DFT calculations

Aromaticity‐promoted C−F Bond Activation in Rhodium Complex: A Facile Tautomerization

Fluorine is the most electronegative element in the periodic table. Thus, activation of the carbon–fluorine (C−F) bond, the strongest single bond to carbon, has attracted considerable interest from both experimentalists and theoreticians. In comparison with numerous approaches to activate C−F bonds, the aromaticity‐promoted method is less developed. Herein, we demonstrate that the C−F bond activation could be achieved by a facile tautomerization, benefitting from aromaticity, which can stabilize both the transition states and products.

To Be Bridgehead or Not to Be? This is a Question of Metallabicycles on the Interplay between Aromaticity and Ring Strain

Transition-metal-containing metallaaromatics have attracted considerable interest from both experimental and computational chemists because they can display properties of both organometallic compounds and aromatic organic compounds. In general, the transition metal in a metallabicycle prefers a nonbridged position to the bridgehead one because of the larger ring strain caused by the rigidity in the bridgehead position, as exemplified by metallanaphthalene and metallanaphthalyne.

Synthesis and Characterization of a Metallacyclic Framework with Three Fused Five-membered Rings

Polycyclic complexes containing a bridgehead transition metal are interesting species because the transition metal is shared by all the rings simultaneously. In this study, we present a novel osmium–bridgehead system with three fused five-membered rings. This novel framework can be viewed as a 10-atom carbon chain coordinating to the osmium center. In sharp contrast to the nonplanar organic analogue, this unique metallacycle exhibits good planarity, which was unambiguously verified by means of X-ray diffraction.

Comprehensive Comparison Between the Gas-phase SN2 Reactions at Carbon and at Nitrogen

As one of the most important chemical reactions, SN2 reactions play a central role in both synthetic chemistry and the development of mechanistic paradigms. Most of the previous attention has centered on substitution at carbon, whereas displacement at nitrogen is clearly less studied and less understood. The SN2@N reactions have enormous synthetic potential, especially in heterocyclic chemistry, which is a cornerstone of medicinal chemistry, and has been receiving increasing attention, both experimentally and computationally.

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.

http://pubs.rsc.org/en/content/articlelanding/2015/cc/c5cc08291a#!divAbstract

Why Does Activation of the Weaker C═S Bond in CS2 by P/N-Based Frustrated Lewis Pairs Require More Energy Than That of the C═O Bond in CO2? A DFT Study

The sequestration of carbon disulfide (CS2), a common pollutant in environmental systems, is of great importance due to its physical harm to human beings. Compared with CO2 capture, that of CS2 is much less developed. The use of P/N-based frustrated Lewis pairs (FLPs) has been proven, both experimentally and theoretically, to be an alternative strategy to efficiently sequestrate CO2. Therefore, we pose the question of whether the analogue CS2 could also be sequestrated by the same FLPs, given that the C═S bond in CS2 is weaker than the C═O bond in CO2.

Theoretical study on the interconversion of silabenzenes and their monocyclic non-aromatic isomers via the [1,3]-substituent shift: Interplay of aromaticity and Bent's rule

Density functional theory (DFT) calculations were performed to examine the substituent effects on the interconversion of silabenzenes and their monocyclic non-aromatic isomers. A previous study suggested that aromaticity is the driving force for this process. Interestingly, our systematic calculations reveal that the contribution from aromaticity can be evaluated quantitatively (ca. 30 kcal mol-1). Thus it is the interplay of aromaticity and Bent's rule that determine their relative stabilities.