Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Stabilization of elusive silicon oxides

Nature Chemistry volume 7, pages 509–513 (2015)Cite this article

Subjects

This article has been updated

Abstract

Molecular SiO2 and other simple silicon oxides have remained elusive despite the indispensable use of silicon dioxide materials in advanced electronic devices. Owing to the great reactivity of silicon–oxygen double bonds, as well as the low oxidation state of silicon atoms, the chemistry of simple silicon oxides is essentially unknown. We now report that the soluble disilicon compound, L:Si=Si:L (where L: = :C{N(2,6-iPr2C6H3)CH}2), can be directly oxidized by N2O and O2 to give the carbene-stabilized Si2O3 and Si2O4 moieties, respectively. The nature of the silicon oxide units in these compounds is probed by spectroscopic methods, complementary computations and single-crystal X-ray diffraction.

This is a preview of subscription content

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

Buy

All prices are NET prices.

Figure 1: Elusive silicon–oxide clusters.
Figure 2: Synthetic scheme for 2 and 3.
Figure 3: Molecular structures of the carbene-stabilized Si2O3 and Si2O4 species.
Figure 4: LMOs of the 2-Ph model.
Figure 5: Resonance contributors of 2 and 3.

Change history

  • 23 April 2015

    In the version of this Article originally published online, the first sentence of the final paragraph of 'Results and discussion' should have referred to 'room temperature'. This has now been corrected in all versions of the Article.

References

  1. Greenwood, N. N. & Earnshaw, A. Chemistry of the Elements 2nd edn (Butterworth-Heinemann, 1997).

    Google Scholar 

  2. Halmann, M. M. & Steinberg, M. Greenhouse Gas Carbon Dioxide Mitigation: Science and Technology (Lewis, 1998).

    Book  Google Scholar 

  3. Anderson, J. S. & Ogden, J. S. Matrix isolation studies of group-IV oxides. I. Infrared spectra and structures of SiO, Si2O2, and Si3O3 . J. Chem. Phys. 51, 4189–4196 (1969).

    CAS  Article  Google Scholar 

  4. Mehner, T., Göcke, H. J., Schunck, S. & Schnöckel, H. Molecular silicon dioxide, matrix IR investigations and ab initio SCF-calculations. Z. Anorg. Allg. Chem. 580, 121–130 (1990).

    CAS  Article  Google Scholar 

  5. Wang, L-S., Wu, H., Desai, S. R., Fan, J. & Colson, S. D. A photoelectron spectroscopic study of small silicon oxide clusters: SiO2, Si2O3, and Si2O4 . J. Phys. Chem. 100, 8697–8700 (1996).

    CAS  Article  Google Scholar 

  6. Goldberg, N., Iraqi, M., Koch, W. & Schwarz, H. Gas-phase characterization of the neutral and cationic Si2O2 molecules. A combined experimental and ab initio study. Chem. Phys. Lett. 225, 404–409 (1994).

    CAS  Article  Google Scholar 

  7. Wang, L-S., Desai, S. R., Wu, H. & Nicholas, J. B. Small silicon oxide clusters: chains and rings. Z. Phys. D 40, 36–39 (1997).

    CAS  Article  Google Scholar 

  8. Iraqi, M., Goldberg, N. & Schwarz, H. Neutralization-reionization mass spectrometry experiments confirm the predicted existence of cyclic silicon oxide (Si2O) and silicon nitride (Si2N) cluster molecules. J. Phys. Chem. 97, 11371–11372 (1993).

    CAS  Article  Google Scholar 

  9. Jutzi, P. & Schubert, U. Silicon Chemistry: From the Atom to Extended Systems (Wiley-VCH, 2003).

    Book  Google Scholar 

  10. Mehner, T., Köppe, R. & Schnöckel, H. Evidence for [PdSiO] from IR spectroscopy. Angew. Chem. Int. Ed. 31, 638–640 (1992).

    Article  Google Scholar 

  11. Mehner, T., Schnöckel, H., Almond, M. J. & Downs, A. J. Transition-metal derivatives of monomeric silicon oxide (SiO). Interaction of molecular SiO with silver atoms in an argon matrix. J. Chem. Soc. Chem. Commun. 117–119 (1988).

  12. Chenier, J. H. B., Howard, J. A., Joly, H. A., Mile, B. & Timms, P. L. Studies of the reactions of SiO and silver atoms in hydrocarbon matrixes at 77 K. Chem. Commun. 581–582 (1990).

