Scandium-catalysed intermolecular hydroaminoalkylation of olefins with aliphatic tertiary amines.

A homoleptic scandium trialkyl complex in combination with a borate compound served as an excellent catalyst for the C-H addition of aliphatic tertiary amines to olefins. This highly regiospecific, 100% atom efficient C-H bond alkylation reaction was applicable to a wide variety of tertiary amines and olefins, including functionalised styrenes and unactivated α-olefins. This work represents the first example of rare-earth catalysed olefin hydroaminoalkylation and also the first example of catalytic C-H addition of aliphatic tertiary amines to olefins with any catalyst.

Bis(σ-B-H) complexes of copper(i): precursors to a heterogeneous amine-borane dehydrogenation catalyst.

A series of bis(σ-B-H) complexes of copper(i) have been prepared by displacement of arene solvent from a β-diketiminate copper(i) complex by four-coordinate boranes, H3B-L (L = NMe3, lutidine). In the presence of the same copper arene complex, the secondary amine-borane H3B-NMe2H undergoes dehydrogenation. We provide evidence for formation of a heterogengous catalyst from decomposition of the solution species.

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.

Mechanistic and cytotoxicity studies of group IV β-diketonate complexes.

Group IV metal complexes have previously shown promise as novel anticancer agents. Here, we discuss the mechanistic and cytotoxic nature of a series of group IV β-diketonate coordination complexes. Clear evidence that the ligands are exchangeable on the metal centre and that the β-diketonate ligands can act as potential drug delivery vehicles of the group IV metal ions was obtained.

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.