Carbon–carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride


The cleavage of carbon−carbon (C−C) bonds by transition metals is of great interest, especially as this transformation can be used to produce fuels and other industrially important chemicals from natural resources such as petroleum and biomass. Carbon−carbon bonds are quite stable and are consequently unreactive under many reaction conditions. In the industrial naphtha hydrocracking process, the aromatic carbon skeleton of benzene can be transformed to methylcyclopentane and acyclic saturated hydrocarbons through C−C bond cleavage and rearrangement on the surfaces of solid catalysts1,2,3,4,5,6. However, these chemical transformations usually require high temperatures and are fairly non-selective. Microorganisms can degrade aromatic compounds under ambient conditions, but the mechanistic details are not known and are difficult to mimic7. Several transition metal complexes have been reported to cleave C−C bonds in a selective fashion in special circumstances, such as relief of ring strain, formation of an aromatic system, chelation-assisted cyclometallation and β-carbon elimination8,9,10,11,12,13,14,15. However, the cleavage of benzene by a transition metal complex has not been reported16,17,18,19. Here we report the C−C bond cleavage and rearrangement of benzene by a trinuclear titanium polyhydride complex. The benzene ring is transformed sequentially to a methylcyclopentenyl and a 2-methylpentenyl species through the cleavage of the aromatic carbon skeleton at the multi-titanium sites. Our results suggest that multinuclear titanium hydrides could serve as a unique platform for the activation of aromatic molecules, and may facilitate the design of new catalysts for the transformation of inactive aromatics.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Reactions of a trinuclear titanium heptahydride complex (1) with benzene and benzene-d6.
Figure 2: Reaction of complex 1 with toluene.

Accession codes

Data deposits

X-ray crystallographic coordinates of 2, 4, 5 and 6 have been deposited at the Cambridge Crystallographic Database under accession numbers 981670–981673.


  1. 1

    Jones, D. S. J. & Pujadó, P. R. Handbook of Petroleum Processing (Springer, 2006)

    Google Scholar 

  2. 2

    Weitkamp, J. Handbook of Heterogeneous Catalysis Vol. 1, 2nd edn (eds Ertl, G., Knözinger, H., Schüth, F. & Weitkamp, J. ) Ch. 14.2 (Wiley-VCH, 2008)

    Google Scholar 

  3. 3

    Watanabe, R., Suzuki, T. & Okuhara, T. Skeletal isomerization of alkanes and hydroisomerization of benzene over solid strong acids and their bifunctional catalysts. Catal. Today 66, 123–130 (2001)

    CAS  Article  Google Scholar 

  4. 4

    McVicker, G. B. et al. Selective ring opening of naphthenic molecules. J. Catal. 210, 137–148 (2002)

    CAS  Article  Google Scholar 

  5. 5

    Benitez, V. M., Grau, J. M., Yori, J. C., Pieck, C. L. & Vera, C. R. Hydroisomerization of benzene-containing paraffinic feedstocks over Pt/WO3-ZrO2 catalysts. Energy Fuels 20, 1791–1798 (2006)

    CAS  Article  Google Scholar 

  6. 6

    Kazakov, M. O. et al. Hydroisomerization of benzene-containing gasoline fractions on a Pt/SO42−-ZrO2-Al2O3 catalyst: I. Effect of chemical composition on the phase state and texture characteristics of SO42−-ZrO2-Al2O3 supports. Kinet. Catal. 51, 438–443 (2010)

    CAS  Article  Google Scholar 

  7. 7

    Bugg, T. D. H. & Winfield, C. J. Enzymatic cleavage of aromatic rings: mechanistic aspects of the catechol dioxygenases and later enzymes of bacterial oxidative cleavage pathways. Nat. Prod. Rep. 15, 513–530 (1998)

    CAS  Article  Google Scholar 

  8. 8

    Bishop, K. C. Transition metal catalysed rearrangements of small ring organic molecules. Chem. Rev. 76, 461–486 (1976)

    CAS  Article  Google Scholar 

  9. 9

    Crabtree, R. H. The organometallic chemistry of alkanes. Chem. Rev. 85, 245–269 (1985)

    CAS  Article  Google Scholar 

  10. 10

    Jones, W. D. The fall of the C–C bond. Nature 364, 676–677 (1993)

    ADS  Article  Google Scholar 

  11. 11

    Rybtchinski, B. & Milstein, D. Metal insertion into C–C bonds in solution. Angew. Chem. Int. Ed. 38, 870–883 (1999)

    Article  Google Scholar 

  12. 12

    Jun, C. Transition metal-catalysed carbon–carbon bond activation. Chem. Soc. Rev. 33, 610–618 (2004)

    CAS  Article  Google Scholar 

  13. 13

    Murakami, M. & Matsuda, T. Metal-catalysed cleavage of carbon-carbon bonds. Chem. Commun. 47, 1100–1105 (2011)

    CAS  Article  Google Scholar 

  14. 14

    Ruhland, K. Transition-metal-mediated cleavage and activation of C–C single bonds. Eur. J. Org. Chem. 2012, 2683–2706 (2012)

    CAS  Article  Google Scholar 

  15. 15

    Takao, T. & Suzuki, H. Skeletal rearrangement of hydrocarbyl ligands on a triruthenium core induced by chemical oxidation. Coord. Chem. Rev. 256, 695–708 (2012)

