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.
Highlights
Small-molecule activation is a topic of growing importance from both academic and societal aspects [1,2,3]
In 2017, Cloke made a similar reaction with a low-valent uranium reinforcing the subtle differences between the different pathways and the crucial role of the sterics in complex [16]
Whereas most of the small differences between the metric of 1 and the one of Cp*2Sm(C≡C–Ph)(thf) can find their source small differences between the metric of 1 and the one of Cp*2 Sm(C≡C–Ph)(thf) can find their source in the variation of the hindrance caused by the Cptt ligand, the different C≡C distance would better in the variation of the hindrance caused by the Cptt ligand, the different C≡C distance would better be explained by different electronic properties of the two complexes
Summary
Small-molecule activation is a topic of growing importance from both academic and societal aspects [1,2,3]. In 2017, Cloke made a similar reaction with a low-valent uranium reinforcing the subtle differences between the different pathways and the crucial role of the sterics in complex [16]. In 2017, Cloke made a similar reaction with a low-valent uranium complex [16] Based on these very important studies, we recently have reported the reductive disproportionation disproportionation of CO2 with bulky divalent samarium incorporating Cptt and Cpttt ligand
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