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Zur Reaktivität von Titanocenkomplexen [Ti(Cp′) 2 (η 2 ‐Me 3 SiC≡CSiMe 3 )] (Cp′ = Cp, Cp*) gegenüber Benzoldicarbonsäuren
Author(s) -
Albrecht Carolin,
Krüger Thomas,
Wagner Christoph,
Rüffer Tobias,
Lang Heinrich,
Steinborn Dirk
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200800350
Subject(s) - reactivity (psychology) , chemistry , stereochemistry , crystallography , methyl iodide , iodide , crystal structure , medicinal chemistry , inorganic chemistry , medicine , alternative medicine , pathology
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.