Planar hypercoordinate structures are gaining immense attention due to the shift from common para... more Planar hypercoordinate structures are gaining immense attention due to the shift from common paradigm. Herein, our high level ab initio calculations predict that planar pentacoordinate aluminium and gallium centres in Cu5Al2+ and Cu5Ga2+ clusters are global minima in their singlet ground states. These clusters are thermodynamically and kinetically very stable. Detailed electronic structure analyses reveal the presence of σ-aromaticity which is the driving force for the stability of the planar form.
Quantum chemical calculations have been performed on B3 ring stabilized Y-Y interaction (Y = Be, ... more Quantum chemical calculations have been performed on B3 ring stabilized Y-Y interaction (Y = Be, Mg, Ca) to understand the possibility of binuclear sandwich type complex formation. Calculations indicate single reference character of the studied systems. The complexes have been found to be stable towards dissociation into different fragments. Thermodynamic consideration also indicates the favourability of their formation. Increase in aromaticity of the parent B3 ring upon complexation is observed which is expected to provide extra stability to the complexes.
Planar pentacoordinate zinc group elements, (M = Zn, Cd, Hg) were computationally found to be at ... more Planar pentacoordinate zinc group elements, (M = Zn, Cd, Hg) were computationally found to be at a global minimum in Li5M+ clusters. The stability of these clusters is due to the presence of multicentric bonds. The central element (Zn, Cd, Hg) in each cluster features a negative oxidation state owing to the in-plane electron donation by the Li5+ framework. A similar global minimum planar pentacoordinate structure is found in Na5Zn+ and Na5Cd+ clusters.
Sandwich complexes find their interests among the chemists after the breakthrough discovery of fe... more Sandwich complexes find their interests among the chemists after the breakthrough discovery of ferrocene. Since then, a number of sandwich and half sandwich complexes were predicted and synthesized. Herein, we have theoretically proposed a series of half-sandwich complexes involving a neutral Be3 ring and transition metal. Quantum chemical calculations have shown that the proposed complexes are quite stable involving high bond dissociation energies. The thermodynamics of their formation is also favorable. The Be3 ring in all cases posses dual aromaticity which has been ascertained based on magnetic as well as topological feature of electron density.
Quantum chemical calculations were carried out to establish the half-sandwich structural behaviou... more Quantum chemical calculations were carried out to establish the half-sandwich structural behaviour between heavier group-14 elements (Si-Pb) and neutral Be3 ring. The proposed complexes are found to be global minima on the potential energy surface. Quantum chemical investigation revealed that the complexes found possess high bond dissociation energy and also favorable thermodynamics of their formation. The complexes were also found to possess significant aromatic behaviour. In addition, the half-sandwich complexes were found to possess promising chemical properties to be useful for potential H2 storage material under reversible conditions.
Planar hypercoordinate structures are gaining immense attention due to the shift from common para... more Planar hypercoordinate structures are gaining immense attention due to the shift from common paradigm. Herein, our high level ab initio calculations predict that planar pentacoordinate aluminium and gallium centres in Cu5Al2+ and Cu5Ga2+ clusters are global minima in their singlet ground states. These clusters are thermodynamically and kinetically very stable. Detailed electronic structure analyses reveal the presence of σ-aromaticity which is the driving force for the stability of the planar form.
Quantum chemical calculations have been performed on B3 ring stabilized Y-Y interaction (Y = Be, ... more Quantum chemical calculations have been performed on B3 ring stabilized Y-Y interaction (Y = Be, Mg, Ca) to understand the possibility of binuclear sandwich type complex formation. Calculations indicate single reference character of the studied systems. The complexes have been found to be stable towards dissociation into different fragments. Thermodynamic consideration also indicates the favourability of their formation. Increase in aromaticity of the parent B3 ring upon complexation is observed which is expected to provide extra stability to the complexes.
Planar pentacoordinate zinc group elements, (M = Zn, Cd, Hg) were computationally found to be at ... more Planar pentacoordinate zinc group elements, (M = Zn, Cd, Hg) were computationally found to be at a global minimum in Li5M+ clusters. The stability of these clusters is due to the presence of multicentric bonds. The central element (Zn, Cd, Hg) in each cluster features a negative oxidation state owing to the in-plane electron donation by the Li5+ framework. A similar global minimum planar pentacoordinate structure is found in Na5Zn+ and Na5Cd+ clusters.
Sandwich complexes find their interests among the chemists after the breakthrough discovery of fe... more Sandwich complexes find their interests among the chemists after the breakthrough discovery of ferrocene. Since then, a number of sandwich and half sandwich complexes were predicted and synthesized. Herein, we have theoretically proposed a series of half-sandwich complexes involving a neutral Be3 ring and transition metal. Quantum chemical calculations have shown that the proposed complexes are quite stable involving high bond dissociation energies. The thermodynamics of their formation is also favorable. The Be3 ring in all cases posses dual aromaticity which has been ascertained based on magnetic as well as topological feature of electron density.
Quantum chemical calculations were carried out to establish the half-sandwich structural behaviou... more Quantum chemical calculations were carried out to establish the half-sandwich structural behaviour between heavier group-14 elements (Si-Pb) and neutral Be3 ring. The proposed complexes are found to be global minima on the potential energy surface. Quantum chemical investigation revealed that the complexes found possess high bond dissociation energy and also favorable thermodynamics of their formation. The complexes were also found to possess significant aromatic behaviour. In addition, the half-sandwich complexes were found to possess promising chemical properties to be useful for potential H2 storage material under reversible conditions.
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