Themed collection d0 organometallics in catalysis

Welcome to this themed issue of Dalton Transactions entitled “d⁰ organometallics in catalysis”.

Selected examples concerning effects of both cyclopentadienyl fragment (Cp′) and anionic donor ligand (Y) in nonbridged modified half-titanocenes of the type, Cp′TiX₂(Y) (X = halogen, alkyl), as new type of olefin polymerisation catalysts have been reviewed.

From a series of N,N′-disubstituted-1,1′-binaphthyl-2,2′-diamines, several group 3 metal complexes were synthesized and applied to catalysis of intramolecular alkene hydroamination.

Variation of the N-substituent of chiral imidazoline ligands has a profound effect on the ligand redistribution in calcium complexes; the effect on catalytic hydroamination/cyclisation has been probed.

The catalytic dehydrogenation of dimethylamine borane using well-defined group 4 metallocene alkyne complexes and homoleptic group 4 amido complexes is presented.

The mononuclear titanium compounds supported with a silyl-linked bis(amidinate) ligand were prepared, and showed good activity towards ethylene polymerization after activation with MAO.

Relating to the catalytic dehydrocoupling of secondary phosphine substrates, zirconium phosphide complexes supported by triamidoamine and pentamethylcyclopentadienyl ligands exhibit different stability that is attributed to β-hydride elimination.

Reactions of tert-butylisocyanide with a cyclometalated ditantalum hydride were investigated.

The intermolecular hydroamination of oxygen-substituted allenes serves as a route toward amine proligands which in turn can be used for the synthesis of N,O-chelating complexes of zirconium and titanium. The new complexes are also effective aminoalkene cyclohydroamination precatalysts.

The molecular structures of both TaMe₃Cl₂ and Ta(PMe₃)₂Me₃Cl₂ have been determined by X-ray diffraction thereby demonstrating that, in the solid state, these complexes respectively adopt trigonal bipyramidal and capped trigonal prismatic geometries.

Titanium hydroamination rates are enhanced by the addition of electron-withdrawing aryl groups in the 3-position of a dipyrrolylmethane ancillary ligand.

Key intermediates of thiol oxidation catalyzed by amavadin have been investigated by means of DFT and QTAIM methods.

The first monomeric anhydrous scandium tris(8-quinolinolate) complex has been synthesized and characterized by X-ray analysis and DFT calculations.

Bis(indenyl)zirconium and ansa-titanium dinitrogen complexes were explored as isolable reduced metallocene species for the cyclisation of α,ω-dienes.

Four-coordinate, cationic, M–Me (M = Nb, Ta) complexes were synthesized and tested for their reactivity toward unsaturated and protic small-molecule substrates.

Scandium amide complexes containing a cyclen-derived (NNNN) macrocyclic ligand initiated the ring-opening polymerization of meso-lactide.

Heteroleptic and homoleptic group 2 silylamides catalyse the dehydrocoupling of dialkylamine boranes, R₂NH·BH₃, via an apparent elimination/insertion mechanism. Key intermediates containing [R₂NBH₂R₂NBH₃]⁻ anions are formed by M–N insertion of olefin-isoelectronic R₂NBH₂ species.

Rare earth alkyl complexes activated by aluminium alkyls and organoborates exhibited high trans-1,4 selectivity for butadiene and isoprene homo- and co-polymerizations.

Five and four-coordinate titanium complexes with tridentate dianionic arylsulfide ligands have been synthesized, characterized and applied for ethylene polymerization.

Arene substituted constrained geometry catalyst precursors are prepared, characterized and an examination of their activities for the polymerization and copolymerization of styrene and ethylene are reported.