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Metal carbon dioxide complex

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Metal carbon dioxide complexes are coordination complexes that contain carbon dioxide ligands. Aside from the fundamental interest in the coordination chemistry of simple molecules, studies in this field are motivated by the possibility that transition metals might catalyze useful transformations of CO2. This research is relevant both to organic synthesis and to the production of "solar fuels" that would avoid the use of petroleum-based fuels.[1]

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Illustrative structures of transition metal carbon dioxide complexes, from the left: Ni(η2-CO2)(PCy3)2, Rh(η1-CO2)ClL4 (L4 = (diars)2), the metallacarboxylic ester CpFe(CO)2(η1:η1-CO2)Re(CO)5, and another dimetalla-ester.

Carbon dioxide binds to metals in only a few ways. The bonding mode depends on the electrophilicity and basicity of the metal centre.[2] Most common is the η2-CO2 coordination mode as illustrated by Aresta's complex, Ni(CO2)(PCy3)2, which was the first reported complex of CO2.[3][4] This square-planar compound is a derivative of Ni(II) with a reduced CO2 ligand. In rare cases, CO2 binds to metals as a Lewis base through its oxygen centres, but such adducts are weak and mainly of theoretical interest. A variety of multinuclear complexes are also known often involving Lewis basic and Lewis acidic metals, e.g. metallacarboxylate salts (C5H5)Fe(CO)2CO2−K+. In multinuclear cases (compounds containing more than one metal), more complicated and more varied coordination geometries are observed. One example is the unsymmetrical compound containing four rhenium centres, [(CO)5ReCO2Re(CO)4]2.[citation needed] Carbon dioxide can also bind to ligands on a metal complex (vs just the metal), e.g. by converting hydroxy ligands to carbonato ligands.[citation needed]

Reactions

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Transition metal carbon dioxide complexes undergo a variety of reactions. Metallacarboxylic acids protonate at oxygen and eventually convert to metal carbonyl complexes:

[LnMCO2]− + 2 H+ → [LnMCO]+ + H2O

This reaction is relevant to the potential catalytic conversion of CO2 to fuels.[5]

Carbonation of metal-carbon bonds

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Insertion into Cu-C bonds

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N-heterocyclic carbene (NHC) supported CuI complexes catalyze carboxylation of organoboronic esters.[6] The catalyst forms in situ from CuCl, an NHC ligand, and KOtBu. Copper tert-butoxide can transmetallate with the organoboronic ester to generate the CuI-C bond, which intermediate can insert into CO2 smoothly to get the respective carboxylate. Salt metathesis with KOtBu releases product and regenerates catalyst (Scheme 2).

Scheme 2 Copper catalyzed carboxylation of organoboronic ester
Scheme 2 Copper catalyzed carboxylation of organoboronic ester

Apart from transmetallation, there are other approaches forming Cu-C bond. C-H functionalization is a straightforward and atom economic method. Base can help deprotonate acidic C-H protons and form Cu-C bond. [(Phenanthroline)Cu(PR3)] catalyst effect C-H carboxylation on terminal alkynes together with Cs2CO3.[7] NHC-Cu-H species to deprotonate acidic proton to effect carboxylation of terminal alkynes.[8] Cu-H species were generated from Cu-F and organosilanes. The carboxylate product was trapped by silyl fluoride to get silyl ether. For non-acidic C-H bonds, directed metalation with iBu3Al(TMP)Li is adopted followed by transmetallation with copper to get Cu-C bond. Allylic C-H bonds and phenyl C-H bonds got carboxylated with this approach by Hou and co-workers:[9][10]

Scheme 3 Copper catalysed boracarboxylation of internal alkynes
Scheme 3 Copper catalysed boracarboxylation of internal alkynes

Carbometallation to alkynes and allenes using organozinc and organoaluminum reagents followed by transmetallation to copper is also a strategy to initiate carboxylation. Trimethylaluminium is able to insert into unbiased aliphatic internal alkynes with syn fashion directed by ether directing group. Vinyl copper complexes are formed by transmetallation and carboxylation is realized with a similar pathway giving tetrasubstituted aliphatic vinyl carboxylic acids.[11] In this case, regioslectivity is controlled by the favor of six-membered aluminum ring formation. Furthermore, carboxylation can be achieved on ynamides and allenamides using less reactive dimethyl zinc via similar approach.[12][13]

