Rhodaoxetane: Synthesis, Structure, and Theoretical Evaluation

Maria J. Calhorda, Adelino M. Galvão, Canan Ünaleroglu, Andrei A. Zlota, Felix Frolow, David Milstein

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Abstract

Oxidative addition of Rh(PMe3)3Cl to HOCMe2CH2Br leads to the β-hydroxy complex 4. Deprotonation of 4 with (Me3Si)2NK leads to the rhodaoxetane 5. 4 and 5 were crystallographically characterized, allowing direct evaluation of the structural consequences of ring closure. The oxetane ring in 5 is planar and it exhibits RhC [2.069(10) Å] and CO [1.416(12) Å], significantly shorter than the equivalent bonds in 4. The planarity of the oxetane ring was assigned to a minimization of repulsive interactions between filled orbitals of the metal and oxygen in this geometry, a result of a theoretical study based on extended Hückel calculations. 4 also shows a substantial Cl⋯H hydrogen bond. 5 can also be obtained by direct oxidative addition of Rh(PMe3)3Br to isobutylene oxide, providing the first direct demonstration of oxidative addition of a metal complex to a simple epoxide to yield a metallaoxetane. Calculations were done in order to probe the reactivity of the metallacycle.

Original languageEnglish
Pages (from-to)3316-3325
Number of pages10
JournalOrganometallics
Volume12
Issue number8
DOIs
Publication statusPublished - Jan 1 1993

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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    Calhorda, M. J., Galvão, A. M., Ünaleroglu, C., Zlota, A. A., Frolow, F., & Milstein, D. (1993). Rhodaoxetane: Synthesis, Structure, and Theoretical Evaluation. Organometallics, 12(8), 3316-3325. https://doi.org/10.1021/om00032a062