Submitted Successfully!
To reward your contribution, here is a gift for you: A free trial for our video production service.
Thank you for your contribution! You can also upload a video entry or images related to this topic.
Version Summary Created by Modification Content Size Created at Operation
1 -- 4198 2022-04-06 12:49:48 |
2 For brevity -3662 word(s) 536 2022-04-06 23:59:16 | |
3 format correct + 462 word(s) 998 2022-04-08 07:56:44 | |
4 format correct + 31 word(s) 1029 2022-04-08 08:15:40 |

Video Upload Options

Do you have a full video?

Confirm

Are you sure to Delete?
Cite
If you have any further questions, please contact Encyclopedia Editorial Office.
Nielsen, M.; Piccirilli, L.; Pinheiro, D. Pincer Transition Metal Catalysts for Sustainability. Encyclopedia. Available online: https://encyclopedia.pub/entry/21403 (accessed on 20 June 2024).
Nielsen M, Piccirilli L, Pinheiro D. Pincer Transition Metal Catalysts for Sustainability. Encyclopedia. Available at: https://encyclopedia.pub/entry/21403. Accessed June 20, 2024.
Nielsen, Martin, Luca Piccirilli, Danielle Pinheiro. "Pincer Transition Metal Catalysts for Sustainability" Encyclopedia, https://encyclopedia.pub/entry/21403 (accessed June 20, 2024).
Nielsen, M., Piccirilli, L., & Pinheiro, D. (2022, April 06). Pincer Transition Metal Catalysts for Sustainability. In Encyclopedia. https://encyclopedia.pub/entry/21403
Nielsen, Martin, et al. "Pincer Transition Metal Catalysts for Sustainability." Encyclopedia. Web. 06 April, 2022.
Pincer Transition Metal Catalysts for Sustainability
Edit

Sustainable solutions are needed to avoid global warming and climate change. Homogeneous catalysis might play a fundamental role for this. Pincer-type complexes are promising in terms of stability, selectivity, efficiency and the use of mild reaction conditions. Pincer complexes have been used in many sustainable chemical reactions, for example hydrogen release and upconversion of CO2, N2, and biomass.

pincer complexes sustainability biomass valorization hydrogen carbon dioxide valorization nitrogen fixation

1. Introduction

Pincer complexes are highly promising catalysts for numerous sustainable processes. High catalytic activity under mild reaction conditions, low catalyst loading, and high selectivity are the general main advantages important for sustainable reactions as guided by the green chemistry guidelines [1]. Increased robustness because of the pincer stabilization results in increasinly stable homogeneous catalytic systems [2][3][4].
The pincer complex, of the PCP type, was synthetized by Shaw in 1976 [5]. Numeous pincer complexes have since been synthetized as well as used in catalysis[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][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99][100][101][102][103][104][105][106][107][108][109][110][111][112][113][114][115][116][117][118][119][120][121][122][123][124][125][126][127]. Examples are [128][129][130], hydroamination [131][132][133], hydrocarboxylation [134], hydrovinylation [135], aminomethylation [136], alkane dehydrogenation [137][138][139][140][141][142], alkane metathetis [143], amine N-formylation [144][145], secondary alcohol C-alkylation [146][147], ketone α-alkylation [148][149], and amine alkylation [150][151][152][153][154], aniline alkylation [155], vicinal diol deoxydehydration [104][105][156][157][158][159], and water splitting [12][160][161][162][163][164][165][166][167].

2. Dehydrogenation Reactions

2.1. Early Works

In the 1960s, Charman showed the first example of acceptorless alcohol dehydrogenation by homogeneous catalysis [168]. In the mid-1970s, Robinson demonstrated the dehydrogenation of isopropanol, 1-butanol, ethanol, methanol, and glycerol [169][170][171][172].  In 2004, Milstein presented the first example of metal–ligand cooperating pincer ligands in AAD for synthetic purposes [173][174]. In 2015, Li reported computational mechanistic studies on several reactions using the Milstein PNP and PNN catalysts [175]. Simultaneously, the Beller group started exploring the in situ influence of various phosphines and nitrogen containing ligands mixed with ruthenium catalyst precursors for the dehydrogenation of isopropanol [176]. In a following work from 2011, Beller tested both known catalyst as well as the in situ formation of active species using combinations of Ru-precursors and N-containing pincer ligands. In 2013, Beller showed the efficient conversion of ethanol into ethyl acetate using Ru-MACHO, reported in 2012 to efficiently catalyze ester hydrogenation [177]. In 2014, Beller showed that it is feasible to generate hydrogen from ethanol/water mixtures as well as from industrial bio-ethanol obtained from fermentation processes, without prior removal of the water content (5%) [178].

2.2.1. Methanol Dehydrogenation

In 2017, Beller proposed a manganese catalyst for aqueous methanol dehydrogenation [179]. Ethanol, paraformaldehyde, and formic acid were also dehydrogenated. Beller also showed that an iridium-PNP catalyst promotes methanol dehydrogenation under mild conditions [180]. In 2019, Beller improved the activity of Ru-PNP catalysts for methanol dehydrogenation using a bi-catalytic system [181]

2.2.2. Formic Acid Dehydrogenation

Formic acid as hydrogen carrier and storage system has been reviewed in many works [182][183][184][185][186][187][188][189][190][191][192][193]. For example, Milstein showed iron pincer complexes with a lutidine moiety as catalysts for hydrogenation of ketones [194][195], CO2 hydrogenation to formate [196], and formic acid dehydrogenation [197].

3. Hydrogenation Reactions

Pincer complexes have been used in the (transfer) hydrogenation of many substrates, such as ketones [194][198][199][200][201][202][203], esters [38][204][177][195][205][206][207][208][209][210][211][212][213][214][215][216][217][218][219][220], aldehydes [221][222][223], amides [65][224][225][226][227][228], and imines [229][230].
CO2 is potentially a C1 building block, increasing sustainability [231][232][233]. CO2 capture from the atmosphere or from localized emission sources have been studied [234][235][236][237][238][239][240][241][242][243]. CO2 is subsequently stored ior utilized in synthesis of value-added products [244][245][246][247][248][249]. The industry uses several million tons of CO2 for producing e.g. urea, salicylic acid, cyclic carbonates, and polypropylenecarbonate [250][251][252].
Catalytic hydrogenation of CO2 has gained attention for storing green hydrogen with seminal works by Asinger [253], Leitner [254][255], Noyori [256], and Olah [257][258][259][260]. The synthesis of methanol from CO2 is typically carried out at high temperatures and pressures by heterogeneous catalysts such as Cu/ZnO/Al2O3 [261][262][263][264]. Homogeneous catalytic systems have been usedfor the hydrogenation of CO2 into green fuels [265][266][256][267][268][269][270][271][272][273][274][275][276][277][278][279][280][281][282][283][284][285][286].

3.1. CO2 Hydrogenation

3.1.1. Early Works

The hydrogenation of carbon dioxide by means of homogeneous catalysis has grown extensively in the last decade. An overview of the best performing systems for CO2 hydrogenation up to 2010 can be found in the work of Beller [287], while in 2018 and 2019 Prakash reviewed the topic in depth including the use of pincer type complexes [288][289]
Up to 2010, the best performing catalytic system was represented by the iridium-PNP catalyst 9, reported by Nozaki in 2009, which overcame previously reported Ru [290][291][292][293], Rh [294][295][296], and Ir [297] homogeneous systems. In 2011, Milstein and co-workers published the first example of hydrogenation of carbonates into alcohols and carbamates into alcohol and amines as an indirect route for the synthesis of methanol from CO2 [298].  The same year, Sanford proposed a cascade reaction mechanism for CO2 hydrogenation using the Milstein catalyst 24-H in combination with other two homogeneous catalysts, i.e., (PMe3)4Ru-(Cl)(OAc) and Sc(OTf)3 [299]. In 2011, Leitner performed computational studies on 38 different rhodium pincer alkyl complexes with varied steric and electronic environment for the CO2 association and insertion into the metal–carbon bond, resulting in the corresponding carboxylate species [300]. In 2015, Leitner employed catalyst 55 for the hydrogenation of CO2 into methanol without the need of an alcohol additive [301]

3.1.2. CO2 Hydrogenation to Methanol

In 2016, Himeda and Laurenczy reported an iridium complex to catalyse bicarbonate hydrogenation to formate as well as formic acid dehydrogenation [302], and for the production of methanol from CO2 in the presence of sulfuric acid [303]. In 2015, Sanford employed a ruthenium-based catalytic hydrogenation of CO2 to methanol with dimethylamine as capturing agent [304]. The same year, Milstein developed indirect CO2 hydrogenation by prior CO2 capture by amino alcohols followed by hydrogenation of the resulting oxazolidinone to form MeOH [305]. The year after, Olah and Prakash demonstrated a catalytic system for a one-pot CO2 capture as well as conversion to methanol employing polyamine and Ru-MACHO-BH [306].  In 2018, Prakash showed another system for the integrative CO2 capture (trapped in the form of carbamate and bicarbonate salts) followed by hydrogenation to methanol, using a biphasic 2-methyltetrahydrofuran (2-MTHF)/water solvent system [307].

3.1.3. CO2 Hydrogenation to Formate Salts

In 2014, Hazari and Schneider demonstrated Fe-PNP complexes as catalysts with a Lewis acid as co-catalyst for the dehydrogenation of formic acid [308]. One year later, the hydrogenation of CO2 catalyzed by the same system was demonstrated by Hazari and Bernskoetter [309].  In 2016, a comprehensive overview of the state-of-the-art for CO2 hydrogenation, as well as formic acid/methanol dehydrogenation using first-row metal complexes, was published by Bernskoetter and Hazari [310]. The authors provide comparisons between selected iron and cobalt pincers with known Ru-PNP catalysts, and investigate the role of Lewis acid additives in the improvement of these promising base metal catalysts. The same year, Bernskoetter showed the synthesis, as well as crystallographic characterization, of cobalt(I)-PNP complexes derived from the pincer ligand Me-N[CH2CH2(PiPr2]2 [311].

