Reactivity of Yttrium Methyl Complexes: Hydrido Transfer
Capability of Selected Alkylalanes
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Abstract
The
reactivity of alkylaluminum hydrides HAlMe<sub>2</sub>, HAl(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>, and H<sub>2</sub>AlMes* (Mes*
= C<sub>6</sub>H<sub>2</sub><i>t</i>Bu<sub>3</sub>-2,4,6)
toward yttrium methyl complexes was assessed. From the reaction with
[Cp<sub>2</sub>YMe]<sub>2</sub> the corresponding methylated alkylaluminum
compounds could be isolated and characterized along with [Cp<sub>2</sub>Y(thf)(μ-H)]<sub>2</sub>, obtained upon workup in thf (Cp =
C<sub>5</sub>H<sub>5</sub> = cyclopentadienyl). Structurally characterized
complexes Cp<sub>14</sub>Y<sub>6</sub>H<sub>3</sub>Cl and Cp<sub>15</sub>Y<sub>6</sub>H<sub>3</sub> represent side-products of the transformation.
The reactions of [YMe<sub>3</sub>]<sub><i>n</i></sub> and
[(C<sub>5</sub>Me<sub>5</sub>)YMe<sub>2</sub>]<sub>3</sub> indicated
occurrence of hydrido transfer for H<sub>2</sub>AlMes* and led to
product mixtures for HAl(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>. Following the reaction of HAlMe<sub>2</sub> with these compounds
as well as the half-sandwich derivatives (C<sub>5</sub>Me<sub>4</sub>R)Y(AlMe<sub>4</sub>)<sub>2</sub> (R = Me, SiMe<sub>3</sub>) indicated
reversible hydrido binding, leading ultimately to the formation of
insoluble hydride clusters. The organoaluminum compounds [HAl(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>]<sub>3</sub>, [(μ-H)(Me)AlMes*]<sub>2</sub>, and Me<sub>2</sub>AlMes* were analyzed by X-ray crystallography
