Diatomic carbon (C2) is historically an elusive chemical species. It has long been believed that the generation of C2 requires extremely high physical energy, such as an electric carbon arc or multiple photon excitation, and so it has been the general consensus that the inherent nature of C2 in the ground state is experimentally inaccessible. Here, we present the chemical synthesis of C2 from a hypervalent alkynyl-λ3-iodane in a flask at room temperature or below, providing experimental evidence to support theoretical predictions that C2 has a singlet biradical character with a quadruple bond, thus settling a long-standing controversy between experimental and theoretical chemists, and that C2 serves as a molecular element in the bottom-up chemical synthesis of nanocarbons such as graphite, carbon nanotubes, and C60.
Diatomic carbon (C2) exists in carbon vapor, comets, the stellar atmosphere, and interstellar matter, but although it was discovered in 18571, it has proven frustratingly difficult to characterize, since C2 gas occurs only at extremely high temperatures (above 3500 °C)2. Considerable efforts have been made to generate/capture C2 experimentally and to measure its physicochemical properties. The first successful example of artificial generation of C2, which was confirmed spectroscopically, involved the use of an electric carbon arc under high vacuum conditions3. Subsequent chemical trapping studies pioneered by Skell indicated that C2 behaves as a mixture of singlet dicarbene and triplet biradical states in a ratio of 7:3 to 8:2 (Fig. 1a)4,5,6,7. Multiple photon dissociation of two-carbon small molecules (acetylene, ethylene, tetrabromoethylene, etc.) by infrared or UV irradiation in the gas phase was also developed to generate C2, but this photo-generated C2 also exhibited several electronic states8. Recently, other approaches for the isolation of C2 have been reported, using potent electron-donating ligands to stabilize C2 by means of dative interactions (L:→C2←:L), but such stabilized complexes no longer retain the original character of C2 (Fig. 1b)9,10,11,12. Instead, theoretical/computational simulation has been applied recently, and the results indicated that C2 has a quadruple bond with a singlet biradical character in the ground state13,14.
These various theoretical and experimental findings have sparked extensive debate on the molecular bond order and electronic state of C2 in the scientific literature, probably because of the lack of a method for the synthesis of ground-state C2. Here, we present a straightforward room-temperature/pressure synthesis of C2 in a flask. We show that C2 generated under these conditions behaves exclusively as a singlet biradical with quadruple bonding, as predicted by theory. We also show that spontaneous, solvent-free reaction of in situ generated C2 under an argon atmosphere results in the formation of graphite, carbon nanotubes (CNTs), and fullerene (C60) at room temperature. This not only represents a bottom-up chemical synthesis of nanocarbons at ordinary temperature and pressure, but it also provides experimental evidence that C2 may serve as a key intermediate in the formation of various carbon allotropes (Fig. 1c).
Chemical synthesis of C2
The key strategy underlying the present achievement is the use of hypervalent iodane chemistry15,16,17, aiming to utilize the phenyl-λ3-iodanyl moiety as a hyper-leaving group (ca. 106 times greater leaving ability than triflate (–OSO2CF3), a so-called super-leaving group)18. We designed [β-(trimethylsilyl)ethynyl](phenyl)-λ3-iodane 1a19, in the expectation that it would generate C2 upon desilylation of 1a with fluoride ion to form anionic ethynyl-λ3-iodane 11, followed by facile reductive elimination of iodobenzene. Gratifyingly, exposure of 1a to 1.2 equivalents of tetra-n-butylammonium fluoride (Bu4NF) in dichloromethane resulted in smooth decomposition at −30 °C with the formation of acetylene and iodobenzene, indicating the generation of C2! However, all attempts to capture C2 with a range of ketones and olefins, such as acetone (3), 1,3,5,7-cyclooctatetraene (4), styrene (7), and 1,3,5-cycloheptatriene, failed, though they smoothly reacted with arc-generated C2 on an argon matrix at −196 °C3,4,5,20. These findings immediately suggested that the putative C2 synthesized here at −30 °C has a significantly different character from C2 generated under high-energy conditions (Supplementary Fig. 1).
