Chemical bonding in the hexamethylbenzene–SO2+ dication

Pecher, Lisa; Pan, Sudip; Frenking, Gernot

doi:10.1007/s00214-019-2434-1

Cited by 21 publications

(11 citation statements)

References 32 publications

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“…Lastly, Δ E disp represents the dispersion interaction between the two fragments. This method is very widely used to analyze the bonding situation in different type of systems [61,62,63,64,65,66,67,68,69,70,71].…”

Section: Ng Compounds Under the Light Of Theoretical Chemistrymentioning

confidence: 99%

How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account

et al. 2019

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Noble gases (Ngs) are the least reactive elements in the periodic table towards chemical bond formation when compared with other elements because of their completely filled valence electronic configuration. Very often, extreme conditions like low temperatures, high pressures and very reactive reagents are required for them to form meaningful chemical bonds with other elements. In this personal account, we summarize our works to date on Ng complexes where we attempted to theoretically predict viable Ng complexes having strong bonding to synthesize them under close to ambient conditions. Our works cover three different types of Ng complexes, viz., non-insertion of NgXY type, insertion of XNgY type and Ng encapsulated cage complexes where X and Y can represent any atom or group of atoms. While the first category of Ng complexes can be thermochemically stable at a certain temperature depending on the strength of the Ng-X bond, the latter two categories are kinetically stable, and therefore, their viability and the corresponding conditions depend on the size of the activation barrier associated with the release of Ng atom(s). Our major focus was devoted to understand the bonding situation in these complexes by employing the available state-of-the-art theoretic tools like natural bond orbital, electron density, and energy decomposition analyses in combination with the natural orbital for chemical valence theory. Intriguingly, these three types of complexes represent three different types of bonding scenarios. In NgXY, the strength of the donor-acceptor Ng→XY interaction depends on the polarizing power of binding the X center to draw the rather rigid electron density of Ng towards itself, and sometimes involvement of such orbitals becomes large enough, particularly for heavier Ng elements, to consider them as covalent bonds. On the other hand, in most of the XNgY cases, Ng forms an electron-shared covalent bond with X while interacting electrostatically with Y representing itself as [XNg]+Y−. Nevertheless, in some of the rare cases like NCNgNSi, both the C-Ng and Ng-N bonds can be represented as electron-shared covalent bonds. On the other hand, a cage host is an excellent moiety to examine the limits that can be pushed to attain bonding between two Ng atoms (even for He) at high pressure. The confinement effect by a small cage-like B12N12 can even induce some covalent interaction within two He atoms in the He2@B12N12 complex.

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Section: Ng Compounds Under the Light Of Theoretical Chemistrymentioning

confidence: 99%

How Far Can One Push the Noble Gases Towards Bonding?: A Personal Account

et al. 2019

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“…Here we have examined two bonding scenario, one being donor–acceptor interaction between two singlet fragments and another being electron-shared double bonds between two triplet fragments. When more than one scheme is available, the size of the Δ E orb is a very efficient probe to decide the best choice of the interacting fragments. − The scheme resulting in the smallest Δ E orb value is the best to represent the electronic structure of the systems as it needs the least alteration in the electronic charge distribution of both fragments. Our results show that, irrespective of the systems, the C center always prefers to form an electron-shared double bond with C cAAC over the donor–acceptor interaction, whereas the reverse situation is true for Si–C cAAC bond.…”

Section: Resultsmentioning

confidence: 99%

Donor–Acceptor vs Electron-Shared Bonding: Triatomic Si_nC_3–n(n≤ 3) Clusters Stabilized by Cyclic Alkyl(amino) Carbene

2019

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Si n C3–n (n ≤ 3) clusters are interstellar species that are transient in nature at ambient conditions. Herein, the structure, stability, and nature of bonding in cyclic alkyl(amino) carbene (cAAC) protected Si n C3–n (n ≤ 3) clusters are studied in silico. The Si3(cAAC)3 complex was previously reported to be synthesized in large scale. The present results indicate that because the C–CcAAC bond is stronger than the Si–CcAAC bond, C3(cAAC)3 and SiC2(cAAC)3 complexes have significantly larger stability with respect to ligand dissociation than the Si3(cAAC)3 complex, while Si2C(cAAC)3 has almost the same stability as in the latter complex. Moreover, considering the Si3(cAAC)3 complex as a precursor, the hypothetical successive single Si substitution process by a single C atom in Si3(cAAC)3 complex is exergonic in nature. The bonding situation is analyzed by employing natural bond orbital (NBO), electron density, and energy decomposition analyses in combination with the natural orbital for chemical valence theory. These studies show that the nature of bonding in C–CcAAC and Si–CcAAC bonds differs significantly from each other. The former bonds are best described as an electron-shared double bond, whereas the latter bonds are of donor–acceptor type consisting of two components, Si←CcAAC σ-donation and Si→CcAAC π-back-donation. Nevertheless, in the former bonds, covalent character is larger than the ionic one but in the latter bonds the reverse is true. For some Si–CcAAC bonds, the π-natural orbital cannot be located by the NBO method, presumably because of slightly lower occupancy than the cutoff values, but the electron density analysis confirms that different Si–CcAAC bonds in a given complex are almost equivalent in terms of electron density distribution. This paper reports an interesting change in bonding pattern when one replaces Si by a C atom in triatomic silicon carbide clusters stabilized by a ligand.

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“…The best fragmentation scheme to reflect the bonding situation in the molecule is understood by using the size of the orbital interaction (E orb ) as a probe. [85][86][87][88][89] The fragments which give the lowest E orb value is the best to reflect the actual bonding situation in the molecule since it requires the least change in the electronic charge of the fragments to get the electronic structure of the final molecule. Table S2 provides the numerical results of EDA considering Ga and Be 6 Au 6 in different charges and electronic states as interacting…”

Section: Bondingmentioning

confidence: 99%