Estimating the stability and reactivity of novel bicyclic germylenes at density functional theory. (6th April 2021)

• Record Type: Journal Article
• Authors: Abedini, Nastaran; Kassaee, Mohamad Z.
• Is Part Of: Journal of physical organic chemistry. Volume 34:Number 8(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-04-06
• Subjects: coordinate covalent bond -- germylene -- nucleophilicity -- stability; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.4208
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract: The effects of nitrogen substituent on stability (ΔΕs–t ) of novel germylenes with one, two, and three germylene centers are compared and contrasted at B3LYP/6‐311++G** level of theory. These singlet and triplet germylenes (1 s –18 s and 1 t –18 t, respectively) appear as minimum on its energy surface, and the order of their stability estimated by singlet (s)–triplet (t) energy difference (ΔEs–t = Et − Es ) is 16 > 6 > 1 > 15 > 17 > 2 > 8 > 3 > 9 > 11 > 7 > 10 > 12 > 14 > 5 > 4 > 18 > 13 . Hence, every singlet germylene shows more stability than its corresponding triplet. Germylene 13 with the lowest stability (ΔEs–t = 4.31 kcal/mol) has the highest nucleophilicity (4.47 eV). Applying suitable isodesmic reactions, we show that the σ‐acceptor nitrogen substituents stabilize not only the singlet but also the triplet states with their positive ΔE. The aim of the present work is to recognize the influence of nitrogen and germylene centers on the stability and band gap (ΔΕHOMO–LUMO ), electrophilicity ( ω ), nucleophilicity ( N ), and etc. They can be used as accumulated multidentate ligands. Abstract : Substituent effects on stability of novel germylenes are compared and contrasted at B3LYP/6‐311++G** level of theory. The highest stability belongs to germylene 16 . Germylenes 3 s, 5 s, 6 s, 7 s, 8 s, 9 s, 11 s, 14 s, and 15 s have a coordinate covalent bond between nitrogen and empty p orbital of the germylene center. The purpose of the present work is to assess the influence of nitrogen and germylene center on the stability and other properties. Also, they can be used as accumulated multidentate ligands.