Twenty five years of organic chemistry with diiodosamarium

Small molecule activation with divalent samarium triflate: a synergistic effort to cleave O2

“…On the other hand divalent lanthanides do not allow multiple electron transfers 4,6,18,19 since the trivalent form is the most stable one, except for Ce III that is easily oxidized to formal Ce IV . 5,6,[20][21][22][23][24] However, once the single electron transfer step has occurred, the development of a radical on the small molecule often leads to further reactivity, either radicalcoupling reactions 25,26 or the formation of dianionic species by combination of the radical intermediate with a second coordination metal compound. 27 The synergy between two metallic fragments provides two electrons for the reduction of the substrate and the reaction with N 2 O forms oxo dimers,…”

“…The chemistry of low-valent coordination compounds has multiple assets in which the small molecules activation is prominent because of the growing importance of transforming abundant, such as N 2 , H 2 O and O 2 . [1][2][3][4][5][6] and/or pollutant molecules, such as N 2 O, 7 NO x , 8 CO 9, 10 and CO 2 , 11 at low economical and environmental cost. In this context, electron rich transition metals complexes or low-valent uranium are often used since they allow multiple electron-transfer steps leading to the complete reductive cleavage of the considered small molecule.…”

N-aromatic heterocycle adducts of bulky [1,2,4-(Me3C)3C5H2]2Sm: synthesis, structure and solution analysis

“…The capacity that divalent lanthanides complexes have to transfer a single electron is of great interest since this monoelectronic reduction may lead to interesting chemical reactivity exemplified by the use of SmI 2 as a reducing agent in organic chemistry. 1,2 Moreover, the synthesis and reactivity of organometallic complexes of divalent lanthanides featuring Cp-type ligands has been studied for several decades [3][4][5][6][7][8] and, aside from the classical divalent lanthanides Eu, 9 Yb 10 and Sm, 11 non-classical molecular divalent lanthanides have emerged using bulky substituents branched on the cyclopentadienyl to stabilise the divalent metal centre. 8 These new complexes are not only a synthetic challenge but also lead to interesting reductive reactivity of small molecules, including reduction of N 2 , 12 CO 2 and CO. 6 Another aspect of this reactivity is the reaction with pyridine that features a coupling in the 4,4′-positions of the latter.…”

Atom economical coupling of benzophenone and N-heterocyclic aromatics with SmI2

“…[20][21][22][23][24][25] In particular, Kagan reported the reaction of ketones for the preparation of alcohols or pinacols, depending upon the reaction conditions. 26 After some of us demonstrated that this typical radical coupling induced by divalent lanthanides was reversible in multiple cases, [27][28][29][30] we were interested in investigating the Kagan reaction with benzophenone and SmI 2 in THF. The reaction with 1 eq.…”