Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRhIII-H/D]+ macrocyclic complexes by methyl radicals in aqueous solutions

Lioubov Kats; Eric Maimon; Dan Meyerstein

doi:10.1002/chem.200902632

Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRh^III-H/D]⁺ macrocyclic complexes by methyl radicals in aqueous solutions

Lioubov Kats, Eric Maimon, Dan Meyerstein

Department of Chemical Sciences

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

2 Scopus citations

Abstract

Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRh^III-H/D]⁺ macrocyclic complexes by methyl radicals in aqueous solutions were studied. All solutions were prepared from analytical grade chemicals and distilled water that was passed through a Millipore setup, the final resistance being above 10 Mωcm^-1. The trans and cis- [(L)ClRh^III-H]⁺ complexes were synthesized. Gas chromatography analysis was performed on a HP 5890 gas chromatograph on a pack Q column with FID and TCD detectors. It was concluded that methyl radicals abstract an hydrogen atom and not a chlorine atom from [(L)ClRh ^III(H₂O)}⁺. The results suggest that the mechanism of hydrogen abstraction from M-H groups might differ considerably from C-H groups.

Original language	English
Pages (from-to)	460-463
Number of pages	4
Journal	Chemistry - A European Journal
Volume	16
Issue number	2
DOIs	https://doi.org/10.1002/chem.200902632
State	Published - 11 Jan 2010

Keywords

Elimination
Isotope effects
Radical reactions
Rhodium

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10.1002/chem.200902632

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title = "Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRhIII-H/D]+ macrocyclic complexes by methyl radicals in aqueous solutions",

abstract = "Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRhIII-H/D]+ macrocyclic complexes by methyl radicals in aqueous solutions were studied. All solutions were prepared from analytical grade chemicals and distilled water that was passed through a Millipore setup, the final resistance being above 10 Mωcm-1. The trans and cis- [(L)ClRhIII-H]+ complexes were synthesized. Gas chromatography analysis was performed on a HP 5890 gas chromatograph on a pack Q column with FID and TCD detectors. It was concluded that methyl radicals abstract an hydrogen atom and not a chlorine atom from [(L)ClRh III(H2O)\}+. The results suggest that the mechanism of hydrogen abstraction from M-H groups might differ considerably from C-H groups.",

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AU - Meyerstein, Dan

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N2 - Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRhIII-H/D]+ macrocyclic complexes by methyl radicals in aqueous solutions were studied. All solutions were prepared from analytical grade chemicals and distilled water that was passed through a Millipore setup, the final resistance being above 10 Mωcm-1. The trans and cis- [(L)ClRhIII-H]+ complexes were synthesized. Gas chromatography analysis was performed on a HP 5890 gas chromatograph on a pack Q column with FID and TCD detectors. It was concluded that methyl radicals abstract an hydrogen atom and not a chlorine atom from [(L)ClRh III(H2O)}+. The results suggest that the mechanism of hydrogen abstraction from M-H groups might differ considerably from C-H groups.

AB - Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRhIII-H/D]+ macrocyclic complexes by methyl radicals in aqueous solutions were studied. All solutions were prepared from analytical grade chemicals and distilled water that was passed through a Millipore setup, the final resistance being above 10 Mωcm-1. The trans and cis- [(L)ClRhIII-H]+ complexes were synthesized. Gas chromatography analysis was performed on a HP 5890 gas chromatograph on a pack Q column with FID and TCD detectors. It was concluded that methyl radicals abstract an hydrogen atom and not a chlorine atom from [(L)ClRh III(H2O)}+. The results suggest that the mechanism of hydrogen abstraction from M-H groups might differ considerably from C-H groups.

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KW - Isotope effects

KW - Radical reactions

KW - Rhodium

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Substantial inverse isotope effects in the hydrogen atom abstraction from [(L)ClRh^III-H/D]⁺ macrocyclic complexes by methyl radicals in aqueous solutions

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