Yttrium-catalysed dehydrocoupling of alanes with amines.

We report [Y{N(SiMe3)2}3] as a precatalyst for the dehydrocoupling of sterically demanding amines with β-diketiminate stabilised aluminium dihydrides. While simple fluorinated anilines readily undergo Al-H/N-H dehydrocoupling under thermal conditions, catalytic methods are required to achieve reasonable rates of reaction for ortho-substituted anilines or hindered aliphatic amines.

Preparation and properties of a series of structurally diverse aluminium hydrides supported by β-diketiminate and bis(amide) ligands.

The synthesis of a diverse series of hydride complexes of aluminium coordinated by N,N'-chelating ligands is reported. Reaction of [{2,6-(i)Pr2C6H3}NC(Me)CHC(Me)N(H)CH2CH2NMe2] with either LiAlH4 or Me3N·AlH3 allows isolation of the corresponding five-coordinate aluminium dihydride [κ(3)-{(2,6-(i)Pr2C6H3)NC(Me)CHC(Me)NCH2CH2NMe2}AlH2] (2). The latter complex demonstrates trigonal bipyramidal geometry in the solid-state.

Zirconocene dichloride catalyzed hydrodefluorination of C(sp 2)-F bonds.

A two-metal job: Four-coordinate aluminum dihydrides such as 1 are reported as terminal reductants for the selective title reaction. The heterobimetallic complex 2 has been isolated and shown to be catalytically competent.