Rhodaoxetane: Synthesis, structure, and theoretical evaluation

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

Research output: Contribution to journalArticle

39 Citations (Scopus)

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
Publication statusPublished - 1993

    Fingerprint

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

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.