Organoaluminum Silylamido Complexes

The reaction between [Et<INF>2</INF>AlCl] and 1 equiv of HN(SiMe<INF>3</INF>)<INF>2</INF> in CH<INF>2</INF>Cl<INF>2</INF> afforded colorless crystals of [Et<INF>2</INF>AlCl{NH(SiMe<INF>3</INF>)<INF>2</INF>}] (<BO>1</BO>). In contrast, reaction of [Et<INF>2</INF>AlCl] with 1 equiv of HN(SiMe<INF>2</INF>H)<INF>2</INF> or HN^tBu(SiMe<INF>3</INF>) resulted in the isolation of dimers, of the type [EtAlCl{NH(R‘)}]<INF>2</INF> (<BO>2</BO>, R‘ = SiMe<INF>2</INF>H; <BO>3</BO>, R‘ = ^tBu). Reaction of [Et<INF>3</INF>Al] with 1 equiv of HN(SiMe<INF>2</INF>H)<INF>2</INF> or HN(SiMe<INF>3</INF>)<INF>2</INF> yielded the expected dimeric complexes, [Et<INF>2</INF>Al{N(SiMe<INF>2</INF>H)<INF>2</INF>}]<INF>2</INF> (<BO>4</BO>) and [Et<INF>2</INF>Al{N(SiMe<INF>3</INF>)<INF>2</INF>}]<INF>2</INF> (<BO>5</BO>), via ethane elimination. The related reaction between [MeAlCl<INF>2</INF>] and HN^tBu(SiMe<INF>3</INF>) in CH<INF>2</INF>Cl<INF>2</INF> solution resulted in the formation of the 1:1 adduct [MeAlCl<INF>2</INF>{NH<INF>2</INF>(^tBu)}] (<BO>6</BO>). The structures of compounds <BO>1</BO> and <BO>6</BO> have been determined by X-ray crystallography. In addition, the decomposition of <BO>1</BO> and <BO>6</BO> has been studied by thermal gravimetric analysis.