Chem. Commun.

Chemical Communications

[Bi6Mo3(CO)9]4−: a multiple local σ-aromatic cluster containing a distorted Bi6 triangular prism

The first Zintl cluster containing a distorted Bi6 triangular prism, [Bi6Mo3(CO)9]4−, has been synthesized and structurally characterized. Quantum chemical calculations indicated that the distorted cage cluster features multiple local σ-aromaticity.!divAbstract

Main group metal–ligand cooperation of N-heterocyclic germylene: an efficient catalyst for hydroboration of carbonyl compounds

N-heterocyclic ylide-like germylene effectively promotes the hydroboration of aldehydes and ketones under mild conditions with broad substrate tolerance, operational simplicity of procedure and excellent yields. A key intermediate in this catalytic system featuring a bicyclo[2,2,2]octane-like core has been successfully isolated and characterized, suggesting a new type of mechanism that involves the activation mode that mimics that of transition metal catalysts.

Synthesis of digermylene-stabilized linear tetraboronate and boroxine

Two newly discovered linear compounds tetraboronate and boroxine stabilized by digermylene are reported, which feature a B4O5 chain and a B3O3 ring, respectively. DFT calculations reveal that not only can digermylene stabilize the electron-deficient boron centers, but also increase the energies of the LUMOs of the boron moiety. Our results provide a hint for the development of boronate covalent organic frameworks.

Unexpected higher stabilisation of two classical antiaromatic frameworks with a ruthenium fragment compared to the osmium counterpart: origin probed by DFT calculations

Density functional theory (DFT) calculations were carried out to investigate the stability and aromaticity of metallapentalocyclobutadienes. The results reveal unexpected higher stabilisation achieved with a 3d ruthenium fragment compared to the 4d osmium counterpart. Moreover, direct 1–3 metal–carbon bonding in the metallabutadiene unit of these two complexes is negligible.!divAbstract

The phosphaethynolate anion reacts with unsaturated bonds: DFT investigations into [2+2], [3+2] and [4+2] cycloadditions

Density functional theory (DFT) calculations were carried out to investigate the [2+2], [3+2] and [4+2] cycloadditions of the phosphaethynolate anion (PCO−). The results reveal that the electronic properties of different unsaturated compounds play a crucial role in reactivity and regioselectivity.!divAbstract

Pd-catalyzed highly regio-, diastereo-, and enantioselective allylic alkylation of α-fluorophosphonates

Highly efficient Pd-catalyzed asymmetric allylic alkylation reaction of ethyl-2-fluoro-2-(diethoxyphosphoryl)acetate with monosubstituted allylic substrates has been developed, affording corresponding α-fluorophosphonates with two chiral centers in high regio-, diastereo- and enantio-selectivities. The usefulness of the products in organic synthesis has been demonstrated.!divAbstract