<em>Ansa</em>-titanocene pyrrolyl complexes: The synthesis and structural characterization of [Me<sub>2</sub>Si(C<sub>5</sub>Me<sub>4</sub>)<sub>2</sub>]Ti(NC<sub>4</sub>H<sub>4</sub>)X (X = H, Me, Cl and NC<sub>4</sub>H<sub>4</sub>) and [Me<sub>2</sub>Si(C<sub>5</sub>Me<sub>4</sub>)(C<sub>5</sub>Me<sub>3</sub>CH<sub>2</sub>)]Ti(NC<sub>4</sub>H<sub>4</sub>)

A series of titanium–pyrrolyl compounds, namely [Me2Si(C5Me4)2]Ti(NC4H4)X (X=H, Me, Cl, NC4H4) and [Me2Si(C5Me4)(C5Me3CH2)]Ti(NC4H4) has been synthesized and structurally characterized by X-ray diffraction. Analysis of the TiNC4H4 bond lengths in these complexes indicates that pyrrolyl does not, by comparison to dialkylamido, act as an efficient π-donor ligand. The fulvene complex [Me2Si(C5Me4)(C5Me3CH2)]Ti(NC4H4) is obtained via thermal elimination of CH4 and H2 from [Me2Si(C5Me4)2]Ti(NC4H4)Me and [Me2Si(C5Me4)2]Ti(NC4H4)H, respectively. The latter transformation is reversible, with [Me2Si(C5Me4)(C5Me3CH2)]Ti(NC4H4) reacting with H2 to give [Me2Si(C5Me4)2]Ti(NC4H4)H at room temperature. In accord with this reversibility, treatment of [Me2Si(C5Me4)2]Ti(NC4H4)H with D2 results in incorporation of deuterium into the hydride and one ring methyl group of each cyclopentadienyl ring of the [Me2Si(C5Me4)2] ligand.

一系列钛 - 吡咯化合物，即[Me₂Si(C₅Me₄)₂]Ti(NC₄H₄)X（X = H、Me、Cl、NC₄H₄）和[Me₂Si(C₅Me₄)(C₅Me₃CH₂)]Ti(NC₄H₄)已被合成，并通过X射线衍射进行了结构表征。对这些配合物中Ti - NC₄H₄键长的分析表明，与二烷基氨基相比，吡咯不是一种有效的π - 供体配体。富烯配合物[Me₂Si(C₅Me₄)(C₅Me₃CH₂)]Ti(NC₄H₄)是分别通过[Me₂Si(C₅Me₄)₂]Ti(NC₄H₄)Me和[Me₂Si(C₅Me₄)₂]Ti(NC₄H₄)H热消除CH₄和H₂而得到的。后一种转化是可逆的，[Me₂Si(C₅Me₄)(C₅Me₃CH₂)]Ti(NC₄H₄)在室温下与H₂反应生成[Me₂Si(C₅Me₄)₂]Ti(NC₄H₄)H。与这种可逆性一致，用D₂处理[Me₂Si(C₅Me₄)₂]Ti(NC₄H₄)H会导致氘掺入到氢化物以及[Me₂Si(C₅Me₄)₂]配体的每个环戊二烯基环的一个环甲基中。