Affiliation:
1. Department of Chemistry Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University Shanghai 200433 China
2. 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
3. Institute for Theoretical Chemistry University of Stuttgart Pfaffenwaldring 55 Stuttgart 70569 Germany
Abstract
AbstractThe new 6π‐electron four‐membered ring compound 3‐fluoro‐1λ2,2,4,3λ3‐thiadiazaphosphetidine, FP(μ‐N)2S, has been generated in the gas phase through high‐vacuum flash pyrolysis (HVFP) of thiophosphoryl diazide, FP(S)(N3)2, at 1000 K. Subsequent isolation of FP(μ‐N)2S in cryogenic matrices (Ar, Ne, and N2) allows its characterization with matrix‐isolation IR and UV‐vis spectroscopy by combination with 15N‐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 SN2 under subsequent UV‐irradiation at 365 nm. In sharp contrast to the square planar structure for the isolobal four‐membered ring S2N2, a puckered structure with significant biradical character has been found for FP(μ‐N)2S.
Funder
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis,Organic Chemistry