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 language | English |
|---|---|
| Pages (from-to) | 3316-3325 |
| Number of pages | 10 |
| Journal | Organometallics |
| Volume | 12 |
| Issue number | 8 |
| Publication status | Published - 1993 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
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 journal › Article
}
TY - JOUR
T1 - Rhodaoxetane
T2 - Synthesis, structure, and theoretical evaluation
AU - Calhorda, Maria J.
AU - Galvão, Adelino M.
AU - Ünaleroglu, Canan
AU - Zlota, Andrei A.
AU - Frolow, Felix
AU - Milstein, David
PY - 1993
Y1 - 1993
N2 - 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.
AB - 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.
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M3 - Article
VL - 12
SP - 3316
EP - 3325
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 8
ER -