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3 results on '"Mathieu Xémard"'

1. Phenylacetylene and Carbon Dioxide Activation by an Organometallic Samarium Complex

Author

Violaine Goudy, Mathieu Xémard, Simon Karleskind, Marie Cordier, Carlos Alvarez Lamsfus, Laurent Maron, and Grégory Nocton

Subjects
small molecule activation, samarium complexes, C–H activation, Inorganic chemistry, QD146-197
Abstract

Small molecule activation is a topic of growing importance and the use of low-valent f-elements to perform these reactions is nowadays well established. The complex Cptt2Sm(thf) (1, Cptt = 1,3-(tBu)2Cp) is shown to activate the alkyne C–H bond of phenylacetylene to form the Cptt2Sm(C≡C–Ph)(thf) complex. The subsequent reaction of this Sm(III) complex with CO2 leads to the CO2 insertion, yielding a dimeric [Cptt2Sm(O2C–C≡C–Ph)]2 complex (2), in which the carbon dioxide has been inserted in the Sm–C bond. Along with the experimental chemical structure analysis, theoretical calculations have been performed in order to rationalize the formation of 1 and 2.

Published
2018
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2. Small molecule activation with divalent samarium triflate: a synergistic effort to cleave O

Author

Mathieu, Xémard, Marie, Cordier, Elisa, Louyriac, Laurent, Maron, Carine, Clavaguéra, and Grégory, Nocton

Abstract

The divalent samarium triflate salt does not react with CO2 or water, but does react with traces of O2 or N2O to form a tetrameric bis-oxo samarium motif. The reaction with O2 is a 4e- reductive cleavage where the electrons are coming from four different samarium centers. This highlights a rare synergistic effect for cleaving O2, which has no precedent in divalent lanthanide complexes. Additionally, the addition of CO2 to the tetrameric bis-oxo intermediate leads to the formation of a tetrameric bis-carbonate samarium triflate. Thus, the concomitant reaction of CO2 with traces of O2 leads to the same bis-carbonate tetrameric assembly.

Published
2018

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