Insertion in Pd-C bonds

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In the presence of palladium acetate under 1-30 bar of CO2, simple aromatic compounds convert to aromatic carboxylic acids.[14][15][16][17][18] A PSiP-pincer ligand (5) promotes carboxylation of allene without using pre-functionalized substrates.[19] Catalyst regeneration, Et3Al was added to do transmetallation with palladium. Catalyst is regenerated by the following β-H elimination. Apart from terminal allenes, some of internal allenes are also tolerated in this reaction, generating allyl carboxylic acid with the yield between 54% and 95%. This system was also applied to 1,3-diene, generating carboxylic acid in 1,2 addition fashion.[20] In 2015, Iwasawa et al. reported the germanium analogue (6) and combined CO2 source together with hydride source to formate salts.[21]

Scheme 4 Pincer Pd complexes for catalytic carboxylation
Scheme 4 Pincer Pd complexes for catalytic carboxylation

Palladium has shown huge power to catalyze C-H functionalization. If the Pd-C intermediate in carboxylation reaction comes from C-H activation, such methodology must promote metal catalyzed carboxylation to a much higher level in utility. Iwasawa and co-workers reported direct carboxylation by styrenyl C-H activation generating coumarin derivatives.[22] Benzene rings with different electronic properties and some heteroaromatic rings are tolerated in this reaction with yield from 50% to 90%. C-H activation was demonstrated by crystallography study.

Insertion by Rh-C bonds

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Similar to Cu(I) chemistry mentioned above, Rh(I) complexes can also transmetallate with arylboronic esters to get aryl rhodium intermediates, to which CO2 is inserted giving carboxylic acids.[23] Later, Iwasawa et al. described C-H carboxylation strategy. Rh(I) undergoes oxidative addition to aryl C-H bond followed by transmetallation with alkyl aluminum species. Ar-Rh(I) regenerates by reductive elimination releasing methane. Ar-Rh(I) attacks CO2 then transmetallates with aryl boronic acid to release the boronic acid of product, giving final carboxylic acid by hydrolysis. Directed and non-directed versions are both achieved.[24][25][26]

Iwasawa and co-workers developed Rh(I) catalyzed carbonation reaction initiated by Rh-H insertion to vinylarenes. In order to regenerate reactive Rh-H after nucleophilic addition to CO2, photocatalytic proton-coupled electron transfer approach was adopted.[27] In this system, excess amount of diethylpropylethylamine works as sacrificial electron donor (Scheme 5).

Photocatalyzed carboxylation
Photocatalyzed carboxylation

Insertion by Ni-C bond

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Carboxylation of benzyl halides has been reported.[28] The reaction mechanism is proposed to involve oxidative addition of benzyl chloride to Ni(0). The Ni(II) benzyl complex is reduced to Ni(I), e.g., by zinc, which inserts CO2 delivering the nickel carboxylate. Reduction of the Ni(I) carboxylate to Ni(0) releases the zinc carboxylate (Scheme 6). Similarly, such carboxylation has been achieved on aryl and benzyl pivalate,[29] alkyl halides,[30][31] and allyl esters.[32]

Scheme 6 Nickel catalysed carboxylation of benzyl halides
Scheme 6 Nickel catalysed carboxylation of benzyl halides

