: One‐Pot
Synthesis of α,β‐Unsaturated Carboxylic Acid Salts.” Chem. Eur. J. 2014, 20,
16858–16862. (b) Hendriksen, C.; Pidko, E. A.; Yang, G.; Schäffner, B.; Vogt,
(20) Schmidt, V. A.; Kennedy, C. R.; Bezdek, M. J.; Chirik, P. J. “Selective
[1,4]-Hydrovinylation of 1,3-Dienes with Unactivated Olefins Enabled by Iron
Diimine Catalysts” J. Am. Chem. Soc. 2018, 140, 3443–3453.
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