Spectroscopic and structural properties of N-sulfinyl-benzenamine, O=S=N-C6H5

ROSANA M. ROMANO; CARLOS O. DELLA VÉDOVA; PETER HILDEBRANDT

JOURNAL OF MOLECULAR STRUCTURE

Año: 1999 vol. 508 p. 5 - 17

0022-2860

N-sulfinyl-benzeneamine, OySyN–C6H5, was studied by spectroscopic and quantum chemical methods. It was shown that the ground state exhibits a planar structure with a Z configuration with regard to the C–N single and SyO double bonds. This configuration which has recently been determined for the crystalline state is evidently a general structural motif for this class of compounds in the liquid state and in solution. This configuration is also energetically favoured in those derivatives which carry sterically demanding substituents at the ortho positions of the ring. The analysis of the resonance Raman spectra in the region between 514 and 420 nm reveals a preferential enhancement for the totally symmetric modes. These results demonstrate that the Cs point group is unchanged upon excitation in resonance with the p! p* transition of the NSO chromophore. For some of the modes, evidence is provided for a coupling with further electronic transitions, i.e., an n! p* and a p! p* transition of the NSO and aromatic chromophore, respectively.-sulfinyl-benzeneamine, OySyN–C6H5, was studied by spectroscopic and quantum chemical methods. It was shown that the ground state exhibits a planar structure with a Z configuration with regard to the C–N single and SyO double bonds. This configuration which has recently been determined for the crystalline state is evidently a general structural motif for this class of compounds in the liquid state and in solution. This configuration is also energetically favoured in those derivatives which carry sterically demanding substituents at the ortho positions of the ring. The analysis of the resonance Raman spectra in the region between 514 and 420 nm reveals a preferential enhancement for the totally symmetric modes. These results demonstrate that the Cs point group is unchanged upon excitation in resonance with the p! p* transition of the NSO chromophore. For some of the modes, evidence is provided for a coupling with further electronic transitions, i.e., an n! p* and a p! p* transition of the NSO and aromatic chromophore, respectively.Z configuration with regard to the C–N single and SyO double bonds. This configuration which has recently been determined for the crystalline state is evidently a general structural motif for this class of compounds in the liquid state and in solution. This configuration is also energetically favoured in those derivatives which carry sterically demanding substituents at the ortho positions of the ring. The analysis of the resonance Raman spectra in the region between 514 and 420 nm reveals a preferential enhancement for the totally symmetric modes. These results demonstrate that the Cs point group is unchanged upon excitation in resonance with the p! p* transition of the NSO chromophore. For some of the modes, evidence is provided for a coupling with further electronic transitions, i.e., an n! p* and a p! p* transition of the NSO and aromatic chromophore, respectively.ortho positions of the ring. The analysis of the resonance Raman spectra in the region between 514 and 420 nm reveals a preferential enhancement for the totally symmetric modes. These results demonstrate that the Cs point group is unchanged upon excitation in resonance with the p! p* transition of the NSO chromophore. For some of the modes, evidence is provided for a coupling with further electronic transitions, i.e., an n! p* and a p! p* transition of the NSO and aromatic chromophore, respectively.s point group is unchanged upon excitation in resonance with the p! p* transition of the NSO chromophore. For some of the modes, evidence is provided for a coupling with further electronic transitions, i.e., an n! p* and a p! p* transition of the NSO and aromatic chromophore, respectively.! p* and a p! p* transition of the NSO and aromatic chromophore, respectively.