Exohedral complexation of B39- with ECp∗+ half-sandwich complexes (E Si, Ge, Sn, Pb): A DFT study

Majumder, Ayan ; Ghara, Manas ; Chattaraj, Pratim K. (2018) Exohedral complexation of B39- with ECp∗+ half-sandwich complexes (E Si, Ge, Sn, Pb): A DFT study Computational and Theoretical Chemistry, 1140 . pp. 49-55. ISSN 2210271X

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Official URL: http://doi.org/10.1016/j.comptc.2018.07.018

Related URL: http://dx.doi.org/10.1016/j.comptc.2018.07.018

Abstract

The hexagonal and heptagonal holes of allow its complexation with a half sandwich complex ECp∗+ (Edouble bondSi, Ge, Sn, Pb). Structure and the nature of bonding of (η6/7-B39)E(η5-Cp∗) are explored through the density functional theory based computation. (η6-B39)E(η5-Cp∗) isomers are more stable than (η7-B39)E(η5-Cp∗) and the energy difference between these two isomers decreases down the group from Si to Pb. The dissociation path, (η6/7-B39)E(η5-Cp∗) → + ECp∗+ is studied. For all E, (η6/7-B39)E(η5-Cp∗) is formed exergonically at 298 K temperature as given by the ΔG values of dissociation path [60.1(Si) to 68.3(Pb) kcal/mol for (η6-B39)E(η5-Cp∗) and 58.3(Si) to 67.8(Pb) kcal/mol for (η7-B39)E(η5-Cp∗)]. The adduct becomes bent around the central E atom when gets attached to ECp∗+ and the amount of bending increases gradually down the group from Si to Pb. Bonding analysis of the stable isomer, (η6-B39)E(η5-Cp∗) has been done by natural bonding orbital (NBO) and energy decomposition analyses (EDA). The electron density from is transferred to the ECp∗+ moiety as revealed by the NBO analysis. All the complexes are mainly stabilized by the electrostatic and orbital interactions between and ECp∗+ fragments as highlighted by the EDA results.

Item Type:Article
Source:Copyright of this article belongs to Elsevier B.V
Keywords:Sandwich compound;Borospherene;Thermochemical stability;Electron density analysis
ID Code:133559
Deposited On:29 Dec 2022 06:17
Last Modified:29 Dec 2022 06:17

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