Infrared spectra, structures, and force constants of the matrix-isolated thiazyl halides CISN and BrSN

Maximising rovibrational assignments in the ν1 band of NSCl by spectral analysis by subtraction of simulated intensities (SASSI)

“…The vibrational assignments of all seven bands were consistent with their relative intensities (as given in Table 1), with the expected shifts in their band centres, and with the rotational constants from microwave data for all three isotopomers in their ground vibrational states and for 14 N 34 S 35 Cl in the 2 1 , 3 1 and 3 2 states. The band centre in 14 N 34 S 35 Cl 1 1 0 is isotopically shifted by À11.8 cm À1 relative to 14 N 32 S 35 Cl 1 1 0 , the same shift seen in Ar matrix spectra [7]. As a result, some of the P-branch transitions of 14 N 34 S 35 Cl 1 1 0 are more exposed which helped their assignment.…”

“…Its IR spectrum has been studied at low resolution in the gas phase by Mü ller et al [5,6], in argon matrix by Peake and Downs [7], and in low temperature solid films by Emken et al [8]. The geometry of NSCl has been determined by microwave spectroscopy of various isotopomers [9,10] and, later, by electron diffraction [11].…”

High resolution FTIR spectroscopy of the ν1band of NSCl

“…The low resolution IR spectrum was first measured in the gas phase by Mu¨ller et al, 1,2 who deduced a bent molecular structure of C s symmetry with the sulfur atom in the centre. Six isotopomers, including some with 37 Cl, 15 N or 34 S atoms, were examined in a matrix IR study 3 and low temperature IR spectra of solid films have also been measured recently. 4 Microwave spectroscopy data was used to determine the bond lengths and angles of NSCl through isotopic substitution, 5 and to determine the dipole moment and centrifugal distortion parameters.…”

“…6 The geometry ascertained by electron diffraction is consistent with the microwave results. 7 Several empirically determined harmonic force fields have been reported [1][2][3]5,6,8 along with anharmonic force fields computed ab initio at the Hartree-Fock level. 9,10 High level ab initio molecular orbital calculations have been used to compute anharmonic vibrational wavenumber values, 11 and to show that thiazyl chloride is around 22 kcal mol À1 more stable than thionitrosyl chloride ion, ClNS.…”

The preparation of thiazyltrifluoromethane, CF3SN, the hexachloro-3-cyclopentenylidenaminosulfides C5Cl6NSX (X = CF3, Cl, NSO, SCF3, C5Cl6N) and the crystal structures of C5Cl6NSX (X = CF3, Cl)

“…The reactivity of I1 is comparable to that of other sulfanyl chlorides. With Hg(SCF3)2 C5C16NSSCF3 forms in good yields and with SbC15 in SO2 the reaction takes place according to reaction [3]. Again it is evident that ClSN reacts as a nitrene with C5C16.…”