1. School of Physical Science and Technology Shanghai Tech University Shanghai 201210 China
2. Anhui Province Key Laboratory of Biomass Clean Energy Department of Chemistry University of Science and Technology of China Hefei 230026 China
In the present review, we summarize the progress for thermal reductive transformations of CO2 catalyzed by small homogeneous catalysts using earth-abundant elements. Three main types of transformations categorized by the use of different reductants (hydrogen, hydrosilanes, and boranes), in which no C-C bond formation is involved, are surveyed.
 Jolla L. CO2 concentration at Mauna Loa observatory.
 Aresta M, Dibenedetto A, Angelini A. Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. Technological use of CO2. Chem Rev, 2014, 114: 1709-1742
 Suib SL. New and Future Developments in Catalysis. Vol. 4. Oxford: Elsevier, 2013. 81-147
 Tanaka R, Yamashita M, Chung LW, Morokuma K, Nozaki K. Mechanistic studies on the reversible hydrogenation of carbon dioxide catalyzed by an Ir-PNP complex. Organometallics, 2011, 30: 6742-6750
 Sanderson RT. Polar Covalence. New York: Academic Press, 1983
 Sanderson RT. Chemical Bonds and Bond Energy. New York, London: Academic Press, 1971
 Inoue Y, Izumida H, Sadaki Y, Hashimoto H. Catalytic fixation of carbon dioxide to formic acid by transition-metal complexes under mild condition. Chem Lett, 1976: 863-864
 Federsel C, Boddien A, Jackstell R, Jennerjahn R, Dyson PJ, Scopelliti R, Laurenczy G, Beller M. A well-defined iron catalyst for the reduction of bicarbonates and carbon dioxide to formates, alkyl formates, and formamides. Angew Chem Int Ed, 2010, 49: 9777-9780
 Ziebart C, Federsel C, Anbarasan P, Jackstell R, Baumann W, Spannenberg A, Beller M. Well-defined iron catalyst for improved hydrogenation of carbon dioxide and bicarbonate. J Am Chem Soc, 2012, 134: 20701-20704
 Drake JL, Manna CM, Byers JA. Enhanced carbon dioxide hydrogenation facilitated by catalytic quantities of bicarbonate and other inorganic salts. Organometallics, 2013, 32: 6891-6894
 Yang XZ. Hydrogenation of carbon dioxide catalyzed by PNP pincer iridium, iron, and cobalt complexes: a computational design of base metal catalysts. ACS Catal, 2011, 1: 849-854
 Langer R, Diskin-Posner Y, Leitus G, Shimon LJW, Ben-David Y, Milstein D. Low-pressure hydrogenation of carbon dioxide catalyzed by an iron pincer complex exhibiting noble metal activity. Angew Chem Int Ed, 2011, 50: 9948-9952
 Federsel C, Ziebart C, Jackstell R, Baumann W, Beller M. Catalytic hydrogenation of carbon dioxide and bicarbonates with a well defined cobalt dihydrogen complex. Chem Eur J, 2012, 18: 72-75
 Matthew SJ, Michael TM, Appel AM, Linehan JC. A cobalt-based catalyst for the hydrogenation of CO2 under ambient conditions. J Am Chem Soc, 2013, 135: 11533-11536
 Kumar N, Camaioni DM, Dupuis M, Raugei S, Appel AM. Mechanistic insights into hydride transfer for catalytic hydrogenation of CO2 with cobalt complexes. Dalton Trans, 2014, 43: 11803-11806
 Badiet YM, Wang WH, Hull JF, Szalda DJ, Himeda Y, Fujita E. Muckerman JT, Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media. Inorg Chem, 2013, 52: 12576-12586
 Hou C, Jiang JX, Zhang SD, Wang G, Zhang ZH, Ke ZF, Zhao CY Hydrogenation of carbon dioxide using half-sandwich cobalt, rhodium, and iridium complexes: DFT study on the mechanism and metal effect. ACS Catal, 2014, 4: 2990-2997