  13. Schnöckel, H. IR spectroscopic detection of molecular SiO2 . Angew. Chem. Int. Ed. 17, 616–617 (1978).

    Article  Google Scholar 

  14. Chakraborty, S., Yanchulova, P. & Thiemens, M. H. Mass-independent oxygen isotopic partitioning during gas-phase SiO2 formation. Science 342, 463–466 (2013).

    CAS  Article  Google Scholar 

  15. Hu, C. C. Modern Semiconductor Devices for Integrated Circuits (Prentice Hall, 2010).

    Google Scholar 

  16. Wang, N., Tang, Y. H., Zhang, Y. F., Lee, C. S. & Lee, S. T. Nucleation and growth of Si nanowires from silicon oxide. Phys. Rev. B 58, R16024–R16026 (1998).

    CAS  Article  Google Scholar 

  17. Shi, W-S. et al. Synthesis of large areas of highly oriented, very long silicon nanowires. Adv. Mater. 12, 1343–1345 (2000).

    CAS  Article  Google Scholar 

  18. Negrila, C. C. et al. ARXPS analysis of silicon oxide films. J. Optoelectron. Adv. Mater. 10, 1379–1383 (2008).

    CAS  Google Scholar 

  19. Du, H-B. et al. Electronic and vibrational properties of stable isomers of (SiO)n(0,±) (n = 2–7) clusters. J. Phys. Chem. A 118, 8893–8900 (2014).

    CAS  Article  Google Scholar 

  20. Kisa, M., Minton, T. K. & Yang, J. C. Structural comparisons of SiOx and Si/SiOx formed by the exposure of silicon (100) to molecular oxygen and to hyperthermal atomic oxygen. J. Appl. Phys. 97, 023520 (2005).

    Article  Google Scholar 

  21. Murad, E. Spacecraft interaction with atmospheric species in low earth orbit. J. Spacecr. Rockets 33, 131–136 (1996).

    CAS  Article  Google Scholar 

  22. Wang, Y. et al. A stable silicon(0) compound with a Si=Si double bond. Science 321, 1069–1071 (2008).

    CAS  Article  Google Scholar 

  23. Dyker, C. A. & Bertrand, G. Soluble allotropes of main-group elements. Science 321, 1050–1051 (2008).

    CAS  Article  Google Scholar 

  24. Xiong, Y., Yao, S. & Driess, M. Chemical tricks to stabilize silanones and their heavier homologues with E=O bonds (E = Si–Pb): from elusive species to isolable building blocks. Angew. Chem. Int. Ed. 52, 4302–4311 (2013).

    CAS  Article  Google Scholar 

  25. Sen, S. S. A stable silanone with a three-coordinate silicon atom: a century-long wait is over. Angew. Chem. Int. Ed. 53, 8820–8822 (2014).

    CAS  Article  Google Scholar 

  26. Avakyan, V. G., Sidorkin, V. F., Belogolova, E. F., Guselnikov, S. L. & Gusel'nikov, L. E. AIM and ELF electronic structure/G2 and G3 π-bond energy relationship for doubly bonded silicon species, H2Si=X (X = E14H2, E15H, E16). Organometallics 25, 6007–6013 (2006).

    CAS  Article  Google Scholar 

  27. Wang, Y. & Robinson, G. H. Carbene stabilization of highly reactive main-group molecules. Inorg. Chem. 50, 12326–12337 (2011).

    CAS  Article  Google Scholar 

  28. Wang, Y. & Robinson, G. H. N-heterocyclic carbene-main-group chemistry: a rapidly evolving field. Inorg. Chem. 53, 11815–11832 (2014).

    CAS  Article  Google Scholar 

  29. Martin, D., Melaimi, M., Soleilhavoup, M. & Bertrand, G. A brief survey of our contribution to stable carbene chemistry. Organometallics 30, 5304–5313 (2011).

    CAS  Article  Google Scholar 

  30. Martin, C. D., Soleilhavoup, M. & Bertrand, G. Carbene-stabilized main group radicals and radical ions. Chem. Sci. 4, 3020–3030 (2013).

    CAS  Article  Google Scholar 

  31. Yao, S-L., Xiong, Y. & Driess, M. Zwitterionic and donor-stabilized N-heterocyclic silylenes (NHSis) for metal-free activation of small molecules. Organometallics 30, 1748–1767 (2011).

    CAS  Article  Google Scholar 

  32. Ghadwal, R. S., Azhakar, R. & Roesky, H. W. Dichlorosilylene: a high temperature transient species to an indispensable building block. Acc. Chem. Res. 46, 444–456 (2013).

