Keywords
diazabutadienes
diimino ligands
erbium complexes
lanthanides
salt metathesis
structure.
terbium complexes
Abstract
Treatment of 1,4-diazabutadienes (DADs) of formula DippN=C(R)C(R)=NDipp (Dipp = 2,6-Pr2iC6H3, R = H or Me) with 2 or 1 equiv. of potassium metal in THF leads to the corresponding dianions (DAD2-) or radical anions (DAD•−), respectively. The subsequent salt metathesis between LnCl3 (Ln = Tb or Er) and the above dianions affords dimeric monochlorido complexes [(DAD2-)Ln(THF)2(μ-Cl)]2 with bridging chlorine atoms between the lanthanides. The reaction of the radical anion species with LnCl3, if R = H, gives monomeric dichlorido complexes (DAD•−)Ln(THF)2Cl2; however, if R = Me, the activation of one methyl group occurs, which in the reaction with TbCl3 leads to the formation of a product with shifted double bonds [DippN=C(Me)C(=CH2)N(Dipp)]Tb(THF)2Cl2.
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