    CAS  Article  Google Scholar 

  16. 16

    Sattler, A. & Parkin, G. Cleaving carbon–carbon bonds by inserting tungsten into unstrained aromatic rings. Nature 463, 523–526 (2010)

    CAS  ADS  Article  Google Scholar 

  17. 17

    Kira, M., Ishida, S., Iwamoto, T. & Kabuto, C. Excited-state reactions of an isolable silylene with aromatic compounds. J. Am. Chem. Soc. 124, 3830–3831 (2002)

    CAS  Article  Google Scholar 

  18. 18

    Ellis, D., McKay, D., Macgregor, S. A., Rosair, G. M. & Welch, A. J. Room-temperature C–C bond cleavage of an arene by a metallacarborane. Angew. Chem. Int. Ed. 49, 4943–4945 (2010)

    CAS  Article  Google Scholar 

  19. 19

    Szyszko, B., Latos-Grażyński, L. & Szterenberg, L. A facile palladium-mediated contraction of benzene to cyclopentadiene: transformations of palladium(II) p-benziporphyrin. Angew. Chem. Int. Ed. 50, 6587–6591 (2011)

    CAS  Article  Google Scholar 

  20. 20

    Van Hove, M. A., Lin, R. F. & Somorjai, G. A. Surface structure of coadsorbed benzene and carbon monoxide on the rhodium(III) single crystal analysed with low energy electron diffraction intensities. J. Am. Chem. Soc. 108, 2532–2537 (1986)

    CAS  Article  Google Scholar 

  21. 21

    Dyson, P. J. Arene hydrogenation by homogeneous catalysts: fact or fiction? Dalton Trans. 2964–2974 (2003)

  22. 22

    Tardif, O., Hashizume, D. & Hou, Z. Hydrogenation of carbon dioxide and aryl isocyanates by a tetranuclear tetrahydrido yttrium complex. isolation, structures, and CO2 insertion reactions of methylene diolate and μ3-oxo yttrium complexes. J. Am. Chem. Soc. 126, 8080–8081 (2004)

    CAS  Article  Google Scholar 

  23. 23

    Shima, T. & Hou, Z. Hydrogenation of carbon monoxide by tetranuclear rare earth metal polyhydrido complexes. selective formation of ethylene and isolation of well-defined polyoxo rare earth metal clusters. J. Am. Chem. Soc. 128, 8124–8125 (2006)

    CAS  Article  Google Scholar 

  24. 24

    Nishiura, M. & Hou, Z. Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls. Nature Chem. 2, 257–268 (2010)

    CAS  ADS  Article  Google Scholar 

  25. 25

    Shima, T. et al. Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals. Nature Chem. 3, 814–820 (2011)

    CAS  ADS  Article  Google Scholar 

  26. 26

    Shima, T. et al. Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex. Science 340, 1549–1552 (2013)

    CAS  ADS  Article  Google Scholar 

  27. 27

    Brookhart, M. & Green, M. L. H. Carbon-hydrogen-transition metal bonds. J. Organomet. Chem. 250, 395–408 (1983)

    CAS  Article  Google Scholar 

  28. 28

    Suzuki, H., Takaya, Y., Takemori, T. & Tanaka, M. Selective carbon-carbon bond cleavage of cyclopentadiene on a trinuclear ruthenium pentahydride complex. J. Am. Chem. Soc. 116, 10779–10780 (1994)

    CAS  Article  Google Scholar 

  29. 29

    Brown, D. B. et al. Cluster-mediated ring contraction: synthesis and characterisation of [Ru6(μ3-H)(μ4-η2-CO)2(CO)13(η5-C5H4Me)] and [Ru6(μ3-H)(μ4-η2-CO)2(CO)13(η5-C5H3C3H6)]. J. Chem. Soc. Dalton Trans. 1909–1914 (1997)

  30. 30

    Takao, T. et al. Synthesis and property of diruthenium complexes containing bridging cyclic diene ligands and the reaction of diruthenium tetrahydrido complex with benzene forming a μ-η2:η2-cyclohexadiene complex via partial hydrogenation on a Ru2 centre. Organometallics 30, 5057–5067 (2011)

    CAS  Article  Google Scholar 

Download references


This work was supported by a Grant-in-Aid for Young Scientists (B) (no. 26810041), a Grant-in-Aid for Scientific Research (C) (no. 26410082) and a Grant-in-Aid for Scientific Research (S) (no. 26220802) from JSPS, and an Incentive Research Grant from RIKEN. We thank J. Cheng for help with X-ray structure analyses, and A. Karube for conducting elemental analyses.

Author information




Z.H., S.H. and T.S. had the idea for and designed the experiments. S.H. and T.S. conducted the experiments. Z.H. and S.H. wrote the manuscript. All authors participated in data analyses and discussions. Z.H. directed the project.

Corresponding author

Correspondence to Zhaomin Hou.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary text and Data, Supplementary Figures 1-49 and Supplementary References. (PDF 4916 kb)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Hu, S., Shima, T. & Hou, Z. Carbon–carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride. Nature 512, 413–415 (2014).

Download citation

Further reading


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.


Sign up for the Nature Briefing newsletter for a daily update on COVID-19 science.
Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing