Property and reactivity of polyselenides and polysulfides: a quantum chemistry study. (4th May 2023)

• Record Type: Journal Article
• Authors: Pi, Hui-Chu; Hu, Ching-Han
• Is Part Of: Journal of sulfur chemistry. Volume 44:Number 3(2023)
• Page Start: 304
• Page End: 319
• Publication Date: 2023-05-04
• Subjects: Polysulfide -- polyselenide -- thiolate -- selenolate -- nucleophilicity; Sulfur -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.72305
• DOI: 10.1080/17415993.2022.2152284
• Languages: English
• ISSNs: 1741-5993

Abstract

Abstract : High-level ab initio and density functional theory were applied to investigate property and reactivity of polyselenides and polysulfides. With CH3 Xn H (X = S or Se) we found that the deprotonation energy (and p Ka ) of CH3 Sen H, ionization potential (IP) of, and CH3 Sen −H bond dissociation energy (BDE) are lower than those of their sulfur counterparts. For n = 2, IPs and X−H BDEs are exceptionally small. The relative nucleophilicity of C H 3 X n − vary with substrates. However, CH3 Sen H are more nucleophilic than CH3 Sn H due to their due to their lower deprotonation energy. The nucleophilicity of selenolates versus thiolates are related to the chemical nature. Selenium is more electrophilic than sulfur. GRAPHICAL ABSTRACT: UF0001