Assessing the Viability of Extended Nonmetal Atom Chains in MnF4n+2 (M=S and Se)

• Published in: Angewandte Chemie (International ed.) Vol. 54; no. 5; pp. 1476 - 1480
• Main Authors: Popov, Ivan A., Averkiev, Boris B., Starikova, Alyona A., Boldyrev, Alexander I., Minyaev, Ruslan M., Minkin, Vladimir I.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 26.01.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: chemical bonding; computational chemistry; electronic structure; nonmetal atom chains; sulfur/selenium compounds
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201409418

Theoretical investigations to evaluate the viability of extended nonmetal atom chains on the basis of molecular models with the general formula MnF4n+2 (M=S and Se) and corresponding solid‐state systems exhibiting direct SS or SeSe bonding were performed. The proposed high‐symmetry molecules were found to be minima on the potential energy surface for all SnF4n+2 systems studied (n=2–9) and for selenium analogues up to n=6. Phonon calculations of periodic structures confirmed the dynamic stability of the ‐(SF4–SF4)∞‐ chain, whereas the analogous ‐(SeF4–SeF4)∞‐ chain was found to have a number of imaginary phonon frequencies. Chemical bonding analysis of the dynamically stable ‐(SF4–SF4)∞‐ structure revealed a multicenter character of the SS and SF bonds. A novel definition and abbreviation (ENAC) are proposed by analogy with extended metal atom chain (EMAC) complexes. No end in sight: The viability of extended chains of nonmetal atoms was assessed theoretically on the basis of molecular models MnF4n+2 (M=S or Se, yellow; F turquoise) and corresponding solid‐state systems exhibiting direct SS or SeSe bonding. The proposed molecules were found to be minima for SnF4n+2 systems with n=2–9 and for selenium analogues with n≤6, and the ‐(SF4–SF4)∞‐ structure, unlike ‐(SeF4–SeF4)∞‐, was found to be dynamically stable.