References

  1. Anastas, P.T.; Warner, J.C. Green Chemistry: Theory and Practice 2000; Oxford University Press: New York, NY, USA, 1998; p. 1546.
  2. Grützmacher, H. Cooperating Ligands in Catalysis. Angew. Chem. Int. Ed. 2008, 47, 1814–1818.
  3. Askevold, B.; Roesky, H.W.; Schneider, S. Learning from the Neighbors: Improving Homogeneous Catalysts with Functional Ligands Motivated by Heterogeneous and Biocatalysis. ChemCatChem 2012, 4, 307–320.
  4. Lawrence, M.A.W.; Green, K.A.; Nelson, P.N.; Lorraine, S.C. Review: Pincer ligands—Tunable, versatile and applicable. Polyhedron 2018, 143, 11–27.
  5. Moulton, B.C.J.; Shaw, B.L. 1020 J.C.S.; Dalton: New York, NY, USA, 1975; pp. 1020–1024.
  6. Liu, C.-C.; Liu, Q.-L.; Wu, Z.-Y.; Chen, Y.-C.; Xie, H.-J.; Lei, Q.-F.; Fang, W.-J. Mechanistic insights into small molecule activation induced by ligand cooperativity in PCcarbeneP nickel pincer complexes: A quantum chemistry study. J. Mol. Model. 2015, 21, 242.
  7. Zhao, S.; Wu, J.; Chen, W. Organometallic chemistry of bis (N-heterocyclic carbene) ligands containing a heteroarene spacer. J. Organomet. Chem. 2017, 848, 249–280.
  8. Pugh, D.; Danopoulos, A.A. Metal complexes with ‘pincer’-type ligands incorporating N-heterocyclic carbene functionalities. Coord. Chem. Rev. 2007, 251, 610–641.
  9. Mejuto, C.; García-Eleno, M.A.; Guisado-Barrios, G.; Spasyuk, D.; Gusev, D.; Peris, E. Ruthenium complexes with an N-heterocyclic carbene NNC-pincer ligand: Preparation and catalytic properties. Org. Chem. Front. 2015, 2, 936–941.
  10. Jiang, Y.; Gendy, C.; Roesler, R. Nickel, Ruthenium, and Rhodium NCN-Pincer Complexes Featuring a Six-Membered N-Heterocyclic Carbene Central Moiety and Pyridyl Pendant Arms. Organometallics 2018, 37, 1123–1132.
  11. Sung, S.; Wang, Q.; Krämer, T.; Young, R.D. Synthesis and reactivity of a PCcarbeneP cobalt (i) complex: The missing link in the cobalt PXP pincer series (X = B, C, N). Chem. Sci. 2018, 9, 8234–8241.
  12. Prokopchuk, D.E.; Tsui, B.T.H.; Lough, A.J.; Morris, R.H. Intramolecular C-H/O-h bond cleavage with water and alcohol using a phosphine-free ruthenium carbene NCN Pincer Complex. Chem. A Eur. J. 2014, 20, 16960–16968.
  13. Shimoyama, Y.; Ishizuka, T.; Kotani, H.; Kojima, T. Ruthenium (II) Complexes Having a Pincer-Type Ligand with Two N-Heterocyclic Carbene Moieties. Z. Fur. Anorg. Und. Allg. Chem. 2018, 644, 611–615.
  14. Charra, V.; de Frémont, P.; Braunstein, P. Multidentate N-heterocyclic carbene complexes of the 3d metals: Synthesis, structure, reactivity and catalysis. Coord. Chem. Rev. 2017, 341, 53–176.
  15. Andrew, R.E.; González-Sebastián, L.; Chaplin, A.B. NHC-based pincer ligands: Carbenes with a bite. Dalt. Trans. 2016, 45, 1299–1305.
  16. Cheng, J.; Wang, L.; Wang, P.; Deng, L. High-Oxidation-State 3d Metal (Ti-Cu) Complexes with N-Heterocyclic Carbene Ligation. Chem. Rev. 2018, 118, 9930–9987.
  17. Liddle, S.T.; Mills, D.P.; Wooles, A.J. Early metal bis (phosphorus-stabilised) carbene chemistry. Chem. Soc. Rev. 2011, 40, 2164–2176.
  18. Zhang, D.; Zi, G. N-heterocyclic carbene (NHC) complexes of group 4 transition metals. Chem. Soc. Rev. 2015, 44, 1898–1921.
  19. Polukeev, A.V.; Wendt, O.F. Cyclohexane-Based Phosphinite Iridium Pincer Complexes: Synthesis, Characterization, Carbene Formation, and Catalytic Activity in Dehydrogenation Reactions. Organometallics 2017, 36, 639–649.
  20. Gu, S.; Chen, C.; Qiu, H.; Chen, W. Potentially Hemilabile N-Heterocyclic Carbene Palladium Complexes: Synthesis and Catalytic Applications. Curr. Org. Chem. 2011, 15, 3291–3308.
  21. Peris, E.; Crabtree, R.H. Recent homogeneous catalytic applications of chelate and pincer N-heterocyclic carbenes. Coord. Chem. Rev. 2004, 248, 2239–2246.
  22. Li, H.; Zheng, B.; Huang, K.W. A new class of PN3-pincer ligands for metal-ligand cooperative catalysis. Coord. Chem. Rev. 2015, 293–294, 116–138.
  23. Kisala, J.; Ruman, T. Pincer Complexes Based on Phosphinoaminopyridines: Synthesis, Structural Characterization and Catalytic Applications. Curr. Org. Chem. 2011, 15, 3486–3502.
  24. Benito-Garagorri, D.; Kirchner, K. Modularly designed transition metal PNP and PCP pincer complexes based on aminophosphines: Synthesis and catalytic applications. Acc. Chem. Res. 2008, 41, 201–213.
  25. Deolka, S.; Tarannam, N.; Fayzullin, R.R.; Kozuch, S.; Khaskin, E. Unusual rearrangement of modified PNP ligand based Ru complexes relevant to alcohol dehydrogenation catalysis. Chem. Commun. 2019, 55, 11350–11353.
  26. Henrion, M.; Roisnel, T.; Couturier, J.L.; Dubois, J.L.; Sortais, J.B.; Darcel, C.; Carpentier, J.F. Ruthenium complexes bearing amino-bis (phosphinite) or amino-bis (aminophosphine) ligands: Application in catalytic ester hydrogenation. Mol. Catal. 2017, 432, 15–22.
  27. Yao, C.; Chakraborty, P.; Aresu, E.; Li, H.; Guan, C.; Zhou, C.; Liang, L.C.; Huang, K.W. Monomeric nickel hydroxide stabilized by a sterically demanding phosphorus-nitrogen PN3P-pincer ligand: Synthesis, reactivity and catalysis. Dalt. Trans. 2018, 47, 16057–16065.
  28. Gradiski, M.V.; Tsui, B.T.H.; Lough, A.J.; Morris, R.H. PNN′ & P 2 NN′ ligands via reductive amination with phosphine aldehydes: Synthesis and base-metal coordination chemistry. Dalt. Trans. 2019, 48, 2150–2159.
  29. Kim, Y.; Lee, J.; Son, Y.-H.; Choi, S.-U.; Alam, M.; Park, S. Novel nickel(II), palladium(II), and platinum(II) complexes having a pyrrolyl-iminophosphine (PNN) pincer: Synthesis, crystal structures, and cytotoxic activity. J. Inorg. Biochem. 2020, 205, 111015.
  30. Adams, G.M.; Weller, A.S. POP-type ligands: Variable coordination and hemilabile behaviour. Coord. Chem. Rev. 2018, 355, 150–172.
  31. Leis, W.; Mayer, H.A.; Kaska, W.C. Cycloheptatrienyl, alkyl and aryl PCP-pincer complexes: Ligand backbone effects and metal reactivity. Coord. Chem. Rev. 2008, 252, 1787–1797.
  32. Morales-Morales, D. Recent Applications of Phosphinite POCOP Pincer Complexes towards Organic Transformations. Mini. Rev. Org. Chem. 2008, 5, 141–152.
  33. Gelman, D.; Romm, R. PC(sp3)P Transition Metal Pincer Complexes: Properties and Catalytic Applications. In Topics in Organometallic Chemistry; Springer: Berlin, Germany, 2013; pp. 289–317. ISBN 9783642310805.
  34. Leforestier, B.; Gyton, M.R.; Chaplin, A.B. Synthesis and group 9 complexes of macrocyclic PCP and POCOP pincer ligands. Dalt. Trans. 2020, 49, 2087–2101.
  35. Jensen, C.M. Iridium PCP pincer complexes: Highly active and robust catalysts for novel homogeneous aliphatic dehydrogenations. Chem. Commun. 1999, 3, 2443–2449.
  36. Barrett, B.J.; Iluc, V.M. Coordination of a Hemilabile Pincer Ligand with an Olefinic Backbone to Mid-to-Late Transition Metals. Inorg. Chem. 2014, 53, 7248–7259.
  37. Schörgenhumer, J.; Zimmermann, A.; Waser, M. SNS-Ligands for Ru-Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions. Org. Process Res. Dev. 2018, 22, 862–870.
  38. Spasyuk, D.; Smith, S.; Gusev, D.G. Replacing Phosphorus with Sulfur for the Efficient Hydrogenation of Esters. Angew. Chem. Int. Ed. 2013, 52, 2538–2542.
  39. Valdés, H.; González-Sebastián, L.; Morales-Morales, D. Aromatic para-functionalized NCN pincer compounds. J. Organomet. Chem. 2017, 845, 229–257.
  40. Fernández-Alvarez, F.J.; Lalrempuia, R.; Oro, L.A. Monoanionic NSiN-type ligands in transition metal coordination chemistry and catalysis. Coord. Chem. Rev. 2017, 350, 49–60.
  41. Garbe, S.; Krause, M.; Klimpel, A.; Neundorf, I.; Lippmann, P.; Ott, I.; Brünink, D.; Strassert, C.A.; Doltsinis, N.L.; Klein, A. Cyclometalated Pt Complexes of CNC Pincer Ligands: Luminescence and Cytotoxic Evaluation. Organometallics 2020, 39, 746–756.
  42. Ruan, J.; Wang, D.; Vedernikov, A.N. CH3–X Reductive Elimination Reactivity of PtIVMe Complexes Supported by a Sulfonated CNN Pincer Ligand (X = OH, CF3CO2, PhNMe2+). Organometallics 2020, 39, 142–152.
  43. Heidebrecht, J.; Gendy, C.; Gelfand, B.S.; Roesler, R. Water-soluble NNN-pincer complexes of cobalt, nickel and palladium: Solid-state structures and catalytic activity. Polyhedron 2018, 143, 138–143.
  44. Kozlov, V.A.; Aleksanyan, D.V.; Vasilév, A.A.; Odinets, I.L. Thiophosphoryl-, thiophosphoryloxy-, and thiophosphorylamino-benzene derivatives as novel classes of hybrid pincer ligands. Phosphorus Sulfur Silicon Relat. Elem. 2011, 186, 626–637.
