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Different Inertness of Titanocene [Cp 2 Ti] and Decamethyltitanocene [Cp* 2 Ti] in Reactions with N , N ‐Bis(trimethylsilyl)sulfurdiimide – Elimination of Tetramethylfulvene and Formation of Half‐Titanocene Complexes
Author(s) -
Kaleta Katharina,
Kessler Monty,
Beweries Torsten,
Arndt Perdita,
Spannenberg Anke,
Rosenthal Uwe
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200242
Subject(s) - chemistry , fulvene , trimethylsilyl , alkyne , intramolecular force , ligand (biochemistry) , medicinal chemistry , hydride , tin , dichloromethane , stereochemistry , crystallography , metal , catalysis , organic chemistry , biochemistry , receptor , solvent
The reaction of the titanocene alkyne complex [Cp* 2 Ti(η 2 ‐Me 3 SiC 2 SiMe 3 )] ( 1 ) (Cp* = η 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 C–H and N–S 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* 2 Ti] is less stable than [Cp 2 Ti]; a possible reason was found to be the well‐known intramolecular C–H activation yielding the tautomeric tetramethylfulvene hydride species, from which 1,2,3,4‐tetramethylfulvene ( 3 ) can dissociate.