Experimental evidence for singlet biradical character
Taking account of the fact that quantum chemical calculations suggest a relatively stable singlet biradical C2 with quadruple bonding in the ground state, we next examined an excellent hydrogen donor. 9,10-Dihydroanthracene has very weak C–H bonds (bond dissociation energy of 12: 76.3 kcal mol−1 vs CH2Cl2: 97.3 kcal mol−1)21,22 that might effectively trap the putative singlet biradical C2. When 12 was added to the reaction mixture, anthracene (13) was obtained accompanied with the formation of acetylene (Fig. 2a), which clearly suggests that the generation of C2 and subsequent hydrogen abstraction from 12 gave acetylene. The formation of acetylene was confirmed by Raman spectroscopy after AgNO3 trapping, and the amount of acetylene was estimated by the quantitative analysis of Ag2C2 thus generated (Supplementary Fig. 2). These results strongly support the relatively stable (singlet) biradical nature of our C2, in accordance with the theoretical calculations. Thus, we turned our attention to the galvinoxyl free (stable) radical 14 in order to trap C2 directly. To our delight, O-ethynyl ether 15 was obtained in 14% yield, accompanied with the formation of acetylene (84%) (Fig. 2b). The structure of 15 was fully characterized by 1H/13C NMR spectra: an upfield-shifted acetylenic proton was seen at 1.78 ppm in the 1H NMR, as well as considerably separated 13C NMR chemical shifts of two acetylenic carbons (Cα: 90.4 ppm and Cβ: 30.0 ppm), clearly indicating the presence of an ethynyl ether unit (e.g., ethynyl ethyl ether, Cα: δ 88.2 ppm; Cβ: δ 22.0 ppm)23. In solution, di-galvinoxyl alkyne 16 was undetectable or barely detectable even when excess amounts of 14 were used, though 15 was obtained as almost the sole product in all cases. On the other hand, when we performed the trapping reaction in the presence of two equivalents of 14 under solvent-free conditions, 16 was clearly observed by atmospheric pressure chemical ionization (APCI) mass spectrometry (MS), although in very small quantity (Supplementary Fig. 3)24. These findings are consistent with the valence bond model of a singlet biradical species, according to which the energy barrier of the second hydrogen abstraction is lower by approximately 10 kcal/mol compared with the first hydrogen abstraction, which has to overcome the bonding energy of the singlet biradical25,26. It should be noted that the O-phenylated product was not formed at all, excluding alternative single electron transfer pathways, such as those via ethynyl(phenyl)-λ2-iodanyl radical (Supplementary Fig. 4)27.
In order to obtain more direct information about the generation of C2 “gas,” we designed a connected-flask, solvent-free experiment (Fig. 2c): a solvent-free chemical synthesis of C2 using 1a with three equivalents of CsF was carried out in one of a pair of connected flasks (Flask A), and three equivalents of 14 was placed in the other flask (Flask B). The reaction mixture in Flask A was vigorously stirred at room temperature for 72 h under argon. As the reaction proceeds in Flask A, generated C2 gas should pass from Flask A to Flask B. Indeed, the color of 14 in Flask B gradually changed from deep purple to deep brown as the reaction progressed. After 72 h, the formation of 15 and 16 was confirmed by APCI–MS analysis of the residue in Flask B. We then performed a 13C-labeling experiment using 1b-13Cβ, which was synthesized from H313C–I in eight steps28,29. Treatment of 1b-13Cβ (99% 13C) with Bu4NF in the presence of 14 in CH2Cl2 gave a mixture of 15-13Cα and 15-13Cβ, suggesting that C2 is generated before the O-ethynyl bond-forming reaction with 14 (Fig. 2d). The observed O–13C/12C selectivity (71:29) may be related to very fast radical pairing between C2 and 14 prior to ejection of iodobenzene from the solvent cage30. We also carried out 13C-labeling experiments using 1b-13Cβ in solvents of different viscosities (η). The observed O–13C/12C selectivity decreased as the viscosity decreased, and the regioselectivity was almost lost (52:48) under solvent-free conditions. Similarly, the O–13C/12C selectivity was 51:49 in the connected-flask experiment. All these findings rule out stepwise addition/elimination mechanisms (Supplementary Fig. 5).
