3d–4f heterometallic complexes by the reduction of transition metal carbonyls with bulky LnII amidinates

Abstract

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)₂Sm^II(thf)₂] (DippForm = N,N′-bis(2,6-diisopropylphenyl)formamidinate) with [Co₂(CO)₈] resulted in the formation of a tetranuclear Sm–Co complex, [{(DippForm)₂Sm^III(thf)}₂{(μ-CO)₂Co(CO)₂}₂]. The product of the reaction of [(DippForm)₂Yb^II(thf)₂] and [Co₂(CO)₈] gives the dinuclear Yb–Co complex [{(DippForm)₂Yb^III(thf)}{(μ-CO)Co(CO)₃}] in toluene. The reaction of [(DippForm)₂Sm^II(thf)₂] was also carried with the neighbouring group 8 carbonyl complexes [Fe₂(CO)₉] and [Fe₃(CO)₁₂], resulting in a pentanuclear Sm^III–Fe complex, [{(DippForm)₂Sm^III}₂{(μ₃-CO)₂Fe₃(CO)₉}], featuring a triangular iron carbonyl cluster core.