Calcium Complexes Having Different Amidinate Ligands - Synthesis and Structural Diversity

A one-pot reaction of α-diimine ligand 1,4-disubstituted diazabutadienes (DAD) with potassium benzyl and anhydrous calcium iodide in 1:1:1 molar ratio afforded unprecedented 3-phenylprop-2-ene-di-amido calcium compound [κ2-(THF)4Ca{DippNC(=CHPh)CH2NDipp}] (1) (Dipp = 2,6-diisopropylphenyl) in good yield. The solid-state structure of the compound 1 revealed the formation of dianionic 3-phenylprop-2-ene-di-amido ligand having an exocyclic olefinic bond derived from neutral α-diimine fragment. However, analogous reactions with three different carbodiimides (RN=C=NR; R=Cy, iPr and tBu) with alkyl potassium and anhydrous calcium diiodide yielded corresponding homoleptic calcium compounds with amidinato ligand [κ2-(THF)2Ca{RN=C(CH2Ph)NR}2] [R=Cy (2), iPr (3) and tBu (4)]. A separate reaction of DAD ligand, LiCH2SiMe3 and anhydrous ZnCl2 in diethylether solvent produced tri-coordinated zinc compound [κ2- {DippN=C(CH2SiMe3)CH2NDipp}Zn[κ1-{DippN=C(CH2SiMe3)CH2N-Dipp}] (5) having amidinato moieties in the zinc coordination sphere in high yield. Molecular structures of compounds 2–5 in their solid states were also established