A lithium-aluminium heterobimetallic dimetallocene.

Homobimetallic dimetallocenes exhibiting two identical metal atoms sandwiched between two η bonded cyclopentadienyl rings is a narrow class of compounds, with representative examples being dizincocene and diberyllocene. Here we report the synthesis and structural characterization of a heterobimetallic dimetallocene, accessible through heterocoupling of lithium and aluminylene fragments with pentaisopropylcyclopentadienyl ligands. The Al-Li bond features a high ionic character and profits from attractive dispersion interactions between the isopropyl groups of the cyclopentadienyl ligands.

Merging the Energy Decomposition Analysis with the Interacting Quantum Atoms Approach.

Energy decomposition analysis (EDA) is a well-established approach to dissect the interaction energy into chemically sound components. Despite the inherent requirement of reference states has been a long-standing object of debate, the direct relation with the molecular orbital analysis helps in building up predictive models. The alternative molecular energy decomposition schemes that decompose the total energy into atomic and diatomic contributions, such as the interacting quantum atoms (IQA), has no external reference requirements and also the intra- and intermolecular interactions are treated on equal footing.

Reply to the 'Comment on "The oxidation state in low-valent beryllium and magnesium compounds"' by S. Pan and G. Frenking, , 2022, , DOI: 10.1039/D2SC04231B.

A recent article by Pan and Frenking challenges our assignment of the oxidation state of low valent group 2 compounds. With this reply, we show that our assignment of Be(+2) and Mg(+2) oxidation states in Be(cAAC) and Mg(cAAC) is fully consistent with our data. Some of the arguments exposed by Pan and Frenking were based on visual inspection of our figures, rather than a thorough numerical analysis.

The oxidation state in low-valent beryllium and magnesium compounds.

Low-valent group 2 (E = Be and Mg) stabilized compounds have been long synthetically pursued. Here we discuss the electronic structure of a series of Lewis base-stabilized Be and Mg compounds. Despite the accepted zero(0) oxidation state nature of the group 2 elements of some recent experimentally accomplished species, the analysis of multireference wavefunctions provides compelling evidence for a strong diradical character with an oxidation state of +2.

Unveiling the Electronic Structure of the Bi(+1)/Bi(+3) Redox Couple on NCN and NNN Pincer Complexes.

Low-valent group 15 compounds stabilized by pincer ligands have gained particular interest, given their direct access to fine-tune their reactivity by the coordination pattern. Recently, bismuth has been employed in a variety of catalytic transformations by taking advantage of the (+1/+3) redox couple. In this work, we present a detailed quantum-chemical study on the electronic structure of bismuth pincer complexes from two different families, namely, bis(ketimine)phenyl (NCN) and triamide bismuthinidene (NNN).

Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands.

Metalloradicals are key species in synthesis, catalysis, and bioinorganic chemistry. Herein, two iron radical cation complexes (3-E)GaCl [(3-E) = [{(IPr)C(Ph)E} Fe(CO) ] , E = P or As; IPr = C{(NDipp)CH} , Dipp = 2,6-iPr C H ] are reported as crystalline solids. Treatment of the divinyldipnictenes {(IPr)C(Ph)E} (1-E) with Fe (CO) affords [{(IPr)C(Ph)E} Fe(CO) ] (2-E), in which 1-E binds to the Fe atom in an allylic (η -EEC ) fashion and functions as a 4e donor ligand.

A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack.

A-234, [EtO-P([double bond, length as m-dash]O)(F)-N[double bond, length as m-dash]C(Me)-N(Et)], is the suspected A-type nerve agent used in the Skripal attack on the 4th of March 2018. Studies related to the structure and reactivity of this compound are limited. We, therefore, aimed at understanding the underlying hydrolysis mechanism of A-234 within the DFT framework.