Role as molecular element of nanocarbons
Given that C2 generated at room temperature or below behaves exclusively as a singlet biradical, as theoretically predicted for the ground state, we examined whether this ground-state C2 would serve as a molecular element for the formation of various carbon allotropes. Today, nanocarbons such as graphene, CNTs, and fullerenes, in which sp2 carbon takes the form of a planar sheet, tube, ellipsoid, or hollow sphere, are at the heart of nanotechnology31. But, in contrast with the rapid growth of their practical applications, the mechanisms of their formation remain unclear. Various models and theories for the growth of carbon allotropes have been proposed, most of which include the addition/insertion of C2 into a growing carbon cluster as a key step32,33,34,35,36,37,38,39. However, this idea lacks experimental verification. To investigate this issue, we examined the solvent-free reaction of the present singlet biradical C2 in order to avoid hydrogen quenching. Notably, simple grinding of CsF and 1.5 equivalents of 1a in a mortar and pestle at ambient temperature for 10 min under an argon atmosphere resulted in the formation of a dark-brown solid containing various carbon allotropes, as determined by resonance Raman spectroscopy (Supplementary Fig. 6), matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) MS (Fig. 3a) and electrospray ionization (ESI) MS (Supplementary Fig. 8). Careful examination of the Raman spectra and high-resolution transmission electron micrograph (HRTEM) images indicated that high-quality graphite with few defects and an interlayer distance of 0.33 nm (Fig. 4a–c) and amorphous carbon (ca. 80–30% yields) had been mostly synthesized (Supplementary Fig. 6a), together with very small amounts of C60 (Fig. 3a and Supplementary Figs. 8, 9a, and 10–12) and CNTs/carboncones (Fig. 4d and Supplementary Figs. 6b, and 7)40,41. The chemical synthesis of double/triple-walled CNTs/carboncones has never previously been reported. We did not observe any peaks attributable to larger fullerenes, such as C70, C76, C78, and C84. This specificity may reflect the ambient temperature/pressure condition, as the electric carbon arc method generally affords a fearsome mixture of carbon allotropes.
By using 1b-13Cβ, we further confirmed that C60 is synthesized from C2. Grinding of 1b-13Cβ with CsF under the same reaction conditions as above afforded C60-13C30, which was detected by means of MALDI-TOF and ESI MS, while nonlabeled C60 was not detected at all (Fig. 4c and Supplementary Fig. 9b). The formation of this unique fullerene is solid evidence for the role of C2, as its occurrence probability in nature is extremely small [(0.01)30]. When CuCl was added to the reaction mixture (which can stabilize alkynyl radical termini), a mixture of various fragments of polyynes –[C≡C]n– with different chain lengths was observed by MALDI-TOF MS (Fig. 4b). Such peaks were not observed from authentic C60, graphite, and SWCNTs (<ca. 7 nm in diameter) under the same measurement conditions. Lagow et al. proposed that linear acetylenic carbon biradicals (•[C≡C]n•) are a key intermediate/precursor for the formation of C60, and our results seem to support this view34,39.
In conclusion, we have generated C2 at ordinary temperature and pressure. Further, we have established that it has a singlet biradical character at low temperature, settling a long-standing difference of opinion between experimental and theoretical chemists. We also observed spontaneous formation of carbon allotropes such as graphite, CNTs, carboncones, amorphous carbon, and C60 from C2 at ambient temperature, providing the first experimental support for the generally held belief that the formation mechanism of nanocarbons involves the addition/insertion of C2 into a growing carbon cluster as a key step. This is also represents the first chemical synthesis of nanocarbons at ordinary temperature and pressure from C2 in the ground state. Easy synthetic access to in situ generated C2 should be helpful in opening up additional areas of chemistry and materials science, including further studies on the hot topic of the growth mechanisms of bottom-up synthesis of nanocarbons from C2.
