Zur Reaktivität von Titanocenkomplexen [Ti(Cp′) 2 (η 2 ‐Me 3 SiC≡CSiMe 3 )] (Cp′ = Cp, Cp*) gegenüber Benzoldicarbonsäuren

On the Reactivity of Titanocene Complexes [Ti(Cp′) 2 (η 2 ‐Me 3 SiC≡CSiMe 3 )] (Cp′ = Cp, Cp*) towards Benzenedicarboxylic Acids Titanocene complexes [Ti(Cp′) 2 (BTMSA)] ( 1a , Cp′ = Cp = η 5 ‐C 5 H 5 ; 1b , Cp′ = Cp* = η 5 ‐C 5 Me 5 ; BTMSA = Me 3 SiC≡CSiMe 3 ) were found to react with iodine and methyl iodide yielding [Ti(Cp′) 2 (μ‐I) 2 ] ( 2a / b ; a refers to Cp′ = Cp and b to Cp′ = Cp*), [Ti(Cp′) 2 I 2 ] ( 3a / b ) and [Ti(Cp′) 2 (Me)I] ( 4a / b ), respectively. In contrast to 2a , complex 2b proved to be highly moisture sensitive yielding with cleavage of HCp* [{Ti(Cp*)I} 2 (μ‐O)] ( 7 ). The corresponding reactions of 1a / b with p ‐cresol and thiophenol resulted in the formation of [Ti(Cp′) 2 {O( p ‐Tol)} 2 ] ( 5a / b ) and [Ti(Cp′) 2 (SPh) 2 ] ( 6a / b ), respectively. Reactions of 1a and 1b with 1, n ‐benzenedicarboxylic acids ( n = 2–4) resulted in the formation of dinuclear titanium(III) complexes of the type [{Ti(Cp′) 2 } 2 {μ‐1, n ‐(O 2 C) 2 C 6 H 4 }] ( n = 2, 8a / b ; n = 3, 9a / b ; n = 4, 10a / b ). All complexes were fully characterized analytically and spectroscopically. Furthermore, complexes 7 , 8b , 9a ·THF, 10a / b were also be characterized by single‐crystal X‐ray diffraction analyses.