FP(μ-N) 2 S: A Sulfur-Pnictogen Four-Membered Ring with 6π Electrons.

Autor: Zhu B; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China., Song Y; State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China., Zhu J; State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China., Rauhut G; Institute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, Stuttgart, 70569, Germany., Jiang J; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China., Zeng X; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2023 Aug 10; Vol. 29 (45), pp. e202300251. Date of Electronic Publication: 2023 Jul 18.
DOI: 10.1002/chem.202300251
Abstrakt: The new 6π-electron four-membered ring compound 3-fluoro-1λ 2 ,2,4,3λ 3 -thiadiazaphosphetidine, FP(μ-N) 2 S, has been generated in the gas phase through high-vacuum flash pyrolysis (HVFP) of thiophosphoryl diazide, FP(S)(N 3 ) 2 , at 1000 K. Subsequent isolation of FP(μ-N) 2 S in cryogenic matrices (Ar, Ne, and N 2 ) allows its characterization with matrix-isolation IR and UV-vis spectroscopy by combination with 15 N-isotope labeling and computations at the CCSD(T)-F12a/VTZ-F12 level of theory. Upon visible-light irradiation at 550 nm, this cyclic compound undergoes ring-opening to the thiazyl isomer FPNSN, followed by dissociation to FP and SN 2 under subsequent UV-irradiation at 365 nm. In sharp contrast to the square planar structure for the isolobal four-membered ring S 2 N 2 , a puckered structure with significant biradical character has been found for FP(μ-N) 2 S.
(© 2023 Wiley-VCH Verlag GmbH.)
Databáze: MEDLINE
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