General procedure for solid-state reaction of alkynyl-λ3-iodane 1a with CsF
Alkynyl-λ3-iodane 1a (71 mg, 0.15 mmol) and cesium fluoride (15 mg, 0.10 mmol) were gently mixed in an agate mortar under argon, and the mixture was ground for 10 min. The color of the reaction mixture gradually changed from yellowish white to dark brown during the grinding process. The solid residue was treated with excess t-BuOK in order to remove remaining 1a, and then carefully extracted with toluene (ca. 1 mL × 3) and the combined organic phase was analyzed by MALDI-TOF (Fig. 4a and Supplementary Fig. 12) and ESI MS (Supplementary Figs. 8 and 9a). LC-UV analysis was performed with TSKgel ODS-120T (250 × 4.6 mm) using toluene/MeCN = 50/50 as an eluent (Supplementary Fig. 11). LC-MS analysis was performed with Shim-Pack GIST-HP C18 (150 × 2.1 mm) using toluene/MeCN = 60/40 as an eluent (Supplementary Fig. 9). Yield of fullerene C60 was determined to be 4.0 × 10−5% by using an external standard method. As shown below, a linear calibration curve was obtained for toluene solutions of C60 over the concentration range from 1 to 60 ppb (1, 3, 6, 10, 30, and 60 ppb); the correlation coefficient was R2 = 0.99 (Supplementary Fig. 18).
In a separate experiment, after toluene extraction, the reaction mixture was washed several times with water, dispersed in a small amount of ethanol, and dried on a stainless steel plate, which was analyzed by Raman spectroscopy (Supplementary Fig. 6a). Further oxidative treatment in order to remove amorphous carbon from the reaction mixture was carried out as described below.
Oxidative treatment with hydrogen peroxide
To the reaction mixture (8.0 mg) obtained above experiment was added an excess of 20% H2O2 aqueous solution (ca. 8 mL), and the mixture was heated at 100 °C for 24 h42. After cooling, the mixture was centrifuged (4000 rpm, 10 min) and the supernatant was removed. The residue was washed several times with deionized water and then analyzed by Raman spectroscopy (Fig. 4a and Supplementary Fig. 6b) and HRTEM (Fig. 4b, c).
Oxidative treatment with nitric acid
To the reaction mixture (48 mg) obtained above experiment was added an excess of 3.2 M HNO3 aqueous solution (ca. 48 mL) and the mixture was heated at 100 °C for 24 h43. After cooling, the mixture was filtered and washed with deionized water, followed by four times with 4 M NaOH aqueous solution and finally with deionized water. The residue was then analyzed by Raman spectroscopy and HRTEM (Fig. 4d and Supplementary Fig. 7).
For experimental procedures and spectroscopic data of the compounds, see Supplementary Information. For general procedures for alkynyl-λ3-iodanes 1b-13Cβ and trapping reactions, see Supplementary Methods and Supplementary Figs. 1 and 2. For Raman, HRTEM, ESI mass, LC-ESI mass, UV–Vis, LC-UV chromatograms, and MALDI-TOF mass spectra of a sample obtained by a solvent-free reaction, see Supplementary Figs. 6–12. For NMR spectra see Supplementary Figs. 13–17.
Swan, W. On the prismatic spectra of the flames of compounds of carbon and hydrogen. Trans. R. Soc. Edinburgh 21, 411–430 (1857).
Glockler, G. The heat of sublimation of graphite and the composition of carbon vapor. J. Chem. Phys. 22, 159–161 (1954).
Kopfermann, H. & Schweitzer, H. A band system of diatomic carbon vapour. Z. für Phys. 61, 87–94 (1930).
Pan, W. & Shevlin, P. B. Reaction of atomic and molecular carbon with cyclooctatetraene. J. Am. Chem. Soc. 118, 10004–10005 (1996).
Skell, P. S. & Plonka, J. H. Chemistry of the singlet and triplet C2 molecules. Mechanism of acetylene formation from reaction with acetone and acetaldehyde. J. Am. Chem. Soc. 92, 5620–5624 (1970).