 Inoue Y, Izumid H, Sasaki Y, Hashimoto H. Catalystic fixation of carbon dioxide to acid by transition-metal complexes under mild conditons. Chem Lett, 1976: 863-864
 Tai CC, Chang T, Roller B, Jessop PG. High-pressure combinatorial screening of homogeneous catalysts: hydrogenation of carbon dioxide. Inorg Chem, 2003, 42: 7340-7341
 Motokura K, Kashiwame D, Miyaji A, Baba T. Copper-catalyzed formic acid synthesis from CO2 with hydrosilanes and H2O. Org Lett, 2012, 14: 2642-2645
 Motokura K, Takahashi N, Kashiwame D, Yamaguchi S, Miyaji A, Baba T. Copper-diphosphine complex catalysts for N-formylation of amines under 1 atm of carbon dioxide with polymethylhydrosiloxane. Catal Sci Technol, 2013, 3: 2392-2396
 Zhang L, Cheng J, Hou Z. Highly efficient catalytic hydrosilylation of carbon dioxide by an N-heterocyclic carbene copper catalyst. Chem Commun, 2013, 49: 4782-4784
 Frogneux X, Jacquet O, Cantat T. Iron-catalyzed hydrosilylation of CO2: CO2 conversion to formamides and methylamines. Catal Sci Technol, 2014, 4: 1529-1533
 Jacquet O, Frogneux X, Gomes CDN, Cantat T. CO2 as a C1-building block for the catalytic methylation of amines. Chem Sci, 2013, 4: 2127-2131
 Sattler W, Parkin G. Zinc catalysts for on-demand hydrogen generation and carbon dioxide functionalization. J Am Chem Soc, 2012, 134: 17462-17465
 González-Sebastián L, Flores-Alamo M, García JJ. Nickel-catalyzed hydrosilylation of CO2 in the presence of Et3B for the synthesis of formic acid and related formates. Organometallics, 2013, 32: 7186- 7194
 Scheuermann ML, Semproni Scott P, Chirik PJ. Carbon dioxide hydrosilylation promoted by cobalt pincer complexes. Inorg Chem, 2014, 53: 9463-9465
 Khandelwal M, Wehmschulte RJ. Deoxygenative reduction of carbon dioxide to methane, toluene, and diphenylmethane with [Et2Al]+ as catalyst. Angew Chem Int Ed, 2012, 51: 7323-7326
 Wehmschulte RJ, Saleh M, Powell DR. CO2 activation with bulky neutral and cationic phenoxyalanes. Organometallic, 2013, 32: 6812- 6819
 Riduan SN, Zhang Y, Ying JY. Conversion of carbon dioxide into methanol with silanes over N-heterocyclic carbene catalysts. Angew Chem Int Ed, 2009, 48: 3322-3325
 Huang F, Lu G, Zhao L, Li H, Wang ZX. The catalytic role of N-heterocyclic carbene in a metal-free conversion of carbon dioxide into methanol: a computational mechanism study. J Am Chem Soc, 2010, 132: 12388-12396
 Das Neves Gomes C, Jacquet O, Villiers C, Thuery P, Ephritikhine M, Cantat T. A diagonal approach to chemical recycling of carbon dioxide: organocatalytic transformation for the reductive functionalization of CO2. Angew Chem Int Ed, 2012, 51: 187-190
 Jacquet O, Das Neves Gomes C, Ephritikhine M, Cantat T. Recycling of carbon and silicon wastes: room temperature formylation of N-H bonds using carbon dioxide and polymethylhydrosiloxane. J Am Chem Soc, 2012, 134: 2934-2937
 Berkefeld A, Piers WE, Parvez M. Tandem frustrated lewis pair/ tris(pentafluorophenyl)borane-catalyzed deoxygenative hydrosilylation of carbon dioxide. J Am Chem Soc, 2010, 132: 10660-10661
 Chakraborty S, Zhang J, Krause JA, Guan H. An efficient nickel catalyst for the reduction of carbon dioxide with a borane. J Am Chem Soc, 2010, 132: 8872-8873