  45. Al-Noaimi, M.; Awwadi, F.F.; Talib, W.H.; Atia, S.; Hammud, H.H. Cis and trans- palladium (II) complexes derived from SNN amidrazone pincer ligand: Synthesis, crystal structures and biological evaluation. J. Mol. Struct. 2019, 1197, 282–291.
  46. Okamoto, K.; Kuwabara, J.; Kanbara, T. Secondary Thioamides as Multidentate Ligands for Functional Metal Complexes. Chem. Lett. 2015, 44, 102–110.
  47. Simon, M.; Breher, F. Multidentate silyl ligands in transition metal chemistry. Dalt. Trans. 2017, 46, 7976–7997.
  48. Zhou, Y.P.; Mo, Z.; Luecke, M.P.; Driess, M. Stereoselective Transfer Semi-Hydrogenation of Alkynes to E-Olefins with N-Heterocyclic Silylene–Manganese Catalysts. Chem. A Eur. J. 2018, 24, 4780–4784.
  49. Kumar, A.; Rao, G.K.; Saleem, F.; Singh, A.K. Organoselenium ligands in catalysis. Dalt. Trans. 2012, 41, 11949–11977.
  50. Sharma, K.N.; Satrawala, N.; Srivastava, A.K.; Ali, M.; Joshi, R.K. Palladium (ii) ligated with a selenated (Se, CNHC, N-) -type pincer ligand: An efficient catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling in water. Org. Biomol. Chem. 2019, 17, 8969–8976.
  51. Kameo, H.; Nakazawa, H. Recent developments in the coordination chemistry of multidentate ligands featuring a boron moiety. Chem. Asian J. 2013, 8, 1720–1734.
  52. Yamashita, M. The Organometallic Chemistry of Boron-Containing Pincer Ligands based on Diazaboroles and Carboranes. Bull. Chem. Soc. Jpn. 2016, 89, 269–281.
  53. Balakrishna, M.S. Unusual and rare pincer ligands: Synthesis, metallation, reactivity and catalytic studies. Polyhedron 2018, 143, 2–10.
  54. Van Der Boom, M.E.; Milstein, D. Cyclometalated phosphine-based pincer complexes: Mechanistic insight in catalysis, coordination, and bond activation. Chem. Rev. 2003, 103, 1759–1792.
  55. Peris, E.; Crabtree, R.H. Key factors in pincer ligand design. Chem. Soc. Rev. 2018, 47, 1959–1968.
  56. Toda, T.; Suzuki, S.; Kuwata, S. Metallo-supramolecular assembly of protic pincer-type complexes: Encapsulation of dinitrogen and carbon disulfide into a multiproton-responsive diruthenium cage. Chem. Commun. 2019, 55, 1028–1031.
  57. Nelson, D.J.; Nolan, S.P. Hydroxide complexes of the late transition metals: Organometallic chemistry and catalysis. Coord. Chem. Rev. 2017, 353, 278–294.
  58. Maser, L.; Vondung, L.; Langer, R. The ABC in pincer chemistry—From amine- to borylene- and carbon-based pincer-ligands. Polyhedron 2018, 143, 28–42.
  59. Gusev, D.G.; Madott, M.; Dolgushin, F.M.; Lyssenko, K.A.; Antipin, M.Y. Agostic bonding in pincer complexes of ruthenium. Organometallics 2000, 19, 1734–1739.
  60. Annibale, V.T.; Song, D. Multidentate actor ligands as versatile platforms for small molecule activation and catalysis. RSC Adv. 2013, 3, 11432–11449.
  61. Ananthnag, G.S.; Shetti, V.S. Synthesis, structure and catalysis of organometallic porphyrin-pincer hybrids: A review. Dalt. Trans. 2017, 46, 14062–14082.
  62. Gunanathan, C.; Milstein, D. Bond Activation and Catalysis by Ruthenium Pincer Complexes. Chem. Rev. 2014, 114, 12024–12087.
  63. Younus, H.A.; Ahmad, N.; Su, W.; Verpoort, F. Ruthenium pincer complexes: Ligand design and complex synthesis. Coord. Chem. Rev. 2014, 276, 112–152.
  64. Younus, H.A.; Su, W.; Ahmad, N.; Chen, S.; Verpoort, F. Ruthenium pincer complexes: Synthesis and catalytic applications. Adv. Synth. Catal. 2015, 357, 283–330.
  65. Werkmeister, S.; Junge, K.; Beller, M. Catalytic hydrogenation of carboxylic acid esters, amides, and nitriles with homogeneous catalysts. Org. Process Res. Dev. 2014, 18, 289–302.
  66. Gusev, D.G.; Lough, A.J. Experimental and computational study of pincer complexes of ruthenium with Py, CO, and N2 ligands. Organometallics 2002, 21, 5091–5099.
  67. Gusev, D.G.; Dolgushin, F.M.; Antipin, M.Y. Hydride, borohydride, and dinitrogen pincer complexes of ruthenium. Organometallics 2000, 19, 3429–3434.
  68. Abbel, R.; Abdur-Rashid, K.; Faatz, M.; Hadzovic, A.; Lough, A.J.; Morris, R.H. A succession of isomers of ruthenium dihydride complexes. Which one is the ketone hydrogenation catalyst? J. Am. Chem. Soc. 2005, 127, 1870–1882.
  69. Bruneau, C.; Dixneuf, P.H. Ruthenium in Catalysis; Springer: Berlin, Germany, 2014; ISBN 9783319084817.
  70. Dub, P.A.; Ikariya, T. Quantum chemical calculations with the inclusion of nonspecific and specific solvation: Asymmetric transfer hydrogenation with bifunctional ruthenium catalysts. J. Am. Chem. Soc. 2013, 135, 2604–2619.
  71. Bertoli, M.; Choualeb, A.; Lough, A.J.; Moore, B.; Spasyuk, D.; Gusev, D.G. Osmium and ruthenium catalysts for dehydrogenation of alcohols. Organometallics 2011, 30, 3479–3482.
  72. Chelucci, G.; Baldino, S.; Baratta, W. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions. Acc. Chem. Res. 2015, 48, 363–379.
  73. Bertoli, M.; Choualeb, A.; Gusev, D.G.; Lough, A.J.; Major, Q.; Moore, B. PNP pincer osmium polyhydrides for catalytic dehydrogenation of primary alcohols. Dalt. Trans. 2011, 40, 8941.
  74. Gusev, D.G.; Lough, A.J.; Double, C.-H. activation on osmium and ruthenium centers: Carbene vs olefin products. Organometallics 2002, 21, 2601–2603.
  75. Choi, J.; MacArthur, A.H.R.; Brookhart, M.; Goldman, A.S. Dehydrogenation and Related Reactions Catalyzed by Iridium Pincer Complexes. Chem. Rev. 2011, 111, 1761–1779.
  76. Choualeb, A.; Lough, A.J.; Gusev, D.G. Hemilabile pincer-type hydride complexes of iridium. Organometallics 2007, 26, 5224–5229.
  77. Clarke, Z.E.; Maragh, P.T.; Dasgupta, T.P.; Gusev, D.G.; Lough, A.J.; Abdur-Rashid, K. A family of active iridium catalysts for transfer hydrogenation of ketones. Organometallics 2006, 25, 4113–4117.
  78. Meiners, J.; Scheibel, M.G.; Lemée-Cailleau, M.H.; Mason, S.A.; Boeddinghaus, M.B.; Fässler, T.F.; Herdtweck, E.; Khusniyarov, M.M.; Schneider, S. Square-planar iridium (II) and iridium (III) amido complexes stabilized by a PNP pincer ligand. Angew. Chem. Int. Ed. 2011, 50, 8184–8187.
  79. Goldberg, J.M.; Wong, G.W.; Brastow, K.E.; Kaminsky, W.; Goldberg, K.I.; Heinekey, D.M. The Importance of Steric Factors in Iridium Pincer Complexes. Organometallics 2015, 34, 753–762.
  80. Scheibel, M.G.; Wu, Y.; Stückl, A.C.; Krause, L.; Carl, E.; Stalke, D.; De Bruin, B.; Schneider, S. Synthesis and reactivity of a transient, terminal nitrido complex of rhodium. J. Am. Chem. Soc. 2013, 135, 17719–17722.
  81. Sundermann, A.; Uzan, O.; Milstein, D.; Martin, J.M.L. Selective C-C vs C-H bond activation by rhodium (I) PCP pincer complexes. A computational study. J. Am. Chem. Soc. 2000, 122, 7095–7104.
  82. Urgoitia, G.; Galdón, G.; Churruca, F.; SanMartin, R.; Herrero, M.T.; Domínguez, E. Aerobic oxidation of secondary benzyl alcohols catalyzed by phosphinite-based palladium pincer complexes. Environ. Chem. Lett. 2018, 16, 1101–1108.
  83. Albrecht, M.; Van Koten, G. Platinum group organometallics based on “pincer” complexes: Sensors, switches, and catalysts. Angew. Chem. Int. Ed. 2001, 40, 3750–3781.
  84. Selander, N.; Szabó, K.J. Catalysis by palladium pincer complexes. Chem. Rev. 2011, 111, 2048–2076.
  85. González-Sebastián, L.; Morales-Morales, D. Cross-coupling reactions catalysed by palladium pincer complexes. A review of recent advances. J. Organomet. Chem. 2019, 893, 39–51.
  86. Esteruelas, M.A.; López, A.M.; Oliván, M. Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions. Chem. Rev. 2016, 116, 8770–8847.
  87. Therrien, J.A.; Wolf, M.O.; Patrick, B.O. Synthesis and comparison of nickel, palladium, and platinum bis (N-heterocyclic carbene) pincer complexes for electrocatalytic CO2 reduction. Dalt. Trans. 2018, 47, 1827–1840.
  88. Bauer, G.; Hu, X. Recent developments of iron pincer complexes for catalytic applications. Inorg. Chem. Front. 2016, 3, 741–765.
  89. Dai, H.; Guan, H. Iron Dihydride Complexes: Synthesis, Reactivity, and Catalytic Applications. Isr. J. Chem. 2017, 57, 1170–1203.
  90. Bhattacharya, P.; Guan, H. Synthesis and catalytic applications of iron pincer complexes. Comments Inorg. Chem. 2011, 32, 88–112.
  91. Balaraman, E.; Nandakumar, A.; Jaiswal, G.; Sahoo, M.K. Iron-catalyzed dehydrogenation reactions and their applications in sustainable energy and catalysis. Catal. Sci. Technol. 2017, 7, 3177–3195.
  92. Benito-Garagorri, D.; Puchberger, M.; Mereiter, K.; Kirchner, K. Stereospecific and reversible CO binding at iron pincer complexes. Angew. Chem. Int. Ed. 2008, 47, 9142–9145.
  93. Junge, K.; Schröder, K.; Beller, M. Homogeneous catalysis using iron complexes: Recent developments in selective reductions. Chem. Commun. 2011, 47, 4849.