Skell, P. S., Havel, J. J. & McGlinchey, M. J. Chemistry and the carbon arc. Acc. Chem. Res. 6, 97–105 (1973).
Skell, P. S. & Harris, R. F. Some chemistry of the C2 molecule. J. Am. Chem. Soc. 88, 5933–5934 (1966).
Martin, M. C2 spectroscopy and kinetics. J. Photochem. Photobiol. A 66, 263–289 (1992).
Jin, L., Melaimi, M., Liu, L. & Bertrand, G. Singlet carbenes as mimics for transitionmetals: synthesis of an air stable organic mixed valence compound [M2(C2)+•;M = cyclic(alkyl)(amino)- carbene]. Org.Chem. Front. 1, 351–354 (2014).
Li, Y. et al. C4 Cumulene and the corresponding air-stable radical cation and dication. Angew. Chem. Int. Ed. 53, 4168–4172 (2014).
Wu, D., Li, Y., Gangulyb, R. & Kinjo, R. Synthesis and structural characterization of a C4 cumulene including 4-pyridylidene units, and its reactivity towards ammonia-borane. Chem. Commun. 50, 12378–12381 (2014).
Stang, P. J., Arif, A. M. & Zhdankin, V. V. Reaction of E-1,2-bis[triphenyl(trifluoromethanesulfonyloxy)phospho]ethylene, Ph3PCHCHPPh3·2OTf with bases: Unusual products and evidence for C2-diylide, Ph3PCCPPh3, formation. Tetrahedron 47, 4539–4546 (1991).
Shaik, S. et al. Quadruple bonding in C2 and analogous eight-valence electron species. Nat. Chem. 4, 195–199 (2012).
Shaik, S., Danovich, D., Braida, B. & Hiberty, P. C. The quadruple bonding in C2 reproduces the properties of the molecule. Chem. Eur. J. 22, 4116–4128 (2016).
Varvoglis, A. The Organic Chemistry of Polycoordinated Iodine (VCH, New York, 1992).
Yoshimura, A. & Zhdankin, V. V. Advances in synthetic applications of hypervalent iodine compounds. Chem. Rev. 116, 3328–3435 (2016).
Wirth, T. (ed) Hypervalent Iodine Chemistry. Topic in Current Chemistry, Vol. 373 (Springer, Cham, 2016).
Okuyama, T., Takino, T., Sueda, T. & Ochiai, M. Solvolysis of cyclohexenyliodonium salt, a new precursor for the vinyl cation: remarkable nucleofugality of the phenyliodonio group and evidence for internal return from an intimate ion-molecule pair. J. Am. Chem. Soc. 117, 3360–3367 (1995).
Ochiai, M. et al. Synthesis of ethynyl(phenyl)iodonium tetrafluoroborate. A new reagent for ethynylation of 1,3-dicarbonyl compounds. J. Chem. Soc. 2 118–119 (1991).
Pan, W., Armstrong, B. M., Shevlin, P. B., Crittell, C. H. & Stang, P. J. A potential chemical source of C2. Chem. Lett. 28 849 (1999).
Stein, S. E. & Brown, R. L. Prediction of carbon-hydrogen bond dissociation energies for polycyclic aromatic hydrocarbons of arbitrary size. J. Am. Chem. Soc. 113, 787–793 (1991).
Poutsma, J. C., Paulino, J. A. & Squires, R. R. Absolute heats of formation of CHCl, CHF, and CClF. A gas-phase experimental and G2 theoretical study. J. Phys. Chem. A 101, 5327–5336 (1997).
Bernardi, F., Mangini, A., Epiotis, N. D., Larson, J. R. & Shaik, S. The donating ability of heteroatoms. J. Am. Chem. Soc. 99, 7465–7470 (1977).
Serratosa, F. Acetylene diethers: a logical entry to oxocarbons. Acc. Chem. Res. 16, 170–176 (1983).
Ervin, K. M. et al. Bond strengths of ethylene and acetylene. J. Am. Chem. Soc. 112, 5750–5759 (1990).
