Bulky Hybrid <i>C‐</i> Scorpionate/Amidinate Complexes of Lithium and Zinc

Lithiation of the bis(pyrazolyl)methanes H2C(PzAd,Me)2 (1 a) and H2C(PzPh,Ph)2 b) subsequent addition N,N’-diisopropylcarbodiimide in THF yields [(thf)Li{(PzAd,Me)2HC−C(=NiPr)(NiPr)}] (2 [(thf)Li{(PzPh,Ph)2HC−C(=NiPr)(NiPr)}] b). For comparison reasons, structure [(thf)Li{(PztBu,tBu)2HC−C(=NCy)(NCy)}] (I) has been determined as well. Protolysis with aqueous ammonium chloride solution gives (PzAd,Me)2HC−C(=NiPr)(NHiPr) (3 (PzPh,Ph)2HC−C(=NiPr)(NHiPr) Zincation diethylzinc leads to formation [EtZn{(PzAd,Me)2HC−C(=NiPr)(NiPr)}] (4 [EtZn{(PzPh,Ph)2HC−C(=NiPr)(NiPr)}] The metathetical approach allows preparation isolation [ClZn{(PzPh,Ph)2HC−C(=NiPr)(NiPr)}] (5). A molecular structures lithium zinc complexes elucidate influence electronegativity on structural parameters because tetra-coordinate Li Zn ions have very similar radii.