  94. Bernskoetter, W.H.; Hazari, N. Hydrogenation and dehydrogenation reactions catalyzed by iron pincer compounds. In Pincer Compounds; Elsevier Inc.: Amsterdam, The Netherland, 2018; ISBN 9780128129326.
  95. Rohit, K.R.; Radhika, S.; Saranya, S.; Anilkumar, G. Manganese-Catalysed Dehydrogenative Coupling—An Overview. Adv. Synth. Catal. 2020, 362, 1602–1650.
  96. Waiba, S.; Maji, B. Manganese Catalyzed Acceptorless Dehydrogenative Coupling Reactions. ChemCatChem 2019, 12, 1891–1902.
  97. Maji, B.; Barman, M.K. Recent Developments of Manganese Complexes for Catalytic Hydrogenation and Dehydrogenation Reactions. Synthesis 2017, 49, 3377–3393.
  98. Garbe, M.; Junge, K.; Beller, M. Homogeneous Catalysis by Manganese-Based Pincer Complexes. Eur. J. Org. Chem. 2017, 2017, 4344–4362.
  99. Eberhardt, N.A.; Guan, H. Nickel Hydride Complexes. Chem. Rev. 2016, 116, 8373–8426.
  100. Gafurov, Z.N.; Kagilev, A.A.; Kantyukov, A.O.; Balabaev, A.A.; Sinyashin, O.G.; Yakhvarov, D.G. Classification and synthesis of nickel pincer complexes. Russ. Chem. Bull. 2018, 67, 385–394.
  101. Klein, A.; Sandleben, A.; Vogt, N. Synthesis, Structure and Reactivity of Cyclometalated Nickel (II) Complexes: A Review and Perspective. Proc. Natl. Acad. Sci. India Sect. A Phys. Sci. 2016, 86, 533–549.
  102. Gutsulyak, D.V.; Piers, W.E.; Borau-Garcia, J.; Parvez, M. Activation of water, ammonia, and other small molecules by PC carbeneP nickel pincer complexes. J. Am. Chem. Soc. 2013, 135, 11776–11779.
  103. LaPierre, E.A.; Clapson, M.L.; Piers, W.E.; Maron, L.; Spasyuk, D.M.; Gendy, C. Oxygen Atom Transfer to Cationic PCPNi(II) Complexes Using Amine-N-Oxides. Inorg. Chem. 2018, 57, 495–506.
  104. Chapman, G.; Nicholas, K.M. Vanadium-catalyzed deoxydehydration of glycols. Chem. Commun. 2013, 49, 8199.
  105. Gopaladasu, T.V.; Nicholas, K.M. Carbon Monoxide (CO)- and Hydrogen-Driven, Vanadium-Catalyzed Deoxydehydration of Glycols. ACS Catal. 2016, 6, 1901–1904.
  106. Hanson, S.K.; Baker, R.T.; Gordon, J.C.; Scott, B.L.; Thorn, D.L. Aerobic Oxidation of Lignin Models Using a Base Metal Vanadium Catalyst. Inorg. Chem. 2010, 49, 5611–5618.
  107. Junge, K.; Papa, V.; Beller, M. Cobalt–Pincer Complexes in Catalysis. Chem. A Eur. J. 2019, 25, 122–143.
  108. Liu, W.; Sahoo, B.; Junge, K.; Beller, M. Cobalt Complexes as an Emerging Class of Catalysts for Homogeneous Hydrogenations. Acc. Chem. Res. 2018, 51, 1858–1869.
  109. Ai, W.; Zhong, R.; Liu, X.; Liu, Q. Hydride Transfer Reactions Catalyzed by Cobalt Complexes. Chem. Rev. 2019, 119, 2876–2953.
  110. Lagaditis, P.O.; Schluschaß, B.; Demeshko, S.; Würtele, C.; Schneider, S. Square-Planar Cobalt (III) Pincer Complex. Inorg. Chem. 2016, 55, 4529–4536.
  111. Midya, S.P.; Pitchaimani, J.; Landge, V.G.; Madhu, V.; Balaraman, E. Direct access to: N -alkylated amines and imines via acceptorless dehydrogenative coupling catalyzed by a cobalt (ii)-NNN pincer complex. Catal. Sci. Technol. 2018, 8, 3469–3473.
  112. Ge, H.; Jing, Y.; Yang, X. Computational Design of Cobalt Catalysts for Hydrogenation of Carbon Dioxide and Dehydrogenation of Formic Acid. Inorg. Chem. 2016, 55, 12179–12184.
  113. Gorgas, N.; Kirchner, K. Isoelectronic Manganese and Iron Hydrogenation/Dehydrogenation Catalysts: Similarities and Divergences. Acc. Chem. Res. 2018, 51, 1558–1569.
  114. Reed-Berendt, B.G.; Polidano, K.; Morrill, L.C. Recent advances in homogeneous borrowing hydrogen catalysis using earth-abundant first row transition metals. Org. Biomol. Chem. 2019, 17, 1595–1607.
  115. Anastas, P.T.; Zimmerman, J.B. The periodic table of the elements of green and sustainable chemistry. Green Chem. 2019, 6545–6566.
  116. Kallmeier, F.; Kempe, R. Manganese Complexes for (De) Hydrogenation Catalysis: A Comparison to Cobalt and Iron Catalysts. Angew. Chem. Int. Ed. 2018, 57, 46–60.
  117. Nguyen, D.H.; Morin, Y.; Zhang, L.; Trivelli, X.; Capet, F.; Paul, S.; Desset, S.; Dumeignil, F.; Gauvin, R.M. Oxidative Transformations of Biosourced Alcohols Catalyzed by Earth-Abundant Transition Metals. ChemCatChem 2017, 9, 2652–2660.
  118. Mukherjee, A.; Milstein, D. Homogeneous Catalysis by Cobalt and Manganese Pincer Complexes. ACS Catal. 2018, 8, 11435–11469.
  119. Zell, T.; Langer, R. From Ruthenium to Iron and Manganese—A Mechanistic View on Challenges and Design Principles of Base-Metal Hydrogenation Catalysts. ChemCatChem 2018, 10, 1930–1940.
  120. Filonenko, G.A.; Van Putten, R.; Hensen, E.J.M.; Pidko, E.A. Catalytic (de) hydrogenation promoted by non-precious metals-Co, Fe and Mn: Recent advances in an emerging field. Chem. Soc. Rev. 2018, 47, 1459–1483.
  121. Alig, L.; Fritz, M.; Schneider, S. First-Row Transition Metal (De) Hydrogenation Catalysis Based on Functional Pincer Ligands. Chem. Rev. 2019, 119, 2681–2751.
  122. Zhang, Z.; Butt, N.A.; Zhou, M.; Liu, D.; Zhang, W. Asymmetric Transfer and Pressure Hydrogenation with Earth-Abundant Transition Metal Catalysts. Chin. J. Chem. 2018, 36, 443–454.
  123. Riisager, A.; Fehrmann, R.; Haumann, M.; Wasserscheid, P. Supported Ionic Liquid Phase (SILP) catalysis: An innovative concept for homogeneous catalysis in continuous fixed-bed reactors. Eur. J. Inorg. Chem. 2006, 695–706.
  124. Selvam, T.; MacHoke, A.; Schwieger, W. Supported ionic liquids on non-porous and porous inorganic materials-A topical review. Appl. Catal. A Gen. 2012, 445–446, 92–101.
  125. Brünig, J.; Csendes, Z.; Weber, S.; Gorgas, N.; Bittner, R.W.; Limbeck, A.; Bica, K.; Hoffmann, H.; Kirchner, K. Chemoselective Supported Ionic-Liquid-Phase (SILP) Aldehyde Hydrogenation Catalyzed by an Fe(II) PNP Pincer Complex. ACS Catal. 2018, 8, 1048–1051.
  126. Castro-Amoedo, R.; Csendes, Z.; Brünig, J.; Sauer, M.; Foelske-Schmitz, A.; Yigit, N.; Rupprechter, G.; Gupta, T.; Martins, A.M.; Bica, K.; et al. Carbon-based SILP catalysis for the selective hydrogenation of aldehydes using a well-defined Fe(ii) PNP complex. Catal. Sci. Technol. 2018, 8, 4812–4820.
  127. Sheludko, B.; Cunningham, M.T.; Goldman, A.S.; Celik, F.E. Continuous-Flow Alkane Dehydrogenation by Supported Pincer-Ligated Iridium Catalysts at Elevated Temperatures. ACS Catal. 2018, 8, 7828–7841.
  128. Barman, M.K.; Waiba, S.; Maji, B. Manganese-Catalyzed Direct Olefination via an Acceptorless Dehydrogenative Coupling of Methyl Heteroarenes with Primary Alcohols. Synlett 2019, 30, 12–20.
  129. Thiyagarajan, S.; Gunanathan, C. Ruthenium-Catalyzed α-Olefination of Nitriles Using Secondary Alcohols. ACS Catal. 2018, 8, 2473–2478.
  130. Zhang, G.; Irrgang, T.; Dietel, T.; Kallmeier, F.; Kempe, R. Manganese-Catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-Substituted N-Heteroarenes with Alcohols. Angew. Chem. Int. Ed. 2018, 57, 9131–9135.
  131. Bauer, E.B.; Andavan, G.T.S.; Hollis, T.K.; Rubio, R.J.; Cho, J.; Kuchenbeiser, G.R.; Helgert, T.R.; Letko, C.S.; Tham, F.S. Air-and water-stable catalysts for hydroamination/cyclization. Synthesis and application of CCC-NHC pincer complexes of RH and Ir. Org. Lett. 2008, 10, 1175–1178.
  132. Cho, J.; Hollis, T.K.; Valente, E.J.; Trate, J.M. CCC-N-heterocyclic carbene pincer complexes: Synthesis, characterization and hydroamination activity of a hafnium complex. J. Organomet. Chem. 2011, 696, 373–377.
  133. Castonguay, A.; Spasyuk, D.M.; Madern, N.; Beauchamp, A.L.; Zargarian, D. Regioselective hydroamination of acrylonitrile catalyzed by cationic pincer complexes of nickel (II). Organometallics 2009, 28, 2134–2141.
  134. Takaya, J.; Iwasawa, N. Hydrocarboxylation of allenes with CO2 catalyzed by silyl pincer-type palladium complex. J. Am. Chem. Soc. 2008, 130, 15254–15255.
  135. Serra, D.; Cao, P.; Cabrera, J.; Padilla, R.; Rominger, F.; Limbach, M. Development of platinum (II) and -(IV) CNC pincer complexes and their application in a hydrovinylation reaction. Organometallics 2011, 30, 1885–1895.
  136. Mastalir, M.; Pittenauer, E.; Allmaier, G.; Kirchner, K. Manganese-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as a Sustainable C1 Building Block. J. Am. Chem. Soc. 2017, 139, 8812–8815.
  137. Zhang, Y.; Fang, H.; Yao, W.; Leng, X.; Huang, Z. Synthesis of Pincer Hydrido Ruthenium Olefin Complexes for Catalytic Alkane Dehydrogenation. Organometallics 2016, 35, 181–188.
  138. Kumar, A.; Bhatti, T.M.; Goldman, A.S. Dehydrogenation of Alkanes and Aliphatic Groups by Pincer-Ligated Metal Complexes. Chem. Rev. 2017, 117, 12357–12384.
  139. Das, K.; Kumar, A. Alkane Dehydrogenation Reactions Catalyzed by Pincer-Metal Complexes, 1st ed.; Elsevier Inc.: Amsterdam, The Netherlands, 2019; ISBN 9780128171172.
  140. Renkema, K.B.; Kissin, Y.V.; Goldman, A.S. Mechanism of alkane transfer-dehydrogenation catalyzed by a pincer-ligated iridium complex. J. Am. Chem. Soc. 2003, 125, 7770–7771.
  141. Zhu, K.; Achord, P.D.; Zhang, X.; Krogh-Jespersen, K.; Goldman, A.S. Highly effective pincer-ligated iridium catalysts for alkane dehydrogenation. DFT calculations of relevant thermodynamic, kinetic, and spectroscopic properties. J. Am. Chem. Soc. 2004, 126, 13044–13053.
  142. Göttker-Schnetmann, I.; White, P.; Brookhart, M. Iridium Bis (phosphinite) p -XPCP Pincer Complexes: Highly Active Catalysts for the Transfer Dehydrogenation of Alkanes. J. Am. Chem. Soc. 2004, 126, 1804–1811.
  143. Nawara-Hultzsch, A.J.; Hackenberg, J.D.; Punji, B.; Supplee, C.; Emge, T.J.; Bailey, B.C.; Schrock, R.R.; Brookhart, M.; Goldman, A.S. Rational design of highly active “hybrid” phosphine-phosphinite pincer iridium catalysts for alkane metathesis. ACS Catal. 2013, 3, 2505–2514.
  144. Chakraborty, S.; Gellrich, U.; Diskin-Posner, Y.; Leitus, G.; Avram, L.; Milstein, D. Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study. Angew. Chem. 2017, 129, 4293–4297.
  145. Daw, P.; Chakraborty, S.; Leitus, G.; Diskin-Posner, Y.; Ben-David, Y.; Milstein, D. Selective N-Formylation of Amines with H2 and CO2 Catalyzed by Cobalt Pincer Complexes. ACS Catal. 2017, 7, 2500–2504.
  146. El-Sepelgy, O.; Matador, E.; Brzozowska, A.; Rueping, M. C-Alkylation of Secondary Alcohols by Primary Alcohols through Manganese-Catalyzed Double Hydrogen Autotransfer. ChemSusChem 2019, 12, 3099–3102.
  147. Freitag, F.; Irrgang, T.; Kempe, R. Cobalt-Catalyzed Alkylation of Secondary Alcohols with Primary Alcohols via Borrowing Hydrogen/Hydrogen Autotransfer. Chem. A Eur. J. 2017, 23, 12110–12113.
  148. Barman, M.K.; Jana, A.; Maji, B. Phosphine-Free NNN-Manganese Complex Catalyzed α-Alkylation of Ketones with Primary Alcohols and Friedländer Quinoline Synthesis. Adv. Synth. Catal. 2018, 360, 3233–3238.
  149. Peña-López, M.; Piehl, P.; Elangovan, S.; Neumann, H.; Beller, M. Manganese-Catalyzed Hydrogen-Autotransfer C–C Bond Formation: α-Alkylation of Ketones with Primary Alcohols. Angew. Chem. Int. Ed. 2016, 55, 14967–14971.
  150. Elangovan, S.; Neumann, J.; Sortais, J.B.; Junge, K.; Darcel, C.; Beller, M. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes. Nat. Commun. 2016, 7, 1–8.
  151. Mastalir, M.; Tomsu, G.; Pittenauer, E.; Allmaier, G.; Kirchner, K. Co(II) PCP Pincer Complexes as Catalysts for the Alkylation of Aromatic Amines with Primary Alcohols. Org. Lett. 2016, 18, 3462–3465.
  152. Rösler, S.; Ertl, M.; Irrgang, T.; Kempe, R. Cobalt-Catalyzed Alkylation of Aromatic Amines by Alcohols. Angew. Chem. Int. Ed. 2015, 54, 15046–15050.
  153. Mastalir, M.; Stöger, B.; Pittenauer, E.; Puchberger, M.; Allmaier, G.; Kirchner, K. Air Stable Iron(II) PNP Pincer Complexes as Efficient Catalysts for the Selective Alkylation of Amines with Alcohols. Adv. Synth. Catal. 2016, 358, 3824–3831.
  154. Homberg, L.; Roller, A.; Hultzsch, K.C. A Highly Active PN 3 Manganese Pincer Complex Performing N-Alkylation of Amines under Mild Conditions. Org. Lett. 2019, 21, 3142–3147.
  155. Landge, V.G.; Mondal, A.; Kumar, V.; Nandakumar, A.; Balaraman, E. Manganese catalyzed N-alkylation of anilines with alcohols: Ligand enabled selectivity. Org. Biomol. Chem. 2018, 16, 8175–8180.
  156. Li, J.; Lutz, M.; Klein Gebbink, R.J.M. N,N,O-Coordinated tricarbonylrhenium precatalysts for the aerobic deoxydehydration of diols and polyols. Catal. Sci. Technol. 2020, 10, 3782–3788.
  157. Siu, T.C.; Silva, I.; Lunn, M.J.; John, A. Influence of the pendant arm in deoxydehydration catalyzed by dioxomolybdenum complexes supported by amine bisphenolate ligands. New J. Chem. 2020, 44, 9933–9941.
  158. Petersen, A.R.; Fristrup, P. New Motifs in Deoxydehydration: Beyond the Realms of Rhenium. Chem. A Eur. J. 2017, 23, 10235–10243.
  159. Tshibalonza, N.N.; Monbaliu, J.-C.M. The deoxydehydration (DODH) reaction: A versatile technology for accessing olefins from bio-based polyols. Green Chem. 2020.
  160. Chen, F.; Wang, N.; Lei, H.; Guo, D.; Liu, H.; Zhang, Z.; Zhang, W.; Lai, W.; Cao, R. Electrocatalytic Water Oxidation by a Water-Soluble Copper(II) Complex with a Copper-Bound Carbonate Group Acting as a Potential Proton Shuttle. Inorg. Chem. 2017, 56, 13368–13375.
  161. Lant, H.M.C.; Michaelos, T.K.; Sharninghausen, L.S.; Mercado, B.Q.; Crabtree, R.H.; Brudvig, G.W. N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox-Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution. Eur. J. Inorg. Chem. 2019, 2019, 2115–2123.
  162. Kohl, S.W.; Weiner, L.; Schwartsburd, L.; Konstantinovski, L.; Shimon, L.J.W.; Ben-David, Y.; Iron, M.A.; Milstein, D. Consecutive Thermal H 2 and Light-Induced O 2 Evolution from Water Promoted by a Metal Complex. Science 2009, 324, 74–77.
  163. Sandhya, K.S.; Suresh, C.H. Water splitting promoted by a ruthenium(II) PNN complex: An alternate pathway through a dihydrogen complex for hydrogen production. Organometallics 2011, 30, 3888–3891.
  164. Sandhya, K.S.; Suresh, C.H. DFT study on the mechanism of water-assisted dihydrogen elimination in group 6 octahedral metal hydride complexes. Dalt. Trans. 2012, 41, 11018–11025.
  165. Sandhya, K.S.; Remya, G.S.; Suresh, C.H. Pincer Ligand Modifications to Tune the Activation Barrier for H2 Elimination in Water Splitting Milstein Catalyst. Inorg. Chem. 2015, 54, 11150–11156.
  166. Ma, C.; Piccinin, S.; Fabris, S. Reaction mechanisms of water splitting and H2 evolution by a Ru(II)-pincer complex identified with Ab initio metadynamics simulations. ACS Catal. 2012, 2, 1500–1506.
  167. Yang, X.; Hall, M.B. Mechanism of water splitting and oxygen-oxygen bond formation by a mononuclear ruthenium complex. J. Am. Chem. Soc. 2010, 132, 120–130.
  168. Charman, H.B. Hydride transfer reactions catalysed by metal complexes. J. Chem. Soc. B Phys. Org. 1967, 36, 629–632.
  169. Morton, D.; Cole-Hamilton, D.J. ChemInform Abstract: Molecular Hydrogen Complexes in Catalysis: Highly Efficient Hydrogen Production from Alcoholic Substrates Catalyzed by Ruthenium Complexes. ChemInform 2016, 20, 1154–1156.
  170. Morton, D.; Cole-Hamilton, D.J.; Schofield, J.A.; Pryce, R.J. Rapid thermal hydrogen production from 2,3-butanediol catalyzed by homogeneous rhodium catalysis. Polyhedron 1987, 6, 2187–2189.
  171. Dobscn, A.; Robinson, S.D. Catalytic dehydrogenation of primary and secondary alcohols by Ru(OCOCF3)2(CO)(PPh3)2. J. Organomet. Chem. 1975, 87, 52–53.
  172. Dobson, A.; Robinson, S.D. Complexes of the Platinum Metals. 7. Homogeneous Ruthenium and Osmium Catalysts for the Dehydrogenation of Primary and Secondary Alcohols. Inorg. Chem. 1977, 16, 137–142.
  173. Zhang, J.; Gandelman, M.; Shimon, L.J.W.; Rozenberg, H.; Milstein, D. Electron-rich, bulky ruthenium PNP-type complexes. Acceptorless catalytic alcohol dehydrogenation. Organometallics 2004, 23, 4026–4033.
  174. Zhang, J.; Leitus, G.; Ben-David, Y.; Milstein, D. Facile conversion of alcohols into esters and dihydrogen catalyzed by new ruthenium complexes. J. Am. Chem. Soc. 2005, 127, 10840–10841.
  175. Li, H.; Hall, M.B. Computational mechanistic studies on reactions of transition metal complexes with noninnocent pincer ligands: Aromatization-dearomatization or not. ACS Catal. 2015, 5, 1895–1913.
  176. Junge, H.; Beller, M. Ruthenium-catalyzed generation of hydrogen from iso-propanol. Tetrahedron Lett. 2005, 46, 1031–1034.
  177. Kuriyama, W.; Matsumoto, T.; Ogata, O.; Ino, Y.; Aoki, K.; Tanaka, S.; Ishida, K.; Kobayashi, T.; Sayo, N.; Saito, T. Catalytic hydrogenation of esters. Development of an efficient catalyst and processes for synthesising (R)-1,2-propanediol and 2-(l-Menthoxy)ethanol. Org. Process Res. Dev. 2012, 16, 166–171.
  178. Sponholz, P.; Mellmann, D.; Cordes, C.; Alsabeh, P.G.; Li, B.; Li, Y.; Nielsen, M.; Junge, H.; Dixneuf, P.; Beller, M. Efficient and Selective Hydrogen Generation from Bioethanol using Ruthenium Pincer-type Complexes. ChemSusChem 2014, 7, 2419–2422.
  179. Andérez-Fernández, M.; Vogt, L.K.; Fischer, S.; Zhou, W.; Jiao, H.; Garbe, M.; Elangovan, S.; Junge, K.; Junge, H.; Ludwig, R.; et al. A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol. Angew. Chem. Int. Ed. 2017, 56, 559–562.
  180. Prichatz, C.; Alberico, E.; Baumann, W.; Junge, H.; Beller, M. Iridium–PNP Pincer Complexes for Methanol Dehydrogenation at Low Base Concentration. ChemCatChem 2017, 9, 1891–1896.
  181. Agapova, A.; Junge, H.; Beller, M. Developing Bicatalytic Cascade Reactions: Ruthenium-catalyzed Hydrogen Generation from Methanol. Chem. A Eur. J. 2019, 25, 9345–9349.
  182. Enthaler, S.; von Langermann, J.; Schmidt, T. Carbon dioxide and formic acid—The couple for environmental-friendly hydrogen storage? Energy Environ. Sci. 2010, 3, 1207.
  183. Eppinger, J.; Huang, K.W. Formic Acid as a Hydrogen Energy Carrier. ACS Energy Lett. 2017, 2, 188–195.
  184. Laurenczy, G.; Dyson, P.J. Homogeneous Catalytic Dehydrogenation of Formic Acid: Progress towards a Hydrogen-Based Economy. J. Braz. Chem. Soc. 2014, 25, 2157–2163.
  185. Treigerman, Z.; Sasson, Y. Further Observations on the Mechanism of Formic Acid Decomposition by Homogeneous Ruthenium Catalyst. ChemistrySelect 2017, 2, 5816–5823.
  186. Müller, K.; Brooks, K.; Autrey, T. Hydrogen Storage in Formic Acid: A Comparison of Process Options. Energy Fuels 2017, 31, 12603–12611.
  187. Mellmann, D.; Sponholz, P.; Junge, H.; Beller, M. Formic acid as a hydrogen storage material-development of homogeneous catalysts for selective hydrogen release. Chem. Soc. Rev. 2016, 45, 3954–3988.
  188. Guan, C.; Pan, Y.; Zhang, T.; Ajitha, M.J.; Huang, K.W. An Update on Formic Acid Dehydrogenation by Homogeneous Catalysis. Chem. Asian J. 2020, 15, 937–946.
  189. Enthaler, S.; Loges, B. The Rise of the Iron Age in Hydrogen Evolution? ChemCatChem 2012, 4, 323–325.
  190. Grasemann, M.; Laurenczy, G. Formic acid as a hydrogen source—Recent developments and future trends. Energy Environ. Sci. 2012, 5, 8171.
  191. Fukuzumi, S.; Yamada, Y.; Suenobu, T.; Ohkubo, K.; Kotani, H. Catalytic mechanisms of hydrogen evolution with homogeneous and heterogeneous catalysts. Energy Environ. Sci. 2011, 4, 2754.
  192. Loges, B.; Boddien, A.; Gärtner, F.; Junge, H.; Beller, M. Catalytic Generation of Hydrogen from Formic acid and its Derivatives: Useful Hydrogen Storage Materials. Top. Catal. 2010, 53, 902–914.
  193. Fukuzumi, S. Bioinspired Energy Conversion Systems for Hydrogen Production and Storage. Eur. J. Inorg. Chem. 2008, 2008, 1351–1362.
  194. Langer, R.; Iron, M.A.; Konstantinovski, L.; Diskin-Posner, Y.; Leitus, G.; Ben-David, Y.; Milstein, D. Iron borohydride pincer complexes for the efficient hydrogenation of ketones under mild, base-free conditions: Synthesis and mechanistic insight. Chem. A Eur. J. 2012, 18, 7196–7209.
  195. Zhang, J.; Leitus, G.; Ben-David, Y.; Milstein, D. Efficient homogeneous catalytic hydrogenation of esters to alcohols. Angew. Chem. Int. Ed. 2006, 45, 1113–1115.
  196. Langer, R.; Diskin-Posner, Y.; Leitus, G.; Shimon, L.J.W.; 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.
  197. Zell, T.; Butschke, B.; Ben-David, Y.; Milstein, D. Efficient hydrogen liberation from formic acid catalyzed by a well-defined iron pincer complex under mild conditions. Chem. A Eur. J. 2013, 19, 8068–8072.
  198. Baratta, W.; Ballico, M.; Chelucci, G.; Siega, K.; Rigo, P. Osmium(II) CNN pincer complexes as efficient catalysts for both asymmetric transfer and H2 hydrogenation of ketones. Angew. Chem. Int. Ed. 2008, 47, 4362–4365.
  199. Abdur-Rashid, K.; Clapham, S.E.; Hadzovic, A.; Harvey, J.N.; Lough, A.J.; Morris, R.H. Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium(II) complexes. J. Am. Chem. Soc. 2002, 124, 15104–15118.
  200. Abdur-Rashid, K.; Faatz, M.; Lough, A.J.; Morris, R.H. Catalytic cycle for the asymmetric hydrogenation of prochiral ketones to chiral alcohols: Direct hydride and proton transfer from chiral catalysts trans-Ru(H)2(diphosphine)(diamine) to ketones and direct addition of dihydrogen to the resulting hydridoamid. J. Am. Chem. Soc. 2001, 123, 7473–7474.
  201. Rautenstrauch, V.; Hoang-Cong, X.; Churlaud, R.; Abdur-Rashid, K.; Morris, R.H. Hydrogenation versus Transfer Hydrogenation of Ketones: Two Established Ruthenium Systems Catalyze Both. Chem. A Eur. J. 2003, 9, 4954–4967.
  202. Raja, M.U.; Ramesh, R.; Ahn, K.H. Rhodium(III) NCN pincer complexes catalyzed transfer hydrogenation of ketones. Tetrahedron Lett. 2009, 50, 7014–7017.
  203. Hou, C.; Li, Y.; Zhao, C.; Ke, Z. A DFT study of Co(i) and Ni(ii) pincer complex-catalyzed hydrogenation of ketones: Intriguing mechanism dichotomy by ligand field variation. Catal. Sci. Technol. 2019, 9, 125–135.
  204. Spasyuk, D.; Gusev, D.G. Acceptorless dehydrogenative coupling of ethanol and hydrogenation of esters and imines. Organometallics 2012, 31, 5239–5242.
  205. Chen, T.; Li, H.; Qu, S.; Zheng, B.; He, L.; Lai, Z.; Wang, Z.X.; Huang, K.W. Hydrogenation of esters catalyzed by ruthenium PN3-Pincer complexes containing an aminophosphine arm. Organometallics 2014, 33, 4152–4155.
  206. Filonenko, G.A.; Cosimi, E.; Lefort, L.; Conley, M.P.; Copéret, C.; Lutz, M.; Hensen, E.J.M.; Pidko, E.A. Lutidine-derived Ru-CNC hydrogenation pincer catalysts with versatile coordination properties. ACS Catal. 2014, 4, 2667–2671.
  207. Saudan, L.A.; Saudan, C.M.; Debieux, C.; Wyss, P. Dihydrogen reduction of carboxylic esters to alcohols under the catalysis of homogeneous ruthenium complexes: High efficiency and unprecedented chemoselectivity. Angew. Chem. Int. Ed. 2007, 46, 7473–7476.
  208. Yuwen, J.; Chakraborty, S.; Brennessel, W.W.; Jones, W.D. Additive-Free Cobalt-Catalyzed Hydrogenation of Esters to Alcohols. ACS Catal. 2017, 7, 3735–3740.
  209. Kim, D.; Le, L.; Drance, M.J.; Jensen, K.H.; Bogdanovski, K.; Cervarich, T.N.; Barnard, M.G.; Pudalov, N.J.; Knapp, S.M.M.; Chianese, A.R. Ester Hydrogenation Catalyzed by CNN-Pincer Complexes of Ruthenium. Organometallics 2016, 35, 982–989.
  210. Le, L.; Liu, J.; He, T.; Malek, J.C.; Cervarich, T.N.; Buttner, J.C.; Pham, J.; Keith, J.M.; Chianese, A.R. Unexpected CNN-to-CC Ligand Rearrangement in Pincer–Ruthenium Precatalysts Leads to a Base-Free Catalyst for Ester Hydrogenation. Organometallics 2019, 38, 3311–3321.
  211. Filonenko, G.A.; Aguila, M.J.B.; Schulpen, E.N.; Van Putten, R.; Wiecko, J.; Müller, C.; Lefort, L.; Hensen, E.J.M.; Pidko, E.A. Bis-N-heterocyclic Carbene Aminopincer Ligands Enable High Activity in Ru-Catalyzed Ester Hydrogenation. J. Am. Chem. Soc. 2015, 137, 7620–7623.
  212. He, T.; Buttner, J.C.; Reynolds, E.F.; Pham, J.; Malek, J.C.; Keith, J.M.; Chianese, A.R. Dehydroalkylative Activation of CNN- A nd PNN-Pincer Ruthenium Catalysts for Ester Hydrogenation. J. Am. Chem. Soc. 2019, 141, 17404–17413.
  213. Acosta-Ramirez, A.; Bertoli, M.; Gusev, D.G.; Schlaf, M. Homogeneous catalytic hydrogenation of long-chain esters by an osmium pincer complex and its potential application in the direct conversion of triglycerides into fatty alcohols. Green Chem. 2012, 14, 1178.
  214. Chakraborty, S.; Dai, H.; Bhattacharya, P.; Fairweather, N.T.; Gibson, M.S.; Krause, J.A.; Guan, H. Iron-Based Catalysts for the Hydrogenation of Esters to Alcohols. J. Am. Chem. Soc. 2014, 136, 7869–7872.
  215. Werkmeister, S.; Junge, K.; Wendt, B.; Alberico, E.; Jiao, H.; Baumann, W.; Junge, H.; Gallou, F.; Beller, M. Hydrogenation of esters to alcohols with a well-defined iron complex. Angew. Chem. Int. Ed. 2014, 53, 8722–8726.
  216. Sun, Y.; Koehler, C.; Tan, R.; Annibale, V.T.; Song, D. Ester hydrogenation catalyzed by Ru-CNN pincer complexes. Chem. Commun. 2011, 47, 8349–8351.
  217. Wang, Z.; Chen, X.; Liu, B.; Liu, Q.B.; Solan, G.A.; Yang, X.; Sun, W.H. Cooperative interplay between a flexible PNN-Ru(II) complex and a NaBH4 additive in the efficient catalytic hydrogenation of esters. Catal. Sci. Technol. 2017, 7, 1297–1304.
  218. Yan, X.; Yang, X. Mechanistic insights into the iridium catalysed hydrogenation of ethyl acetate to ethanol: A DFT study. Dalt. Trans. 2018.
  219. Spasyuk, D.; Vicent, C.; Gusev, D.G. Chemoselective hydrogenation of carbonyl compounds and acceptorless dehydrogenative coupling of alcohols. J. Am. Chem. Soc. 2015, 137, 3743–3746.
  220. Qu, S.; Dai, H.; Dang, Y.; Song, C.; Wang, Z.X.; Guan, H. Computational mechanistic study of Fe-catalyzed hydrogenation of esters to alcohols: Improving catalysis by accelerating precatalyst activation with a lewis base. ACS Catal. 2014, 4, 4377–4388.
