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

The oxidative addition of sp2 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 (E)-ß-metalation of the alkene. For this bimetallic system, alkene binding appears to be essential for the reaction to occur. Experimental and computational insights suggest an unusual reaction pathway in which a (2 + 2) cycloaddition intermediate is directly converted into the hydrido vinyl product via an intramolecular sp2 C-H bond activation across the two metals. The key C-H cleavage step proceeds through a highly asynchronous transition state near the boundary between a concerted and a stepwise mechanism influenced by the resonance stabilization ability of the aryl substituent. The metalated alkenes can be further functionalized, which has been demonstrated by the (E)-selective phosphination of the employed styrenes.

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 hydride complex with exogeneous ligands (CO and CNR, R = Me, tBu, Xyl = 2,6-Me2C6H3). Based on DFT calculations we suggest that these reactions occur through a dyotropic rearrangement, this involves initial coordination of the exogenous ligand at Al followed by migration to Fe, with simultaneous migration of a hydride ligand from Fe to Al. Such processes are rare for heterometallic complexes. We study the bonding and mechanism of the dyotropic rearrangement through in-depth computational analysis (NBO, IBOs, CLMO analysis, QTAIM, NCIplot, IMGH), shedding new light on how the electronic structure of the heterometallic core responds to the migration of ligands between metal sites. The dyotropic rearrangement fundamentally changes the nature of the hydride ligands, exposing new nucleophilic reactivity as evidenced by insertion reactions with CO2, isocyanates, as well as isocyanides.

Double Deprotonation of CH3 CN by an Iron-Aluminium Complex.

Herein we present the first double deprotonation of acetonitrile (CH3 CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN]2- dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH2 CN]- complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts.[1, 2] The isolation of a [CHCN]2- dianion through simple deprotonation of CH3 CN also offers the possibility of establishing a broader chemistry of this motif.

Double Deprotonation of CH3CN by an Iron-Aluminium Complex.

Herein we present the first double deprotonation of acetonitrile (CH3CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN]2- dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH2CN]- complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts.[1, 2] The isolation of a [CHCN]2- dianion through simple deprotonation of CH3CN also offers the possibility of establishing a broader chemistry of this motif.

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

Ti(IV) and Ti(III) complexes using the tBuPCP ligand have been synthesized (tBuPCP = C6H3-2,6-(CH2PtBu2)2). The [tBuPCP]Li synthon can be reacted with TiCl4(THF)2 to form (tBuPCP)TiCl3 (1) in limited yields due to significant reduction of the titanium synthon. The Ti(III) complex (tBuPCP)TiCl2 (2) has been further characterized. This can have half an equivalent of halide abstracted to form [{(tBuPCP)TiCl}2{µ-Cl}][B(C6F5)4] (3) and can also be methylated, forming (tBuPCP)TiMe2 (4). All the Ti(III) complexes have been characterized using EPR and X-ray crystallography, giving insight into their electronic structures, which are further supported by DFT calculations.