Different Inertness of Titanocene [Cp2Ti] and Decamethyltitanocene [Cp*2Ti] in Reactions with N,N-Bis(trimethylsilyl)sulfurdiimide - Elimination of Tetramethyl-fulvene and Formation of Half-Titanocene Complexes

作者：Kaleta Katharina; Kessler Monty; Beweries Torsten^*; Arndt Perdita; Spannenberg Anke; Rosenthal Uwe

来源：European Journal of Inorganic Chemistry, 2012, (21): 3388-3393.

DOI：10.1002/ejic.201200242

• C-H activation
• Metallacycles
• Metallocenes
• Titanium
• Structure elucidation

The reaction of the titanocene alkyne complex [Cp*2Ti(?2-Me3SiC2SiMe3)] (1) (Cp* = ?5-pentamethylcyclopentadienyl) with N,N-bis(trimethylsilyl)sulfurdiimide (2) results in the formation of 1,2,3,4-tetramethylfulvene (3) as well as three titanium complexes 4, 5 and 6. During the reaction, formal elimination of one Cp* ligand induces a series of CH and NS bond activation steps, thus yielding the products. The molecular structures of complex 5 and of the free fulvene were determined by X-ray crystallographic analysis. Evidently, in these reactions [Cp*2Ti] is less stable than [Cp2Ti]; a possible reason was found to be the well-known intramolecular CH activation yielding the tautomeric tetramethylfulvene hydride species, from which 1,2,3,4-tetramethylfulvene (3) can dissociate.

• 出版日期2012-7