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One-, Two-, and Three-Electron Reduction of a Cyclic Alkyl(amino)carbene–SbCl3 Adduct

Authors


  • Financial support from the NSF (CHE-1316956) and allocation of computer time from the Institut für Mathematik der TU Berlin are gratefully acknowledged. We thank Dr. M. Melaimi, M. Angelella, and Prof. M. Tauber for assistance with the EPR experiments, and Dr. D. Martin for helpful discussions. R.K. acknowledges the Alexander von Humboldt foundation for a Feodor Lynen Research Fellowship and D.A.R. thanks the U.S. Department of Education for a GAANN fellowship.

Abstract

A cyclic alkyl(amino)carbene readily reacts with SbCl3 to form the corresponding SbIII adduct. One-electron reduction gives rise to the first example of a neutral antimony-centered radical characterized in solution. Two-electron reduction affords a Lewis base stabilized chloro-stibinidene, whereas three-electron reduction gives an antimony diatomic species capped by two carbenes. The radical has been characterized by EPR spectroscopy, while the structure of the other three species has been ascertained by single-crystal X-ray diffraction. In these four species, the formal oxidation state of the metalloid diminishes from III, to II, to I, and finally 0.

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