Heteroleptic Germanium(II) and Tin(II) Chlorides Supported by Anionic Ligands Derived from 2,3‐Dimethyl‐1,4‐diaza‐1,3‐butadiene

The syntheses and structures of heteroleptic germanium(II) and tin(II) chlorides supported by anionic ligands derived from 2,3‐dimethyl‐1,4‐diaza‐1,3‐butadiene are described. The reaction of ArN=C(Me)C(Me)=NAr ( L , Ar = 2,6‐ i Pr 2 C 6 H 3 ) with MeLi in Et 2 O, followed by treatment with GeCl 2 · dioxane or SnCl 2 , afforded [ L 1 ECl] [ L 1 = ArN=C(Me)C(Me) 2 NAr; E = Ge ( 1 ), Sn ( 2 )]. Moreover, L 2 Li [ L 2 = ArN=C(Me)C(=CH 2 )NAr] reacted with GeCl 2 · dioxane in Et 2 O to form [{C(=CH)NAr}{C(Me)=NAr}] 2 (GeCl) 2 ( 3 ). The byproducts are [{C(CH 2 )NAr}{C(Me)=NAr}Ge] 2 ( 4 ) and L 2 H ( 5 ). Furthermore, the reaction of L with LiN i Pr 2 in Et 2 O, followed by treatment with SnCl 2 , afforded [ L 2 SnCl] ( 6 ). Compounds 1 – 4 and 6 have been characterized by NMR spectroscopy and X‐ray crystallography.