Synthese und Thermolyse von α-Titanocenyl-substituierten Dimethylethern: die überraschende Bildung von [(CH₃Cp)Ti(OCH₃)Cl]₄/ Syntheses and Thermolysis of a-Titanocenyl-Substituted Dimethylethers: the Unexpected Formation of [(CH₃Cp)Ti(OCH₃)Cl]₄

Abstract

<jats:title>Abstract</jats:title><jats:p>Reaction of the Grignard-Reagent ClMgCH<jats:sub>2</jats:sub>OCH , (2) with (RCp)<jats:sub>2</jats:sub>TiCl<jats:sub>2</jats:sub> (5a) (R = H). 5b (R = CH,) yields the titanocene(methoxymethyl)chlorides (RCp)<jats:sub>2</jats:sub>Ti(Cl)CH<jats:sub>2</jats:sub>OCH<jats:sub>3</jats:sub>, 7a and 7b. Thermal decomposition of 7b (2 min, 110 °C in toluene) yields the paramagnetic titanium (III) complex [(CH<jats:sub>3</jats:sub>Cp)Ti(OCH<jats:sub>3</jats:sub>)Cl]<jats:sub>4</jats:sub> (8) in addition to the organic products ethylene and dimethvlether. The tetranuclear complex 8 crystallizes in space-group P2<jats:sub>1</jats:sub>/n with a = 9.125(2), b = 8.899(1), c = 20.226(2) Å and β - 92.804(9)°. In 8 the Ti<jats:sub>4</jats:sub>-core is alternatingly doubly-bridged by μ-chloro- and μ-methoxy ligands.</jats:p>