3d-4f heterometallic complexes by the reduction of transition metal carbonyls with bulky Ln${}^{II}$ amidinates

The redox chemistry between divalent lanthanide complexes bearing bulky amidinate ligands has been studied with 3d transition metal carbonyl complexes (iron and cobalt). The reaction of [(DippForm)${}_2$Sm${}^{ǁ}$(thf)${}_2$] (DippForm = N,N′-bis(2,6-diisopropylphenyl)formamidinate) with [Co${}_2$(CO)${}_8$] resulted in the formation of a tetranuclear Sm–Co complex, [{(DippForm)${}_2$Sm${}^{ǁǀ}$(thf)}${}_2${(μ-CO)${}_2$Co(CO)${}_2$}${}_2$]. The product of the reaction of [(DippForm)${}_2$Yb${}^{ǁ}$(thf)${}_2$] and [Co${}_2$(CO)${}_8$] gives the dinuclear Yb–Co complex [{(DippForm)${}_2$Yb${}^{ǁǀ}$(thf)}{(μ-CO)Co(CO)${}_3$}] in toluene. The reaction of [(DippForm)${}_2$Sm${}^{ǁ}$(thf)${}_2$] was also carried with the neighbouring group 8 carbonyl complexes [Fe${}_2$(CO)${}_9$] and [Fe${}_3$(CO)${}_{12}$], resulting in a pentanuclear Sm${}^{ǁǀ}$–Fe complex, [{(DippForm)${}_2$Sm${}^{ǁǀ}$}${}_2${(μ${}_3$-CO)${}_2$Fe${}_2$(CO)${}_9$}], featuring a triangular iron carbonyl cluster core.