3D-aromatic molecules with (distorted) tetrahedral, octahedral, or spherical structures are much less common than typical 2D-aromatic species or even 2D-aromatic-in-3D systems. Closo boranes, [BnHn]2– (5 ≤ n≤ 14) and carboranes are examples of compounds that are singly 3D-aromatic, and we now explore if there are species that are doubly 3D-aromatic. The most widely known example of a species with…
Very Important Paper in CEJ! Unveiling the True Identity of o-Carboryne as o-Carborene
The homolytic elimination of two H atoms from two adjacent carbons in benzene results in the aromatic product o-benzyne. In a similar way, the homolytic elimination of two H atoms from the two adjacent carbons in 1,2-C2B10H12 results in the aromatic product o-carboryne. In this work, we provide experimental and computational evidences that despite the similarity of o-carboryne and o-benzyne,…
NATURE Communications! On the existence of collective interactions reinforcing the metal-ligand bond in organometallic compounds
Recently, Sowlati-Hashjin et al. concluded that the nature of the Li–C chemical bond in LiCF3differs significantly from that in LiCPh3 (Ph = phenyl). Whereas the Li–C bond of LiCF3 is classified as a conventional two-center two-electron bond (exchange-correlation interaction collectivity index, ICIXC = 0.910, ICIXC > 0.9 and close to 1), that of LiCPh3 is categorized as a collective bond (ICIXC = 0.393). The authors claim that…
New in JOC! Controlling the Diradical Character of Thiele Like Compounds
Organic diradicals play an important role in many fields of chemistry, biochemistry, and materials science. In this work, by means of high-level theoretical calculations, we have investigated the effect of representative chemical substituents in p-quinodimethane (pQDM) and Thiele’s hydrocarbons with respect to the singlet–triplet energy gap, a feature characterizing their diradical character. We show how the…
Chemical Science! Insertion of CO2 and CS2 into Bi-N bonds enables catalyzed CH-activation and light-induced bismuthinidene transfer
The uptake and release of small molecules continue to be challenging tasks of utmost importance in synthetic chemistry. The combination of such small molecule activation with subsequent transformations to generate unusual reactivity patterns opens up new prospects for this field of research. Here, we report the reaction of CO2 and CS2 with cationic bismuth(III) amides. CO2-uptake gives…
Published in Chem. Asian J.! Probing Polar-π Interactions Between Tetrazoles and Aromatic RingsPublished in Chem. Asian J.!
The heterocyclic tetrazole, a well-established bioisosteric replacement of carboxylic acid, plays an important role in medicinal chemistry. To deepen the functional understanding of tetrazoles in chemical sciences, it is essential to investigate the noncovalent interactions between the tetrazole ring and aromatic rings. Here, we report synthetic, spectroscopic, structural and quantum chemical analyses on specially designed…
New in JACS! Facile Construction of New Hybrid Conjugation via Boron Cage Extension
Aromatic polycyclic systems have been extensively utilized as structural subunits for the preparation of various functional molecules. Currently, aromatics-based polycyclic systems are predominantly generated from the extension of two-dimensional (2D) aromatic rings. In contrast, polycyclic compounds based on the extension of three-dimensional (3D) aromatics such as boron clusters are less studied. Here, we report three…
Just published in Angewandte! Methyl Substitution Destabilizes Alkyl Radicals
We have quantum chemically investigated how methyl substituents affect the stability of alkyl radicals MemH3−mC⋅ and the corresponding MemH3−mC−X bonds (X = H, CH3, OH; m = 0 – 3) using density functional theory at M06-2X/TZ2P. The state-of-the-art in physical organic chemistry is that alkyl radicals are stabilized upon an increase in their degree of substitution from methyl<primary<secondary<tertiary, and that this…
New in CEJ! Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations
Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst that is able to bind substrates via the induced fit model according…
New in Dalton Transactions! Ni(i)-TPA stabilization by hydrogen bond formation on the second coordination sphere: a DFT characterizationNew in Dalton Transactions!
Ni(I) compounds are less common than those of either Ni(0) or Ni(II). Recently, a series of Ni(I) tris(2-pyridylmethyl)amine (TPA) complexes were synthetized through the reduction of Ni(II)–TPA complexes and their stabilization was attributed to the formation of H-bonds (Chem. Commun., 2021, 57, 753–756). Because of the growing relevance of Ni(I) complexes in the field of catalysis,…
New in Nature Communications! 3D and 2D aromatic units behave like oil and water in the case of benzocarborane derivativesNew in Nature Communications!
A large number of 2D/2D and 3D/3D aromatic fusions that keep their aromaticity in the fused compounds have been synthesized. In addition, we have previously proven the electronic relationship between the 3D aromaticity of boron hydrides and the 2D aromaticity of PAHs. Here we report the possible existence of 3D/2D aromatic fusions that retain the…
New in JOC! Through-Space Stabilization of an Imidazolium Cation by Aromatic RingsNew in JOC!
Imidazole-based compounds are widely found in natural products, synthetic molecules, and biomolecules. Noncovalent interactions between the imidazole ring and other functional groups play an important role in determining the function of diverse molecules. However, there is a limited understanding of the underlying noncovalent interactions between imidazoles and aromatic systems. In this work, we report physical-organic…
Jordi Poater Lab 