Difluoro‐λ⁵‐Phosphinonitrile F₂PN: Matrix Isolation and Photoisomerization into FPNF

Abstract

Splendid isolation: Monomeric phosphazene F(2)PN ((1)A(1)) was prepared for the first time through irradiation of F(2)PN(3) in an argon matrix with an ArF excimer laser (lambda=193 nm). Upon subsequent irradiation with a high-pressure mercury arc lamp (lambda=255 nm), F(2)PN undergoes a 1,2-fluorine shift to give iminophosphane cis-FP=NF.

Gas‐Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN

“…Another type of effective stabilizing interaction is the delocalization of the lone pair from the atom which is directly bonded to the nitrene center, such as in aminonitrene (R 2 N-N), [8] sulfenylnitrene (RS-N), [9] and phosphinonitrene (R 2 P-N). [10] These compounds are singlet nitrenes with favorable Lewis resonance structures of diazene,t hiazyne, and phosphazene,respectively. [11] Sulfinylnitrene RS(O)N was suggested in the 1980s by Maricich et al to be the key intermediate in the decomposition of benzenesulfinyl azide.…”

SN2P2: A Neutral Five‐Membered Sulfur–Pnictogen(III) Ring

“…According to the 15 N-isotopic shifts and calculated vibrational displacement vectors (B3LYP/6-311 + G(3df)), the most intense feature, ñ = 1045.4 cm À1 (Dn( 14/15 N) = 18.6, 6.8, and 27.0 cm À1 ), is mainly attributed to the N-P stretching vibrations. Its frequency is lower than those found in trans-FP = NF (ñ = 1116.8 cm À1 , Dn( 14/15 N) = 25.3 cm À1 , matrix IR) [17] and P 3 N 3 (ñ = 1137 cm À1 , Dn( 14/15 N) = 10, 20, and 30 cm À1 , matrix IR).…”

Structure and Conformational Properties of Azido(difluoro)phosphane, F2PN3

“…[5,6] Recently, the photo-induced decomposition of F 2 PN 3 to F 2 PϵN and N 2 was studied in an Ar matrix, the initially formed F 2 PϵN further isomerizes to FP=NF. [7] For alkoxy, [8] amino, [9] and primary phosphanes, [10] several different conformers with respect to the internal rotation around the R 2 P-X (X = OR, CR 3 , and NR 2 ) bond have been established by vibrational spectroscopy and gasphase electron diffraction (GED) studies. However, analogous experiments on the pseudohalide derivatives F 2 PNCO, F 2 PNCS, [11] and F 2 PNCSe [12] revealed the existence of only one conformer, in which the pseudohalogen groups are in an antiperiplanar (anti) orientation with respect to the bisector of the FPF angle.…”