References

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  1. ^ "Carbon Dioxide as Chemical Feedstock" Edited by Michele Aresta. Wiley-VCH, Weinheim, 2010. ISBN 978-3-527-32475-0.
  2. ^ Gibson, Dorothy H. (1996). "The Organometallic Chemistry Carbon Dioxide". Chem. Rev. 96 (6): 2063–2095. doi:10.1021/cr940212c. PMID 11848822.
  3. ^ Aresta, Michele; Gobetto, Roberto; Quaranta, Eugenio; Tommasi, Immacolata (October 1992). "A bonding-reactivity relationship for (carbon dioxide)bis(tricyclohexylphosphine)nickel: a comparative solid-state-solution nuclear magnetic resonance study (phosphorus-31, carbon-13) as a diagnostic tool to determine the mode of bonding of carbon dioxide to a metal center". Inorganic Chemistry. 31 (21): 4286–4290. doi:10.1021/ic00047a015.
  4. ^ Yeung, Charles S.; Dong, Vy M. (June 2008). "Beyond Aresta's Complex: Ni- and Pd-Catalyzed Organozinc Coupling with CO". Journal of the American Chemical Society. 130 (25): 7826–7827. doi:10.1021/ja803435w. PMID 18510323.
  5. ^ Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J.; Smieja, Jonathan M. (2009). "Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels". Chem. Soc. Rev. 38 (1): 89–99. doi:10.1039/b804323j. PMID 19088968.
  6. ^ Ohishi, Takeshi; Nishiura, Masayoshi; Hou, Zhaomin (21 July 2008). "Carboxylation of Organoboronic Esters Catalyzed by N‐Heterocyclic Carbene Copper(I) Complexes". Angewandte Chemie International Edition. 47 (31): 5792–5795. doi:10.1002/anie.200801857. PMID 18576463.
  7. ^ Gooßen, Lukas J.; Rodríguez, Nuria; Manjolinho, Filipe; Lange, Paul P. (22 November 2010). "Synthesis of Propiolic Acids via Copper-Catalyzed Insertion of Carbon Dioxide into the C-H Bond of Terminal Alkynes". Advanced Synthesis & Catalysis. 352 (17): 2913–2917. doi:10.1002/adsc.201000564.
  8. ^ Fujihara, Tetsuaki; Xu, Tinghua; Semba, Kazuhiko; Terao, Jun; Tsuji, Yasushi (10 January 2011). "Copper-Catalyzed Hydrocarboxylation of Alkynes Using Carbon Dioxide and Hydrosilanes". Angewandte Chemie International Edition. 50 (2): 523–527. doi:10.1002/anie.201006292. PMID 21157832.
  9. ^ Ueno, Atsushi; Takimoto, Masanori; O, Wylie W. N.; Nishiura, Masayoshi; Ikariya, Takao; Hou, Zhaomin (April 2015). "Copper-Catalyzed Formal C-H Carboxylation of Aromatic Compounds with Carbon Dioxide through Arylaluminum Intermediates". Chemistry: An Asian Journal. 10 (4): 1010–1016. doi:10.1002/asia.201403247. PMID 25491488.
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  12. ^ Gholap, Sandeep Suryabhan; Takimoto, Masanori; Hou, Zhaomin (13 June 2016). "Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N-Heterocyclic Carbene-Copper Complex". Chemistry: A European Journal. 22 (25): 8547–8552. doi:10.1002/chem.201601162. PMID 27167688.
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  14. ^ Sugimoto, Hiroshi; Kawata, Itaru; Taniguchi, Hiroshi; Fujiwara, Yuzo (May 1984). "Preliminary communication: Palladium-Catalyzed Carboxylation of Aromatic-Compounds with Carbon-Dioxide". Journal of Organometallic Chemistry. 266 (3): c44–c46. doi:10.1016/0022-328X(84)80150-3.
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  16. ^ Johansson, Roger; Jarenmark, Martin; Wendt, Ola F. (September 2005). "Insertion of Carbon Dioxide into (PCP)Pd-II-Me bonds". Organometallics. 24 (19): 4500–4502. doi:10.1021/om0505561.
  17. ^ Johansson, Roger; Wendt, Ola F. (2007). "Insertion of CO2 into a palladium allyl bond and a Pd(II) catalysed carboxylation of allyl stannanes". Dalton Trans. (4): 488–492. doi:10.1039/B614037H. PMID 17213935.
  18. ^ Johnson, Magnus T.; Johansson, Roger; Kondrashov, Mikhail V.; Steyl, Gideon; Ahlquist, Mårten S. G.; Roodt, Andreas; Wendt, Ola F. (23 August 2010). "=Mechanisms of the CO2 Insertion into (PCP) Palladium Allyl and Methyl sigma-Bonds. A Kinetic and Computational Study". Organometallics. 29 (16): 3521–3529. doi:10.1021/om100325v.