    CAS  Article  Google Scholar 

  33. Xiong, Y., Yao, S. & Driess, M. An isolable NHC-supported silanone. J. Am. Chem. Soc. 131, 7562–7563 (2009).

    CAS  Article  Google Scholar 

  34. Yao, S., Xiong, Y., Brym, M. & Driess, M. An isolable silanoic ester by oxygenation of a stable silylene. J. Am. Chem. Soc. 129, 7268–7269 (2007).

    CAS  Article  Google Scholar 

  35. Xiong, Y., Yao, S., Mueller, R., Kaupp, M. & Driess, M. From silicon(II)-based dioxygen activation to adducts of elusive dioxasiliranes and sila-ureas stable at room temperature. Nature Chem. 2, 577–580 (2010).

    CAS  Article  Google Scholar 

  36. Ghadwal, R. S. et al. Donor–acceptor-stabilized silicon analogue of an acid anhydride. J Am Chem. Soc. 133, 17552–17555 (2011).

    CAS  Article  Google Scholar 

  37. Rodriguez, R. et al. Synthesis of a donor-stabilized silacyclopropan-1-one. Angew. Chem. Int. Ed. 52, 4426–4430 (2013).

    CAS  Article  Google Scholar 

  38. Filippou, A. C., Baars, B., Chernov, O., Lebedev, Y. N. & Schnakenburg, G. Silicon–oxygen double bonds: a stable silanone with a trigonal-planar coordinated silicon center. Angew. Chem. Int. Ed. 53, 565–570 (2014).

    CAS  Article  Google Scholar 

  39. Mondal, K. C. et al. Easy access to silicon(0) and silicon(II) compounds. Inorg. Chem. 52, 4736–4743 (2013).

    CAS  Article  Google Scholar 

  40. Arrington, C. A., West, R. & Michl, J. On the proposed thermal interconversion of matrix-isolated dimethylsilylene and 1-methylsilene: their reactions with oxygen atom donors. J. Am. Chem. Soc. 105, 6176–6177 (1983).

    CAS  Article  Google Scholar 

  41. Wang, Y. et al. Splitting molecular oxygen en route to a stable molecule containing diphosphorus tetroxide. J. Am. Chem. Soc. 135, 19139–19142 (2013).

    CAS  Article  Google Scholar 

  42. Avramov, P. V. et al. Potential energy surfaces of SimOn cluster formation and isomerization. J. Phys. Chem. A 109, 6294–6302 (2005).

    CAS  Article  Google Scholar 

  43. Sohn, H., Tan, R. P., Powell, D. R. & West, R. Structural characterization of 1,3-cyclodisiloxanes. Organometallics 13, 1390–1394 (1994).

    CAS  Article  Google Scholar 

  44. Millevolte, A. J., Powell, D. R., Johnson, S. G. & West, R. Solution and solid-state oxidation chemistry of tetrakis(2,4,6-triisopropylphenyl)disilene. Organometallics 11, 1091–1095 (1992).

    CAS  Article  Google Scholar 

  45. Corey, J. Y. in The Chemistry of Organic Silicon Compounds Vol. 1 (eds Patai, S. & Rappoport, Z.) Ch. 1 (Wiley, 1989).

    Google Scholar 

Download references

Acknowledgements

We are grateful to the National Science Foundation for support: CHE-1265212 (G.H.R., Y.W.), CHE-1057466 (P.v.R.S.) and CHE-1361178 (H.F.S.).

Author information

Affiliations

  1. Department of Chemistry, The University of Georgia, Athens, 30602-2556, Georgia, USA

    Yuzhong Wang, Mingwei Chen, Pingrong Wei, Paul von R. Schleyer & Gregory H. Robinson

  2. Center for Computational Chemistry, The University of Georgia, Athens, 30602-2556, Georgia, USA

    Yaoming Xie, Henry F. Schaefer III & Paul von R. Schleyer

Authors
  1. Yuzhong Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mingwei Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yaoming Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Pingrong Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Henry F. Schaefer III
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Paul von R. Schleyer
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Gregory H. Robinson
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

G.H.R. and Y.W. designed the experiments. Y.W. and M.C. performed all the experiments. P.W. performed the X-ray diffraction studies. Y.X., H.F.S. and P.v.R.S. carried out the computations. Y.W., P.v.R.S. and G.H.R. wrote the paper. All the authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Gregory H. Robinson.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 721 kb)

Supplementary information

Crystallographic data for compound 2.(THF)2 (CIF 577 kb)

Supplementary information

Crystallographic data for compound 2 (CIF 929 kb)

Supplementary information

Crystallographic data for compound 3 (CIF 931 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Wang, Y., Chen, M., Xie, Y. et al. Stabilization of elusive silicon oxides. Nature Chem 7, 509–513 (2015). https://doi.org/10.1038/nchem.2234

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.2234

Further reading

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing