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Capture of hydroxymethylene and its fast disappearance through tunnelling

Nature volume 453, pages 906–909 (2008)Cite this article

Abstract

Singlet carbenes exhibit a divalent carbon atom whose valence shell contains only six electrons, four involved in bonding to two other atoms and the remaining two forming a non-bonding electron pair. These features render singlet carbenes so reactive that they were long considered too short-lived for isolation and direct characterization. This view changed when it was found that attaching the divalent carbon atom to substituents that are bulky and/or able to donate electrons produces carbenes that can be isolated and stored1. N-heterocyclic carbenes are such compounds now in wide use, for example as ligands in metathesis catalysis2. In contrast, oxygen-donor-substituted carbenes are inherently less stable and have been less studied. The pre-eminent case is hydroxymethylene, H–C–OH; although it is the key intermediate in the high-energy chemistry of its tautomer formaldehyde3,4,5,6,7, has been implicated since 1921 in the photocatalytic formation of carbohydrates8, and is the parent of alkoxycarbenes that lie at the heart of transition-metal carbene chemistry, all attempts to observe this species or other alkoxycarbenes have failed9. However, theoretical considerations indicate that hydroxymethylene should be isolatable10. Here we report the synthesis of hydroxymethylene and its capture by matrix isolation. We unexpectedly find that H–C–OH rearranges to formaldehyde with a half-life of only 2 h at 11 K by pure hydrogen tunnelling through a large energy barrier in excess of 30 kcal mol–1.

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Figure 1: Generation of hydroxymethylene (1).
Figure 2: Infrared spectra of 1 and [D 1 ]-1.
Figure 3: Ultraviolet/visible spectrum of 1 and [D 1 ]-1.
Figure 4: Schematic H–C–O–H potential energy hypersurface.

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Acknowledgements

We are grateful for support from the Fonds der Chemischen Industrie, the US Department of Energy, and the Hungarian Scientific Research Fund. We thank J. Bowman and W. Miller for comments on the tunnelling analysis.

Author Contributions P.R.S. and H.P.R. formulated the initial working hypothesis and provided, analysed and interpreted all experimental data. F.C.P. and A.C.S. performed all the electronic structure computations under the direction of W.D.A. The variational vibrational computations were executed by E.M. under the guidance of A.G.C. and W.D.A. The tunnelling analysis was performed by W.D.A., with input from F.C.P. and A.C.S. The manuscript was primarily written by P.R.S. and W.D.A.

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Authors and Affiliations

  1. Institut für Organische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany ,

    Peter R. Schreiner & Hans Peter Reisenauer

  2. Center for Computational Chemistry and Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA,

    Frank C. Pickard IV, Andrew C. Simmonett & Wesley D. Allen

  3. Laboratory of Molecular Spectroscopy, Institute of Chemistry, Eötvös University, H-1518 Budapest 112PO Box 32, Hungary ,

    Edit Mátyus & Attila G. Császár

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  1. Peter R. Schreiner
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Correspondence to Peter R. Schreiner or Wesley D. Allen.

Supplementary information

Supplementary information

The file contains Supplementary Figures and Legends 1 and 2; Supplementary Tables 1-10. The supplementary information contains two figures showing computed molecular structures with structural parameters. One supplementary experimental table summarizes the tunneling experiments at different temperatures and in different matrices. Another 9 supplementary tables contain computed data: xyz coordinates of all structures (supplementary tables 2 and 3) and energies (supplementary tables 4-10). (PDF 1347 kb)

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Schreiner, P., Reisenauer, H., Pickard IV, F. et al. Capture of hydroxymethylene and its fast disappearance through tunnelling. Nature 453, 906–909 (2008). https://doi.org/10.1038/nature07010

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