Zirconium and titanium amido complexes with 3,3-dimethyl-1,5-diaza-8-oxacyclodecane; facile C-H activation of the macrocyclic rim.

Reaction of the dilithium salt of 3,3-dimethyl-1,5-diaza-8-oxacyclodecane, [(NLi)2O], with Zr(NEt2)2Cl2(thf)2 gave the formally 20e- complex [Zr(N2O)2]; metallation of the macrocycle [(NH)2O], with Ti(benzyl)4 gave rise to [(N2O)*Ti(benzyl)]2 in which the trianionic diamido (N2O)* was formed by an unprecedented C-H activation of the carbon [small alpha] to the amido nitrogen.

Studies on high-temperature amination reactions of aromatic chlorides using discrete palladium-N-heterocyclic carbene (NHC) complexes and in situ palladium/imidazolium salt protocols.

The palladium catalysed coupling of aryl chlorides and amines can be readily achieved with short reaction times when carried out at high temperatures under thermal or microwave conditions. These coupling protocols are successful using two co-ordinate palladium-N-heterocyclic carbene complexes, or imidazolium salt protocols.