Chloryl chloride, ClC102, isolated in cryogenic matrices is subjected to photolysis, producing chlorine chlorite, ClOClO, which in turn is converted into dichlorine peroxide, ClOOCl. ClOClO is also formed by the reactions C1+OClO and ClOCl + 0. The products are identified by means of FTIR spectroscopy using 35/37C1 and la/lsO isotopic shifts, with the aid of vibrational spectra of related molecules and results of ab initio calculations. The thresholds for photodecomposition of ClOClO, C1C102, and ClOOCl isolated in an argon matrix are above wavelengths of 665,610, and 360 nm, respectively. Two dissociation channels are observed for both ClOClO and ClOOCl. For ClOClO they are (i) C1+ OC10, leading to ClC102 and (ii) 2C10, yielding ClOOCl. For ClOOCl they are (i) ClOO + C1, resulting in Cl2 + 02, and (ii) 2C10, giving rise to ClOClO. The observation of two photolysis paths for ClOOCl is of importance for the catalytic ozone depletion in the polar stratosphere. Irradiation of ClC102 isolated in a neon matrix resulted in C12 + 0 2 as the only products. The UV spectra of ClC102 in the gas phase and in a neon matrix are reinvestigated.Lower limits for the integral band strengths of ClOClO and ClOOCl are derived relative to those of C1C102. The vibrational data of this study, in conjunction with results of submillimeter spectroscopic investigations, are used to calculate a general valence force field for ClOOCl.

No abstract

No longer up in the air: The radicals SF5Ox (x=0–3) were isolated in a matrix and characterized by IR and UV spectroscopy, photolysis experiments, and quantum chemical calculations. They are probably involved in the atmospheric oxidation of SF6, a gas commonly used in the electricpower industry.

A harmonic force field for difluorodioxirane was derived from fundamental wavenumbers, isotopic shifts, centrifugal distortion constants, and inertial defect differences. The following geometric structure was determined by a joint analysis of gas electron diffraction intensities and rotational constants of the parent species (rz values with 1σ uncertainties):  O−O = 1.578(1), C−O = 1.348(8), C−F = 1.317(6) Å, ∠FCF = 108.8(7)°. The extremely long O−O bond correlates with the small force constant of 2.94 × 102 N m-1.

Tris(pentafluorosulfanyl)amine, N(SF 5 ) 3 , and the bis(pentafluorosulfanyl)aminyl radical, ·N(SF 5 ) 2, have been synthesized and characterized by gas electron diffraction, single crystal XRD, NMR, EPR, FT-IR, Raman, and UV-vis spectroscopy, and by their thermal decompositions. The amine possesses a planar molecular structure of D 3 symmetry with an unusually long N-S bond of 1.829(6) Å. The long N-S bonds are in accordance with the small Arrhenius activation barrier for the decay into ·N(SF 5 ) 2 and ·SF 5 radicals of 6.9 kcal mol -1 , and its half-life at room temperature is only 50 minutes. The aminyl radical possesses C 2 symmetry with N-S = 1.692(4) Å and S-N-S = 135.1(5)°, and its structure is similar to that of FN(SF 5 ) 2 . This radical is much more stable than the amine (half-life at room temperature is 130 minutes). Dimerization and formation of the corresponding hydrazine, (SF 5 ) 2 NN(SF 5 ) 2 , was not observed, nor was the nitrene :NSF 5 or its isomer FN=SF 4 .

O für O: Die Radikale SF5Ox (x=0–3; siehe Bild) wurden in Matrix isoliert und durch IR‐ und UV‐Spektroskopie, Photolyseexperimente und quantenchemische Rechnungen charakterisiert. Ihre mögliche Beteiligung an Reaktionen in der Atmosphäre wird diskutiert.

General valence force fields for SF(3)CN and FS(O)CN are derived from vibrational data taken from the literature and from theoretical calculations. Gas phase electron diffraction studies on both molecules yield the following geometric parameters (r(a) distances and angles with 3sigma uncertainties). SF(3)CN: r(S-F(e)) = 155.2(4) r(S-F(a)) = 165.7(3), r(S-C) = 173.6(8), r(C&tbd1;N) = 115.9(4) pm; angle(F(a)SF(e)) = 86.9(3), angle(F(a)SC) = 86.0(4) angle(F(e)SC) = 98.7(8), angle(F(a)SF(a)) = 169.0(6), angle(SCN) = 171(4) degrees. FS(O)CN: r(S-F) = 159.8(3), r(S=O) = 143.2(2), r(S-C) = 178.3(3), r(C&tbd1;N) = 115.0(3) pm; angle(FSO) = 104.9(4), angle(FSC) = 93.9(4), angle(CSO) = 105.3(5), angle(SCN) = 176(4) degrees. These experimental results are compared to ab initio values (HF/3-21G, HF/6-31G, and MP2/6-31G), and the bonding properties in these sulfur (IV) cyanides are discussed.

2005 IR and Raman spectra C 2530The SF 5 O x Radicals, x: 0-3. -The title radicals are characterized by UV and IR spectroscopy in Ar, Ne, or O2 matrices, and by DFT B3LYP calculations, proving their existence. The significance of SF5Ox radicals in atmospheric chemistry is discussed. -(KRONBERG, M.; VON AHSEN, S.; WILLNER*, H.; FRANCISCO, J. S.; Angew. Chem., Int. Ed. 44 (2005) 2, 253-257; Fachbereich 9, Anorg. Chem.,