Multi-electron redox reactivity of a samarium(ii) hydrido complex.

Abstract

Well-defined low-valent molecular rare-earth metal hydrides are rare, and limited to Yb2+ and Eu2+ centers. Here, we report the first example of the divalent samarium(ii) hydrido complex [(CpAr5)SmII(μ-H)(DABCO)]2 (4) (CpAr5 = C5Ar5, Ar = 3,5-iPr2-C6H3; DABCO = 1,4-diazabicyclooctane) supported by a super-bulky penta-arylcyclopentadienyl ligand, resulting from the hydrogenolysis of the samarium(ii) alkyl complex [(CpAr5)SmII{CH(SiMe3)2}(DABCO)] (3). Complex 4 exhibits multi-electron redox reactivity toward a variety of substrates. Exposure of complex 4 to CO2 results in the formation of the trivalent samarium(iii) mixed-bis-formate/carbonate complex [(CpAr5)SmIII(μ-η2:η1-O2CH)(μ-η2:η2-CO3)(μ-η1:η1-O2CH)SmIII(CpAr5)(DABCO)] (8), mediated by hydride insertion and reductive disproportionation reactions. Complex 4 shows four-electron reduction toward four equivalents of CS2 to afford the trivalent samarium(iii) bis-trithiocarbonate complex [(CpAr5)SmIII(μ-η2:η2-CS3)(DABCO)]2 (9). A mechanistic study of the formation of complex 8 was carried out using DFT calculations.