Rhodaoxetane: Synthesis, Structure, and Theoretical Evaluation

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

doi:10.1021/om00032a062

Rhodaoxetane: Synthesis, Structure, and Theoretical Evaluation

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

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

41 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 language	English
Pages (from-to)	3316-3325
Number of pages	10
Journal	Organometallics
Volume	12
Issue number	8
DOIs	https://doi.org/10.1021/om00032a062
Publication status	Published - Jan 1 1993

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Rhodaoxetane: Synthesis, Structure, and Theoretical Evaluation",

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) {\AA}] and CO [1.416(12) {\AA}], 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 H{\"u}ckel 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.",

author = "Calhorda, {Maria J.} and Galv{\~a}o, {Adelino M.} and Canan {\"U}naleroglu and Zlota, {Andrei A.} and Felix Frolow and David Milstein",

year = "1993",

month = jan,

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doi = "10.1021/om00032a062",

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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 - 1993/1/1

Y1 - 1993/1/1

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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