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

Abstract

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.

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

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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.

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Acknowledgements

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.

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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.

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Correspondence to Zhaomin Hou.

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The authors declare no competing financial interests.

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Hu, S., Shima, T. & Hou, Z. Carbon–carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride. Nature 512, 413–415 (2014). https://doi.org/10.1038/nature13624

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