  19. ^ Takaya, Jun; Iwasawa, Nobuharu (19 November 2008). "Hydrocarboxylation of Allenes with CO2 Catalyzed by Silyl Pincer-Type Palladium Complex". Journal of the American Chemical Society. 130 (46): 15254–15255. doi:10.1021/ja806677w. PMID 18942785.
  20. ^ Takaya, Jun; Sasano, Kota; Iwasawa, Nobuharu (April 2011). "Efficient One-to-One Coupling of Easily Available 1,3-Dienes with Carbon Dioxide". Organic Letters. 13 (7): 1698–1701. doi:10.1021/ol2002094. PMID 21370864.
  21. ^ Zhu, Chuan; Takaya, Jun; Iwasawa, Nobuharu (3 April 2015). "Use of formate salts as a hydride and a co2 source in PGeP-palladium complex-catalyzed hydrocarboxylation of allenes". Organic Letters. 17 (7): 1814–1817. doi:10.1021/acs.orglett.5b00692. PMID 25794110.
  22. ^ Sasano, Kota; Takaya, Jun; Iwasawa, Nobuharu (31 July 2013). "Palladium(II)-Catalyzed Direct Carboxylation of Alkenyl C–H Bonds with CO2". Journal of the American Chemical Society. 135 (30): 10954–10957. doi:10.1021/ja405503y. PMID 23865901.
  23. ^ Ukai, Kazutoshi; Aoki, Masao; Takaya, Jun; Iwasawa, Nobuharu (2006-07-01). "Rhodium(I)-Catalyzed Carboxylation of Aryl- and Alkenylboronic Esters with CO2". Journal of the American Chemical Society. 128 (27): 8706–8707. doi:10.1021/ja061232m. ISSN 0002-7863. PMID 16819845.
  24. ^ Mizuno, Hajime; Takaya, Jun; Iwasawa, Nobuharu (2011-02-09). "Rhodium(I)-Catalyzed Direct Carboxylation of Arenes with CO2 via Chelation-Assisted C−H Bond Activation". Journal of the American Chemical Society. 133 (5): 1251–1253. doi:10.1021/ja109097z. ISSN 0002-7863. PMID 21192682.
  25. ^ Suga, Takuya; Mizuno, Hajime; Takaya, Jun; Iwasawa, Nobuharu (2014-10-23). "Direct carboxylation of simple arenes with CO2 through a rhodium-catalyzed C–H bond activation". Chemical Communications. 50 (92): 14360–14363. doi:10.1039/C4CC06188H. ISSN 1364-548X. PMID 25296263.
  26. ^ Suga, Takuya; Saitou, Takanobu; Takaya, Jun; Iwasawa, Nobuharu (2017-01-30). "Mechanistic study of the rhodium-catalyzed carboxylation of simple aromatic compounds with carbon dioxide". Chemical Science. 8 (2): 1454–1462. doi:10.1039/C6SC03838G. ISSN 2041-6539. PMC 5460598. PMID 28616144.
  27. ^ Murata, Kei; Numasawa, Nobutsugu; Shimomaki, Katsuya; Takaya, Jun; Iwasawa, Nobuharu (2017-03-09). "Construction of a visible light-driven hydrocarboxylation cycle of alkenes by the combined use of Rh(I) and photoredox catalysts". Chemical Communications. 53 (21): 3098–3101. doi:10.1039/C7CC00678K. ISSN 1364-548X. PMID 28243662.
  28. ^ León, Thierry; Correa, Arkaitz; Martin, Ruben (2013-01-30). "Ni-Catalyzed Direct Carboxylation of Benzyl Halides with CO2". Journal of the American Chemical Society. 135 (4): 1221–1224. doi:10.1021/ja311045f. ISSN 0002-7863. PMID 23301781.
  29. ^ Correa, Arkaitz; León, Thierry; Martin, Ruben (2014-01-22). "Ni-Catalyzed Carboxylation of C(sp2)– and C(sp3)–O Bonds with CO2". Journal of the American Chemical Society. 136 (3): 1062–1069. doi:10.1021/ja410883p. hdl:2072/305833. ISSN 0002-7863. PMID 24377699.
  30. ^ Liu, Yu; Cornella, Josep; Martin, Ruben (2014-08-13). "Ni-Catalyzed Carboxylation of Unactivated Primary Alkyl Bromides and Sulfonates with CO2" (PDF). Journal of the American Chemical Society. 136 (32): 11212–11215. doi:10.1021/ja5064586. hdl:2072/305831. ISSN 0002-7863. PMID 25068174.
  31. ^ Börjesson, Marino; Moragas, Toni; Martin, Ruben (2016-06-22). "Ni-Catalyzed Carboxylation of Unactivated Alkyl Chlorides with CO2". Journal of the American Chemical Society. 138 (24): 7504–7507. doi:10.1021/jacs.6b04088. hdl:2072/305936. ISSN 0002-7863. PMID 27269443.
  32. ^ Moragas, Toni; Cornella, Josep; Martin, Ruben (2014-12-24). "Ligand-Controlled Regiodivergent Ni-Catalyzed Reductive Carboxylation of Allyl Esters with CO2". Journal of the American Chemical Society. 136 (51): 17702–17705. doi:10.1021/ja509077a. hdl:2072/305832. ISSN 0002-7863. PMID 25473825.
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