 Chakraborty S, Zhang J, Patel YJ, Krause JA, Guan H. Pincer-ligated nickel hydridoborate complexes: the dormant species in catalytic reduction of carbon dioxide with boranes. Inorg Chem, 2012, 52: 37- 47
 Laitar DS, Müller P, Sadighi JP. Efficient homogeneous catalysis in the reduction of CO2 to CO. J Am Chem Soc, 2005, 127: 17196- 17197
 Zhao H, Lin Z, Marder TB. Density functional theory studies on the mechanism of the reduction of CO2 to CO catalyzed by copper(I) boryl complexes. J Am Chem Soc, 2006, 128: 15637-15643
 Shintani R, Nozaki K. Copper-catalyzed hydroboration of carbon dioxide. Organometallics, 2013, 32: 2459-2462
 Courtemanche MA, Légaré MA, Maron L, Fontaine FG. A highly active phosphine-borane organocatalyst for the reduction of CO2 to methanol using hydroboranes. J Am Chem Soc, 2013, 135: 9326-9329
 Courtemanche MA, Légaré MA, Maron L, Fontaine FG. Reducing CO2 to methanol using frustrated Lewis Pairs: on the mechanism of phosphine-borane mediated hydroboration of CO2. J Am Chem Soc, 2014, 136: 10708-10717
 Courtemanche MA, Larouche J, Légaré MA, Fontaine FG. A tris(triphenylphosphine) aluminum ambiphilic precatalyst for the reduction of carbon dioxide with catecholborane. Organometallics, 2013, 32: 6804-6811
 Wang T, Stephan DW. Carbene-9-BBN ring expansions as a route to intramolecular frustrated Lewis Pairs for CO2 reduction. Chem Eur J, 2014, 20: 3036-3039
 Wang T, Stephan DW. Phosphine catalyzed reduction of CO2 with boranes. Chem Commun, 2014, 50: 7007-7010
 Das Neves Gomes C, Blondiaux E, Thuery P, Cantat T. Metal-free reduction of CO2 with hydroboranes: two efficient pathways at play for the reduction of CO2 to methanol. Chem Eur J, 2014, 20: 7098- 7106
 Enguerrand B, Jacky P, Thibault C. Carbon dioxide reduction to methylamines under metal-free conditions Angew Chem Int Ed, 2014, 53: 12186-12190
 Shang R, Liu L. Transition metal-catalyzed decarboxylative cross- coupling reactions. Sci China Chem, 2011, 54: 1670-1687
 Zhang SL, Fu Y, Shang R. Theoretical analysis of factors controlling Pd-catalyzed decarboxylative coupling of carboxylic acids with olefins. J Am Chem Soc, 2010, 132: 638-646
 Wang S, Huang H, Kahnt J, Mueller AP, Köpke M, Thauer RK. NADP-specific electron-bifurcating [FeFe]-hydrogenase in a functional complex with formate dehydrogenase in Clostridium autoethanogenum grown on CO. J Bacteriol, 2013, 195: 4373-4386
 Schuchmann K, Müller V. Direct and reversible hydrogenation of CO2 to formate by a bacterial carbon dioxide reductase. Science, 2013, 342: 1382-1385
Structures of iron-based catalysts.
Fe-catalyzed hydrogenation of CO2.
Structures of cobalt-based catalysts.
Cu-catalyzed hydrosilylation of CO2.
Structure of the zinc-based catalyst [
Hydrosilylation of CO2 catalyzed by an NHC-supported Cu complex.
Iron-catalyzed formylation of amines using CO2.
Structure of the cobalt-based catalyst [
Structures of the organocatalysts.
Zinc(II)-catalyzed methylation of amines.
Aluminum-catalyzed hydrosilylation of CO2.
Structures of the phosphine-boranes.
Nickel-catalyzed hydroboration of CO2.
Copper catalyzed hydroboration of CO2.
Phosphine-borane catalyzed hydroboration of CO2.
Proazaphosphatrane-catalyzed reduction of secondary amines and CO2 to methylamines.
Copyright 2019 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有