Testing the effectiveness of the isoelectronic substitution principle through the transformation of aromatic osmathiophene derivatives into their inorganic analogues

Vásquez‐Espinal, Alejandro; Poater, Jordi; Solà, Miquel; Tiznado, William; Islas, Rafael

doi:10.1039/c6nj02972h

Cited by 10 publications

(13 citation statements)

References 73 publications

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“…In the case of the azacobaltabicyclo[3.2.0]heptatriene, the difference is even larger (9.7 kcal/mol). Similarly, for the [OsCl 2 (SNC 2 H 3 )(PH 3 ) 2 ] azaosmathiophenes, the most stable isomer is the one having the N in the α-position . To our knowledge, no study discussing the reasons for the preference of the α-position of the N atom in these intermediates has been reported yet.…”

Section: [2 + 2 + 2] Cycloaddition Of Two Alkynes and Cn Multiple Bondsmentioning

confidence: 99%

“…Similarly, for the [OsCl 2 (SNC 2 H 3 )-(PH 3 ) 2 ] azaosmathiophenes, the most stable isomer is the one having the N in the α-position. 243 To our knowledge, no study discussing the reasons for the preference of the α-position of the N atom in these intermediates has been reported yet. However, it is likely that the σ-donor properties of N through its lone pair and the shape of the LUMO orbital with the largest lobe in the C atom favor coupling or insertion with N in the α-position.…”

Section: [2 + 2 + 2] Cycloaddition Of Two Alkynes and Cn Multiple Bondsmentioning

confidence: 99%

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Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

2020

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The development of catalytic methodologies involving the formation of C−C bonds to enable the generation of cyclic systems constitutes a field of great relevance in synthetic organic chemistry. One paradigmatic process to accomplish this goal efficiently is the transition-metal-catalyzed [2 + 2 + 2] cycloaddition reaction, since it permits the formation of a wide range of highly functionalized 6-membered carbo-and heterocyclic molecules in a single step with high efficiency and perfect atom economy. A key feature of these transformations is the mechanistic pathway that they follow, since a deep knowledge of this mechanism may enable us to understand and improve the efficiency of the reaction. This review covers the mechanistic aspects, studied both from theoretical and experimental points of view, of the transition-metal-catalyzed [2 + 2 + 2] cycloaddition reaction involving all kinds of unsaturated substrates with metals such as Co, Ni, Ru, Rh, Ir, Pd, Zr, Ti, Ta, and Nb. A thorough overview is undertaken, from the seminal studies until the present day, of the key mechanistic aspects that influence the reactivity and selectivity of the reaction, comparing the involvement of different unsaturated substrates as well as the different transition metals used.

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Section: [2 + 2 + 2] Cycloaddition Of Two Alkynes and Cn Multiple Bondsmentioning

confidence: 99%

Section: [2 + 2 + 2] Cycloaddition Of Two Alkynes and Cn Multiple Bondsmentioning

confidence: 99%

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

2020

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“…[11][12][13] The B ind has already been employed with the aim of understanding the electronic delocalization of other boron clusters, [14][15][16] and in some other molecules generated by isoelectronic substitutions. [17][18] Plots of the B ind have been also employed in some containing-beryllium clusters. 19 In particular, the B12 isoelectronic analogues under analysis are: B11C + , B11Be -, B10C2 2+ , B10Be2 2-, B10BeC, B9Be2C -, B9BeC2 + and finally, for comparison, the totally boronfree Be6C6.…”

Section: Introductionmentioning

confidence: 99%

Analysis of the electronic delocalization in some isoelectronic analogues of B₁₂ doped with beryllium and/or carbon

Islas

Inostroza

Arias-Olivares

et al. 2020

Phys. Chem. Chem. Phys.

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“…Accordingly, the aromaticity well justifies the clusters' highly symmetric and stable structures. So, numerous planar boron clusters [7][8][9], metal clusters [1,[5][6][7][10][11][12][13][14], and metallabenzenes [15][16][17][18][19] fit well into the concept of aromaticity. Along with πand σ-aromaticity, multiple local π-aromaticity shows to be a helpful concept for rationalizing complex conjugate systems, such as polycyclic hydrocarbons or graphene [20,21].…”

Section: Introductionmentioning

confidence: 95%

Analysis of Local and Global Aromaticity in Si3C5 and Si4C8 Clusters. Aromatic Species Containing Planar Tetracoordinate Carbon

Torres‐Vega¹,

Alcoba

Oña

et al. 2021

Chemistry

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The minimum energy structures of the Si3C5 and Si4C8 clusters are planar and contain planar tetracoordinate carbons (ptCs). These species have been classified, qualitatively, as global (π) and local (σ) aromatics according to the adaptive natural density partitioning (AdNDP) method, which is an orbital localization method. This work evaluates these species’ aromaticity, focusing on confirming and quantifying their global and local aromatic character. For this purpose, we use an orbital localization method based on the partitioning of the molecular space according to the topology of the electronic localization function (LOC-ELF). In addition, the magnetically induced current density is analyzed. The LOC-ELF-based analysis coincides with the AdNDP study (double aromaticity, global, and local). Moreover, the current density analysis detects global and local ring currents. The strength of the global and local current circuit is significant, involving 4n + 2 π- and σ-electrons, respectively. The latter implicates the Si-ptC-Si fragment, which would be related to the 3c-2e σ-bond detected by the orbital localization methods in this fragment.

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Testing the effectiveness of the isoelectronic substitution principle through the transformation of aromatic osmathiophene derivatives into their inorganic analogues

Abstract: Abstract.The objective of the current work is to evaluate the effectiveness of isoelectronic substitution (IS) principle on a series of complexes with general formula OsCl2 (

Cited by 10 publications

References 73 publications

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

Analysis of the electronic delocalization in some isoelectronic analogues of B₁₂ doped with beryllium and/or carbon

Analysis of Local and Global Aromaticity in Si3C5 and Si4C8 Clusters. Aromatic Species Containing Planar Tetracoordinate Carbon

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Testing the effectiveness of the isoelectronic substitution principle through the transformation of aromatic osmathiophene derivatives into their inorganic analogues

Abstract: Abstract.The objective of the current work is to evaluate the effectiveness of isoelectronic substitution (IS) principle on a series of complexes with general formula OsCl2 (

Cited by 10 publications

References 73 publications

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

Analysis of the electronic delocalization in some isoelectronic analogues of B12 doped with beryllium and/or carbon

Analysis of Local and Global Aromaticity in Si3C5 and Si4C8 Clusters. Aromatic Species Containing Planar Tetracoordinate Carbon

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Analysis of the electronic delocalization in some isoelectronic analogues of B₁₂ doped with beryllium and/or carbon