Synthesis and Characterization of Titanium 7‐Azaindolato Complexes and their Lithium Precursors

Two differently 2‐substituted 7‐azaindoles (substituent = H ( 1‐H) , t ‐Bu ( 1‐ t Bu )) react with n ‐butyllithium in tmeda to give different Li complexes. Using the ligand 1‐H , the binuclear complex [(tmeda)Li(azH)] 2 ( 2‐H ) is formed. The sterically more demanding ligand 1‐ t Bu leads to formation of the mononuclear Li complex (tmeda)Li(az t Bu) ( 2‐ t Bu ). The decamethyltitanocene bis(trimethylsilyl)acetylene complex Cp* 2 Ti(η 2 ‐Me 3 SiC 2 SiMe 3 ) ( 3a ) reacts with 7‐azaindole ( 1‐H ) to give the dark red titanocene(III) complex 4 . Using the sterically more demanding 1‐ t Bu ligand upon deprotonation with dialkylmagnesium, followed by subsequent salt metathesis with (Cp 2 TiCl) 2 , the dark green titanocene(III) heterometallacyclic complex 5 is obtained. Complexes 2 ‐ H , 2 ‐ t Bu and 5 were characterized by X‐ray analyses.