  221. Wei, Z.; Jiao, H. Bifunctional Aliphatic PNP Pincer Catalysts for Hydrogenation: Mechanisms and Scope, 1st ed.; Elsevier: Amsterdam, The Netherland, 2019; ISBN 9780128157282.
  222. Hey, D.A.; Reich, R.M.; Baratta, W.; Kühn, F.E. Current advances on ruthenium(II) N-heterocyclic carbenes in hydrogenation reactions. Coord. Chem. Rev. 2018, 374, 114–132.
  223. Elangovan, S.; Topf, C.; Fischer, S.; Jiao, H.; Spannenberg, A.; Baumann, W.; Ludwig, R.; Junge, K.; Beller, M. Selective Catalytic Hydrogenations of Nitriles, Ketones, and Aldehydes by Well-Defined Manganese Pincer Complexes. J. Am. Chem. Soc. 2016, 138, 8809–8814.
  224. Schneck, F.; Assmann, M.; Balmer, M.; Harms, K.; Langer, R. Selective Hydrogenation of Amides to Amines and Alcohols Catalyzed by Improved Iron Pincer Complexes. Organometallics 2016, 35, 1931–1943.
  225. Artús Suàrez, L.; Culakova, Z.; Balcells, D.; Bernskoetter, W.H.; Eisenstein, O.; Goldberg, K.I.; Hazari, N.; Tilset, M.; Nova, A. The Key Role of the Hemiaminal Intermediate in the Iron-Catalyzed Deaminative Hydrogenation of Amides. ACS Catal. 2018, 8, 8751–8762.
  226. Jayarathne, U.; Zhang, Y.; Hazari, N.; Bernskoetter, W.H. Selective Iron-Catalyzed Deaminative Hydrogenation of Amides. Organometallics 2017, 36, 409–416.
  227. Coetzee, J.; Dodds, D.L.; Klankermayer, J.; Brosinski, S.; Leitner, W.; Slawin, A.M.Z.; Cole-Hamilton, D.J. Homogeneous Catalytic Hydrogenation of Amides to Amines. Chem. A Eur. J. 2013, 19, 11039–11050.
  228. Núñez Magro, A.A.; Eastham, G.R.; Cole-Hamilton, D.J. The synthesis of amines by the homogeneous hydrogenation of secondary and primary amides. Chem. Commun. 2007, 30, 3154–3156.
  229. Hernández-Juárez, M.; Vaquero, M.; Álvarez, E.; Salazar, V.; Suárez, A. Hydrogenation of imines catalysed by ruthenium(ii) complexes based on lutidine-derived CNC pincer ligands. Dalt. Trans. 2013, 42, 351–354.
  230. Hernández-Juárez, M.; López-Serrano, J.; Lara, P.; Morales-Cerón, J.P.; Vaquero, M.; Álvarez, E.; Salazar, V.; Suárez, A. Ruthenium(II) complexes containing lutidine-derived pincer CNC ligands: Synthesis, structure, and catalytic hydrogenation of C=N bonds. Chem. A Eur. J. 2015, 21, 7540–7555.
  231. Aresta, M. Carbon Dioxide as Chemical Feedstock; John Wiley & Sons: Hoboken, NJ, USA, 2010; ISBN 9783527324750.
  232. Centi, G.; Perathoner, S. Opportunities and prospects in the chemical recycling of carbon dioxide to fuels. Catal. Today 2009, 148, 191–205.
  233. Gibson, D.H. The organometallic chemistry of carbon dioxide. Chem. Rev. 1996, 96, 2063–2095.
  234. Boot-Handford, M.E.; Abanades, J.C.; Anthony, E.J.; Blunt, M.J.; Brandani, S.; Mac Dowell, N.; Fernández, J.R.; Ferrari, M.-C.; Gross, R.; Hallett, J.P.; et al. Carbon capture and storage update. Energy Environ. Sci. 2014, 7, 130–189.
  235. Goeppert, A.; Czaun, M.; May, R.B.; Prakash, G.K.S.; Olah, G.A.; Narayanan, S.R. Carbon Dioxide Capture from the Air Using a Polyamine Based Regenerable Solid Adsorbent. J. Am. Chem. Soc. 2011, 133, 20164–20167.
  236. Gibbins, J.; Chalmers, H. Carbon capture and storage. Energy Policy 2008, 36, 4317–4322.
  237. Leung, D.Y.C.; Caramanna, G.; Maroto-Valer, M.M. An overview of current status of carbon dioxide capture and storage technologies. Renew. Sustain. Energy Rev. 2014, 39, 426–443.
  238. McCulloch, S.; Keeling, S.; Malischek, R.; Stanley, T. 20 Years of Carbon Capture and Storage; OECD: Paris, France, 2016; ISBN 9789264267800.
  239. Styring, P.; Jansen, D.; de Coninck, H.; Reith, H.; Armstrong, K. Carbon Capture and Utilisation in the Green Economy; Centre for Low Carbon Futures: New York, NY, USA, 2011.
  240. de Coninck, H.; Benson, S.M. Carbon Dioxide Capture and Storage: Issues and Prospects. Annu. Rev. Environ. Resour. 2014, 39, 243–270.
  241. Goeppert, A.; Czaun, M.; Surya Prakash, G.K.; Olah, G.A. Air as the renewable carbon source of the future: An overview of CO2 capture from the atmosphere. Energy Environ. Sci. 2012, 5, 7833.
  242. Cuéllar-Franca, R.M.; Azapagic, A. Carbon capture, storage and utilisation technologies: A critical analysis and comparison of their life cycle environmental impacts. J. CO2 Util. 2015, 9, 82–102.
  243. Takht Ravanchi, M.; Sahebdelfar, S. Carbon dioxide capture and utilization in petrochemical industry: Potentials and challenges. Appl. Petrochem. Res. 2014, 4, 63–77.
  244. von der Assen, N.; Jung, J.; Bardow, A. Life-cycle assessment of carbon dioxide capture and utilization: Avoiding the pitfalls. Energy Environ. Sci. 2013, 6, 2721.
  245. Mac Dowell, N.; Fennell, P.S.; Shah, N.; Maitland, G.C. The role of CO2 capture and utilization in mitigating climate change. Nat. Clim. Chang. 2017, 7, 243–249.
  246. Arakawa, H.; Aresta, M.; Armor, J.N.; Barteau, M.A.; Beckman, E.J.; Bell, A.T.; Bercaw, J.E.; Creutz, C.; Dinjus, E.; Dixon, D.A.; et al. Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities. Chem. Rev. 2001, 101, 953–996.
  247. Behr, A. Carbon Dioxide as an Alternative C1 Synthetic Unit: Activation by Transition-Metal Complexes. Angew. Chem. Int. Ed. Engl. 1988, 27, 661–678.
  248. Qiao, J.; Liu, Y.; Hong, F.; Zhang, J. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 2014, 43, 631–675.
  249. Yin, X.; Moss, J.R. Recent developments in the activation of carbon dioxide by metal complexes. Coord. Chem. Rev. 1999, 181, 27–59.
  250. Sakakura, T.; Choi, J.-C.; Yasuda, H. Transformation of Carbon Dioxide. Chem. Rev. 2007, 107, 2365–2387.
  251. Peters, M.; Köhler, B.; Kuckshinrichs, W.; Leitner, W.; Markewitz, P.; Müller, T.E. Chemical Technologies for Exploiting and Recycling Carbon Dioxide into the Value Chain. ChemSusChem 2011, 4, 1216–1240.
  252. Aresta, M.; Dibenedetto, A. Utilisation of CO2 as a chemical feedstock: Opportunities and challenges. Dalt. Trans. 2007, 2975.
  253. Asinger, F. Methanol—Chemie und Energierohstoff. In Methanol—Chem.-und Energierohstoff; Springer: Berlin/Heidelberg, Germany, 1986.
  254. Leitner, W. Carbon Dioxide as a Raw Material: The Synthesis of Formic Acid and Its Derivatives from CO2. Angew. Chem. Int. Ed. Engl. 1995, 34, 2207–2221.
  255. Leitner, W. The coordination chemistry of carbon dioxide and its relevance for catalysis: A critical survey. Coord. Chem. Rev. 1996, 153, 257–284.
  256. Jessop, P.G.; Ikariya, T.; Noyori, R. Homogeneous Hydrogenation of Carbon Dioxide. Chem. Rev. 1995, 95, 259–272.
  257. Olah, G.A.; Goeppert, A.; Prakash, G.K.S. The “Methanol Economy”: General Aspects. In Beyond Oil and Gas; Wiley: Weinheim, Germany, 2018.
  258. Olah, G.A.; Goeppert, A.; Prakash, G.K.S. Methanol-Based Chemicals, Synthetic Hydrocarbons and Materials. In Beyond Oil and Gas: The Methanol Economy; Wiley: Weinheim, Germany, 2009; pp. 375–386.
  259. Goeppert, A.; Czaun, M.; Jones, J.-P.; Surya Prakash, G.K.; Olah, G.A. Recycling of carbon dioxide to methanol and derived products—Closing the loop. Chem. Soc. Rev. 2014, 43, 7995–8048.
  260. Olah, G.A. Towards Oil Independence Through Renewable Methanol Chemistry. Angew. Chem. Int. Ed. 2013, 52, 104–107.
  261. Malik, K.; Singh, S.; Basu, S.; Verma, A. Electrochemical reduction of CO2 for synthesis of green fuel. Wiley Interdiscip. Rev. Energy Environ. 2017, 6, e244.
  262. Álvarez, A.; Bansode, A.; Urakawa, A.; Bavykina, A.V.; Wezendonk, T.A.; Makkee, M.; Gascon, J.; Kapteijn, F. Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes. Chem. Rev. 2017, 117, 9804–9838.
  263. Behrens, M. Heterogeneous Catalysis of CO2 Conversion to Methanol on Copper Surfaces. Angew. Chem. Int. Ed. 2014, 53, 12022–12024.
  264. Dang, S.; Yang, H.; Gao, P.; Wang, H.; Li, X.; Wei, W.; Sun, Y. A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation. Catal. Today 2019, 330, 61–75.
  265. Eisenstein, O.; Crabtree, R.H. Outer sphere hydrogenation catalysis. New J. Chem. 2013, 37, 21–27.
  266. Yang, X. 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.
  267. Jessop, P.G. Homogeneous Hydrogenation of Carbon Dioxide. In The Handbook of Homogeneous Hydrogenation; WILEY-VCH: Weinheim, Germany, 2007; ISBN 9783527311613.
  268. Wang, W.; Wang, S.; Ma, X.; Gong, J. Recent advances in catalytic hydrogenation of carbon dioxide. Chem. Soc. Rev. 2011, 40, 3703.
  269. Benson, E.E.; Kubiak, C.P.; Sathrum, A.J.; Smieja, J.M. Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels. Chem. Soc. Rev. 2009, 38, 89–99.
