Ligand‐Supported E<sub>3</sub> Clusters (E=Si–Sn)

Pan, Sudip; Saha, Ranajit; Osorio, Edison; Chattaraj, Pratim Kumar; Frenking, Gernot; Merino, Gabriel

doi:10.1002/chem.201700494

Cited by 12 publications

(13 citation statements)

References 164 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As noted in previous reports, in Si 3 (cAAC) 3 , one ligand is bent upward and the another two are bent downward with respect to the plane of the Si 3 cluster. , In the naked Si 3 cluster, one Si–Si distance is longer by 0.532 Å than the other two equal Si–Si distances in the most stable C 2 v geometry, whereas upon complexation with cAAC, the difference between the longest and the shortest Si–Si bond is reduced to only 0.042 Å. This was also observed previously .…”

Section: Resultssupporting

confidence: 86%

“…24 After that, some of us performed a benchmarking study on nine different types of carbenes to explore their relative strength in complexation with Si 3 and expanded this idea to the heavier analogues of the Si 3 cluster. 25 A ligand stabilized C 3 molecule or other species in these series are hitherto unknown. In 2006, the group of Bertrand became successful in isolation of a cyclopropenylidene derivative that is stable at room temperature.…”

Section: ■ Introductionmentioning

confidence: 99%

“…For this purpose, stable carbenes are excellent ligands. − Recently, Mondal et al successfully synthesized a cyclic alkyl(amino) carbene (cAAC) stabilized Si 3 cluster on a large scale at ambient temperature where the cAAC–Si interaction can be described in terms of a donor–acceptor bond . After that, some of us performed a benchmarking study on nine different types of carbenes to explore their relative strength in complexation with Si 3 and expanded this idea to the heavier analogues of the Si 3 cluster . A ligand stabilized C 3 molecule or other species in these series are hitherto unknown.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

2019

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 86%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

“…Such divalent C(0) complexes are termed as carbones . The class of suitable ligands for carbones CL 2 has been extended with the synthesis of N-heterocyclic carbene (NHC) and cyclic (alkyl)(amino) carbene (cAAC) − ligands and they have been widely used to prepare exciting complexes. − The intriguing bonding situation of C(PPh 3 ) 2 stimulated the search for other carbone complexes, which led to the prediction of carbodicarbene, C(NHC) 2 in 2007 . In the following year, two different groups experimentally synthesized a benzoannulated derivative C(NHC Bz ) using different synthetic routes. , It has been gradually extended to a wide varieties of ligands containing a L→C(0)←L bonding motif. − Besides L→C(0)←L σ donation there is also some L←C(0)→L π backdonation, the extent of which depends on the π accepting ability of L. Bonding analysis also showed that the bonding between carbon and cAAC ligands in C(cAAC) 2 is best represented as electron-sharing interaction (cAAC)C(cAAC) .…”

Section: Introductionmentioning

confidence: 99%

Revisiting the Bonding Scenario of Two Donor Ligand Stabilized C₂ Species

et al. 2020

Self Cite

View full text Add to dashboard Cite

Quantum chemical calculations using density functional methods were performed for complexes of type L2C2 with L = NHCMe (1), SNHCMe (2) (S = saturated), cAACMe (3), and diamidocarbene (DACMe) (4). The equilibrium structures of 1–4 possess almost linear C4 cores. A high thermochemical stability of the complexes with respect to dissociation, L2C2 → C2 + 2L, is indicated by the large bond dissociation energy following the order 3 > 4 > 2 > 1. The results show that the use of SNHCMe and DACMe as ligands is preferable over NHCMe. The bonding analysis using charge and energy decomposition methods reveals that (cAACMe)2C2 and (DACMe)2C2 possess genuine cumulene C4 moieties, which results from the electron-sharing bonding between quintet L2 and quintet C2 fragments. In contrast, the bonding in (NHCMe)2C2 and (SNHCMe)2C2 comes from a combination of dative and electron-sharing interactions between doublet L2 + and doublet C2 − fragments.

show abstract

Ligand‐Supported E₃ Clusters (E=Si–Sn)

Cited by 12 publications

References 164 publications

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

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

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

Revisiting the Bonding Scenario of Two Donor Ligand Stabilized C₂ Species

Contact Info

Product

Resources

About

Ligand‐Supported E3 Clusters (E=Si–Sn)

Cited by 12 publications

References 164 publications

Donor–Acceptor vs Electron-Shared Bonding: Triatomic SinC3–n(n≤ 3) Clusters Stabilized by Cyclic Alkyl(amino) Carbene

Donor–Acceptor vs Electron-Shared Bonding: Triatomic SinC3–n(n≤ 3) Clusters Stabilized by Cyclic Alkyl(amino) Carbene

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

Revisiting the Bonding Scenario of Two Donor Ligand Stabilized C2 Species

Contact Info

Product

Resources

About

Ligand‐Supported E₃ Clusters (E=Si–Sn)

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

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

Revisiting the Bonding Scenario of Two Donor Ligand Stabilized C₂ Species