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

Deprotonation
evaluation
rings
Epoxy Compounds
Coordination Complexes
synthesis
Hydrogen bonds
Demonstrations
epoxy compounds
Metals
butenes
Oxygen
metals
closures
Geometry
reactivity
hydrogen bonds
orbitals
optimization
oxides

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.

Rhodaoxetane : Synthesis, structure, and theoretical evaluation. / Calhorda, Maria J.; Galvão, Adelino M.; Ünaleroglu, Canan; Zlota, Andrei A.; Frolow, Felix; Milstein, David.

In: Organometallics, Vol. 12, No. 8, 1993, p. 3316-3325.

Research output: Contribution to journalArticle

Calhorda, MJ, Galvão, AM, Ünaleroglu, C, Zlota, AA, Frolow, F & Milstein, D 1993, 'Rhodaoxetane: Synthesis, structure, and theoretical evaluation', Organometallics, vol. 12, no. 8, pp. 3316-3325.
Calhorda MJ, Galvão AM, Ünaleroglu C, Zlota AA, Frolow F, Milstein D. Rhodaoxetane: Synthesis, structure, and theoretical evaluation. Organometallics. 1993;12(8):3316-3325.
Calhorda, Maria J. ; Galvão, Adelino M. ; Ünaleroglu, Canan ; Zlota, Andrei A. ; Frolow, Felix ; Milstein, David. / Rhodaoxetane : Synthesis, structure, and theoretical evaluation. In: Organometallics. 1993 ; Vol. 12, No. 8. pp. 3316-3325.
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