  270. Sanz, S.; Azua, A.; Peris, E. ‘(η6-arene)Ru(bis-NHC)’ complexes for the reduction of CO2 to formate with hydrogen and by transfer hydrogenation with iPrOH. Dalt. Trans. 2010, 39, 6339.
  271. Li, X.; He, X.; Liu, X.; He, L.N. Ruthenium-promoted reductive transformation of CO2. Sci. China Chem. 2017, 60, 841–852.
  272. Wiedner, E.S.; Linehan, J.C. Making a Splash in Homogeneous CO2 Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms. Chem. A Eur. J. 2018, 24, 16964–16971.
  273. Janes, T.; Yang, Y.; Song, D. Chemical reduction of CO2 facilitated by C-nucleophiles. Chem. Commun. 2017, 53, 11390–11398.
  274. Jiang, C.; Nichols, A.W.; Machan, C.W. A look at periodic trends in d-block molecular electrocatalysts for CO2 reduction. Dalt. Trans. 2019, 48, 9454–9468.
  275. Fernández-Alvarez, F.J.; Iglesias, M.; Oro, L.A.; Polo, V. CO2 activation and catalysis driven by iridium complexes. ChemCatChem 2013, 5, 3481–3494.
  276. Kang, P.; Chen, Z.; Brookhart, M.; Meyer, T.J. Electrocatalytic Reduction of Carbon Dioxide: Let the Molecules Do the Work. Top. Catal. 2015, 58, 30–45.
  277. Jessop, P.G.; Joó, F.; Tai, C.-C. Recent advances in the homogeneous hydrogenation of carbon dioxide. Coord. Chem. Rev. 2004, 248, 2425–2442.
  278. Badiei, Y.M.; Wang, W.-H.; Hull, J.F.; Szalda, D.J.; Muckerman, J.T.; Himeda, Y.; Fujita, E. Cp*Co(III) Catalysts with Proton-Responsive Ligands for Carbon Dioxide Hydrogenation in Aqueous Media. Inorg. Chem. 2013, 52, 12576–12586.
  279. Jeletic, M.S.; Mock, M.T.; Appel, A.M.; Linehan, J.C. A Cobalt-Based Catalyst for the Hydrogenation of CO2 under Ambient Conditions. J. Am. Chem. Soc. 2013, 135, 11533–11536.
  280. Zhang, G.; Vasudevan, K.V.; Scott, B.L.; Hanson, S.K. Understanding the Mechanisms of Cobalt-Catalyzed Hydrogenation and Dehydrogenation Reactions. J. Am. Chem. Soc. 2013, 135, 8668–8681.
  281. Glüer, A.; Schneider, S. Iron catalyzed hydrogenation and electrochemical reduction of CO2: The role of functional ligands. J. Organomet. Chem. 2018, 861, 159–173.
  282. Jeletic, M.S.; Helm, M.L.; Hulley, E.B.; Mock, M.T.; Appel, A.M.; Linehan, J.C. A Cobalt Hydride Catalyst for the Hydrogenation of CO2: Pathways for Catalysis and Deactivation. ACS Catal. 2014, 4, 3755–3762.
  283. Jeletic, M.S.; Hulley, E.B.; Helm, M.L.; Mock, M.T.; Appel, A.M.; Wiedner, E.S.; Linehan, J.C. Understanding the Relationship Between Kinetics and Thermodynamics in CO2 Hydrogenation Catalysis. ACS Catal. 2017, 7, 6008–6017.
  284. Shaffer, D.W.; Johnson, S.I.; Rheingold, A.L.; Ziller, J.W.; Goddard, W.A.; Nielsen, R.J.; Yang, J.Y. Reactivity of a Series of Isostructural Cobalt Pincer Complexes with CO2, CO, and H+. Inorg. Chem. 2014, 53, 13031–13041.
  285. Hojilla Atienza, C.C.; Milsmann, C.; Semproni, S.P.; Turner, Z.R.; Chirik, P.J. Reversible Carbon–Carbon Bond Formation Induced by Oxidation and Reduction at a Redox-Active Cobalt Complex. Inorg. Chem. 2013, 52, 5403–5417.
  286. Dubey, A.; Nencini, L.; Fayzullin, R.R.; Nervi, C.; Khusnutdinova, J.R. Bio-Inspired Mn(I) Complexes for the Hydrogenation of CO2 to Formate and Formamide. ACS Catal. 2017, 7, 3864–3868.
  287. Federsel, C.; Jackstell, R.; Beller, M. State-of-the-art catalysts for hydrogenation of carbon dioxide. Angew. Chem. Int. Ed. 2010, 49, 6254–6257.
  288. Kar, S.; Goeppert, A.; Prakash, G.K.S. Integrated CO2 Capture and Conversion to Formate and Methanol: Connecting Two Threads. Acc. Chem. Res. 2019, 52, 2892–2903.
  289. Kar, S.; Kothandaraman, J.; Goeppert, A.; Prakash, G.K.S. Advances in catalytic homogeneous hydrogenation of carbon dioxide to methanol. J. CO2 Util. 2018, 23, 212–218.
  290. Munshi, P.; Main, A.D.; Linehan, J.C.; Tai, C.C.; Jessop, P.G. Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes: The accelerating effect of certain alcohols and amines. J. Am. Chem. Soc. 2002, 124, 7963–7971.
  291. Urakawa, A.; Jutz, F.; Laurenczy, G.; Baiker, A. Carbon dioxide hydrogenation catalyzed by a ruthenium dihydride: A DFT and high-pressure spectroscopic investigation. Chem. A Eur. J. 2007, 13, 3886–3899.
  292. Jessop, P.G.; Hsiao, Y.; Ikariya, T.; Noyori, R. Homogeneous Catalysis in Supercritical Fluids: Hydrogenation of Supercritical Carbon Dioxide to Formic Acid, Alkyl Formates, and Formamides. J. Am. Chem. Soc. 1996, 118, 344–355.
  293. Jessop, P.G.; Ikariya, T.; Noyori, R. Homogeneous catalytic hydrogenation of supercritical carbon dioxide. Nature 1994, 368, 231–233.
  294. Graf, E.; Leitner, W. Direct formation of formic acid from carbon dioxide and dihydrogen using the –Ph2P(CH2)4PPh2 catalyst system. J. Chem. Soc., Chem. Commun. 1992, 623–624.
  295. Gassner, F.; Leitner, W. Hydrogenation of carbon dioxide to formic acid using water-soluble rhodium catalyststs. J. Chem. Soc. Chem. Commun. 1993, 1465.
  296. Angermund, K.; Baumann, W.; Dinjus, E.; Fornika, R.; Görls, H.; Kessler, M.; Krüger, C.; Leitner, W.; Lutz, F. Complexes as Model Compounds for the Fragment and as Highly Active Catalysts for CO2 Hydrogenation: The Accessible Molecular Surface (AMS) Model as an Approach to Quantifying the Intrinsic Steric Properties of Chelating Ligands i. Chem. A Eur. J. 1997, 3, 755–764.
  297. Himeda, Y.; Onozawa-Komatsuzaki, N.; Sugihara, H.; Kasuga, K. Simultaneous tuning of activity and water solubility of complex catalysts by acid-base equilibrium of ligands for conversion of carbon dioxide. Organometallics 2007, 26, 702–712.
  298. Balaraman, E.; Gunanathan, C.; Zhang, J.; Shimon, L.J.W.; Milstein, D. Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO. Nat. Chem. 2011, 3, 609–614.
  299. Huff, C.A.; Sanford, M.S. Cascade catalysis for the homogeneous hydrogenation of CO2 to methanol. J. Am. Chem. Soc. 2011, 133, 18122–18125.
  300. Ostapowicz, T.G.; Hölscher, M.; Leitner, W. CO2 insertion into metal-carbon bonds: A computational study of RhI pincer complexes. Chem. A Eur. J. 2011, 17, 10329–10338.
  301. Wesselbaum, S.; Moha, V.; Meuresch, M.; Brosinski, S.; Thenert, K.M.; Kothe, J.; vom Stein, T.; Englert, U.; Hölscher, M.; Klankermayer, J.; et al. Hydrogenation of carbon dioxide to methanol using a homogeneous ruthenium-Triphos catalyst: From mechanistic investigations to multiphase catalysis. Chem. Sci. 2015, 6, 693–704.
  302. Hull, J.F.; Himeda, Y.; Wang, W.-H.; Hashiguchi, B.; Periana, R.; Szalda, D.J.; Muckerman, J.T.; Fujita, E. Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures. Nat. Chem. 2012, 4, 383–388.
  303. Sordakis, K.; Tsurusaki, A.; Iguchi, M.; Kawanami, H.; Himeda, Y.; Laurenczy, G. Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature. Chem. A Eur. J. 2016, 22, 15605–15608.
  304. Rezayee, N.M.; Huff, C.A.; Sanford, M.S. Tandem amine and ruthenium-catalyzed hydrogenation of CO2 to methanol. J. Am. Chem. Soc. 2015, 137, 1028–1031.
  305. Khusnutdinova, J.R.; Garg, J.A.; Milstein, D. Combining Low-Pressure CO2 Capture and Hydrogenation to Form Methanol. ACS Catal. 2015, 5, 2416–2422.
  306. Kothandaraman, J.; Goeppert, A.; Czaun, M.; Olah, G.A.; Prakash, G.K.S. Conversion of CO2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst. J. Am. Chem. Soc. 2016, 138, 778–781.
  307. Kar, S.; Sen, R.; Goeppert, A.; Prakash, G.K.S. Integrative CO2 Capture and hydrogenation to methanol with reusable catalyst and amine: Toward a carbon neutral methanol economy. J. Am. Chem. Soc. 2018, 140, 1580–1583.
  308. Bielinski, E.A.; Lagaditis, P.O.; Zhang, Y.; Mercado, B.Q.; Würtele, C.; Bernskoetter, W.H.; Hazari, N.; Schneider, S. Lewis acid-assisted formic acid dehydrogenation using a pincer-supported iron catalyst. J. Am. Chem. Soc. 2014, 136, 10234–10237.
  309. Zhang, Y.; MacIntosh, A.D.; Wong, J.L.; Bielinski, E.A.; Williard, P.G.; Mercado, B.Q.; Hazari, N.; Bernskoetter, W.H. Iron catalyzed CO2 hydrogenation to formate enhanced by Lewis acid co-catalysts. Chem. Sci. 2015, 6, 4291–4299.
  310. Bernskoetter, W.H.; Hazari, N. Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts. Acc. Chem. Res. 2017, 50, 1049–1058.
  311. Spentzos, A.Z.; Barnes, C.L.; Bernskoetter, W.H. Effective Pincer Cobalt Precatalysts for Lewis Acid Assisted CO2 Hydrogenation. Inorg. Chem. 2016, 55, 8225–8233.
More
Information
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register : , ,
View Times: 1.0K
Entry Collection: Organic Synthesis
Revisions: 4 times (View History)
Update Date: 08 Apr 2022
1000/1000
Video Production Service