Usharani, D. et al. A tutorial for understanding chemical reactivity through the valence bond approach. Chem. Soc. Rev. 43, 4968–4988 (2014).
Ochiai, M., Tsuchimoto, Y. & Hayashi, T. Borane-induced radical reduction of 1-alkenyl- and 1-alkynyl-λ3-iodanes with tetrahydrofuran. Tetrahedron Lett. 44, 5381–5384 (2003).
Brand, J. P., Chevalley, C., Scopelliti, R. & Waser, J. Ethynyl benziodoxolones for the direct alkynylation of heterocycles: structural requirement, improved procedure for pyrroles, and insights into the mechanism. Chem. Eur. J. 18, 5655–5666 (2012).
Brunner, A. & Hintermann, L. A Sequential homologation of alkynes and aldehydes for chain elongation with optional 13C-labeling. Chem. Eur. J. 22, 2787–2792 (2016).
Xu, J. & Weiss, R. G. Analyses of in-cage singlet radical-pair motions from irradiations of 1-naphthyl (R)-1-phenylethyl ether and 1-naphthyl (R)-2-phenylpropanoate in n-alkanes. J. Org. Chem. 70, 1243–1252 (2005).
Li, Z., Liu, Z., Sun, H. & Gao, C. Superstructured assembly of nanocarbons: fullerenes, nanotubes, and graphene. Chem. Rev. 115, 7046–7117 (2015).
Irle, S., Zheng, G., Wang, Z. & Morokuma, K. The C60 formation puzzle “solved”: QM/MD simulations reveal the shrinking hot giant road of the dynamic fullerene self-assembly mechanism. J. Phys. Chem. B 110, 14531–14545 (2006).
Rodríguez-Fortea, A., Irle, S. J. & Poblet, M. Fullerenes: formation, stability, and reactivity. Comput. Mol. Sci. 1, 350–367 (2011).
Lagow, R. J. et al. Synthesis of linear acetylenic carbon: the “sp” carbon allotrope. Science 267, 362–367 (1995).
Bewilogua, K. & Hofmann, D. History of diamond-like carbon films—from first experiments to worldwide applications. Surf. Coat. Technol. 242, 214–225 (2014).
Li, P., Li, Z. & Yang, J. Dominant kinetic pathways of graphene growth in chemical vapor deposition: the role of hydrogen. J. Phys. Chem. C 121, 25949–25955 (2017).
Endo, M. & Kroto, H. W. Formation of carbon nanofibers. J. Phys. Chem. 96, 6941–6944 (1992).
Cruz-Silva, R. et al. Fullerene and nanotube growth: new insights using first principles and molecular dynamics. Philos. Trans. R. Soc. A 374, 20150327 (2016).
Page, A. J., Ding, F., Irle, S. & Morokuma, K. Insights into carbon nanotube and graphene formation mechanisms from molecular simulations: a review. Rep. Prog. Phys. 78, 036501 (2015).
Shoyama, K. & Würthner, F. Synthesis of a carbon nanocone by cascade annulation. J. Am. Chem. Soc. 141, 13008–13012 (2019).
Zhu, Z.-Z. et al. Rational synthesis of an atomically precise carboncone under mild conditions. Sci. Adv. 5, eaaw0982 (2019).
Shao, L. et al. Removal of amorphous carbon for the efficient sidewall functionalisation of single-walled carbon nanotubes. Chem. Commun. 47 5090–5092 (2007).
Feng, Y. et al. Room temperature purification of few-walled carbon nanotubes with high yield. ACS Nano 2, 1634–1638 (2008).
This work was supported by grants from JSPS KAKENHI (S) (17H06173), KAKENHI (B) (17H03017), JST CREST (No. JPMJCR19R2), NAGASE Science & Technology Development Foundation, and Sumitomo Foundation.
The authors declare no competing interests.
Peer review information Nature Communications thanks Viktor Zhdankin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Miyamoto, K., Narita, S., Masumoto, Y. et al. Room-temperature chemical synthesis of C2. Nat Commun 11, 2134 (2020). https://doi.org/10.1038/s41467-020-16025-x