Dyotropic Rearrangement of an Iron-Aluminium Complex.

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well-defined Fe-Al dihydride complex with exogenous ligands (CO and CNR, R=Me, Bu, Xyl=2,6-MeCH).

Double Deprotonation of CHCN by an Iron-Aluminium Complex.

Herein we present the first double deprotonation of acetonitrile (CHCN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN] dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions.

Vinylic C-H Activation of Styrenes by an Iron-Aluminum Complex.

The oxidative addition of sp C-H bonds of alkenes to single-site transition-metal complexes is complicated by the competing π-coordination of the C═C double bond, limiting the examples of this type of reactivity and onward applications. Here, we report the C-H activation of styrenes by a well-defined bimetallic Fe-Al complex. These reactions are highly selective, resulting in the ()-β-metalation of the alkene.

PCP Pincer Complexes of Titanium in the +3 and +4 Oxidation States.

Ti(IV) and Ti(III) complexes using the PCP ligand have been synthesized (PCP = CH-2,6-(CHPBu)). The [PCP]Li synthon can be reacted with TiCl(THF) to form (PCP)TiCl () in limited yields due to significant reduction of the titanium synthon. The Ti(III) complex (PCP)TiCl () has been further characterized.

Double Deprotonation of CH CN by an Iron-Aluminium Complex.

Herein we present the first double deprotonation of acetonitrile (CH CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN] dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions.