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

The new 6π-electron four-membered ring compound 3-fluoro-1λ2 ,2,4,3λ3 -thiadiazaphosphetidine, FP(µ-N)2 S, 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)2 S in cryogenic matrices (Ar, Ne, and N2 ) 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 SN2 under subsequent UV-irradiation at 365 nm. In sharp contrast to the square planar structure for the isolobal four-membered ring S2 N2 , a puckered structure with significant biradical character has been found for FP(µ-N)2 S.