A Combined Experimental and Theoretical Investigation of Arene-Supported Actinide and Ytterbium Tetraphenolate Complexes.

Modular tetraphenolate ligands tethered with a protective arene platform (para-phenyl or para-terphenyl) are used to support mononuclear An(IV) (An = Th, U) complexes with an exceptionally large and open axial coordination site at the metal. The base-free complexes and a series of neutral donor adducts were synthesized and characterized by spectroscopies and single-crystal X-ray diffraction. Anionic Th(IV) -ate complexes with an additional axial aryloxide ligand were also synthesized and characterized. The para-phenyl-tethered mononuclear complexes exhibit rare An(IV)-arene interactions, and the An(IV)-arene distance broadly increases with axial donor strength. The para-terphenyl-tethered complexes have almost no interaction with the arene base, isolating the central metal cation. Computational analysis of the mononuclear complexes and their reduced analogues, and Yb(III) congeners, as well as the effect of additional donor ligand binding, seek to elucidate the electronic structure of the metal-arene interactions and establish whether they, or their reduced or oxidized counterparts, could function as molecular qubits.

Instantaneous and Phosphine-Catalyzed Arene Binding and Reduction by U(III) Complexes.

Neutral arenes such as benzene have never been considered suitable ligands for electropositive actinide cations, yet we find that even simple UIII UX3 aryloxide complexes such as U(ODipp)3 bind and reduce arenes spontaneously at room temperature, forming inverse arene sandwich (IAS) complexes XnU(µ-C6D6)UXm (X = ODipp, n=2, m=3; X = OBMes2 n=m=2 or 3) (ODipp = OC6H3iPr2-2,6; Mes = 2,4,6-Me3-C6H2). In some of these cases, further arene reduction has occured as a result of X ligand redistribution. These unexpected spontaneous reactions explain the anomalous spectra and reported lack of further reactivity of strongly reducing UIII centers of U(ODipp)3. Phosphines that are not considered suitable ligands for actinides can catalyze the formation of the IAS complexes. This enables otherwise inaccessible asymmetric and less congested IAS complexes to be isolated and the bonding in this series compared.

Author Correction: Coupling dinitrogen and hydrocarbons through aryl migration.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Coupling dinitrogen and hydrocarbons through aryl migration.

The activation of abundant molecules such as hydrocarbons and atmospheric nitrogen (N2) remains a challenge because these molecules are often inert. The formation of carbon-nitrogen bonds from N2 typically has required reactive organic precursors that are incompatible with the reducing conditions that promote N2 reactivity1, which has prevented catalysis. Here we report a diketiminate-supported iron system that sequentially activates benzene and N2 to form aniline derivatives. The key to this coupling reaction is the partial silylation of a reduced iron-dinitrogen complex, followed by migration of a benzene-derived aryl group to the nitrogen. Further reduction releases N2-derived aniline, and the resulting iron species can re-enter the cyclic pathway. Specifically, we show that an easily prepared diketiminate iron bromide complex2 mediates the one-pot conversion of several petroleum-derived arenes into the corresponding silylated aniline derivatives, by using a mixture of sodium powder, crown ether, trimethylsilyl bromide and N2 as the nitrogen source. Numerous compounds along the cyclic pathway are isolated and crystallographically characterized, and their reactivity supports a mechanism for sequential hydrocarbon activation and N2 functionalization. This strategy couples nitrogen atoms from N2 with abundant hydrocarbons, and maps a route towards future catalytic systems.

Gold-alkynyls in catalysis: alkyne activation, gold cumulenes and nuclearity.

The use of cationic gold(i) species in the activation of substrates containing C[triple bond, length as m-dash]C bonds has become a valuable tool for synthetic chemists. Despite the seemingly simple label of 'alkyne activation', numerous patterns of reactivity and product structure are observed in systems employing related substrates and catalysts. The complications of mechanistic determination are compounded as the number of implicated gold(i) centres involved in catalysis increases and debate about the bonding in proposed intermediates clouds the number and importance of potential reaction pathways. This perspective aims to illustrate some of the principles underpinning gold-alkynyl interactions whilst highlighting some of the contentious areas in the field and offering some insight into other, often ignored, mechanistic possibilities based on recent findings.

Dispersion, solvent and metal effects in the binding of gold cations to alkynyl ligands: implications for Au(I) catalysis.

The coordination modes of the [Au(PPh3)](+) cation to metal alkynyl complexes have been investigated. On addition to ruthenium, a vinylidene complex, [Ru(η(5)-C5H5)(PPh3)2([double bond, length as m-dash]C[double bond, length as m-dash]CPh{AuPPh3})](+), is obtained while addition to a gold(iii) compound gives di- and trinuclear gold complexes depending on the conditions employed. In the trinuclear species, a gold(i) cation is sandwiched between two gold(iii) alkynyl complexes, suggesting that coordination of multiple C-C triple bonds to gold is facile.