Difluorothiophosphoryl isocyanate, F₂P(S)NCO was characterized with UV/vis, NMR, IR (gas and Ar‐matrix), and Raman (liquid) spectroscopy. Its molecular structure was also established by means of gas electron diffraction (GED) and single crystal X‐ray diffraction (XRD) in the gas phase and solid state, respectively. The analysis of the spectroscopic data and molecular structures is complemented by extensive quantum‐chemical calculations. Theoretically, the C_s symmetric syn‐conformer is predicted to be the most stable conformation. Rotation about the P−N bond requires about 9 kJ mol⁻¹ and the predicted existence of an anti‐conformer is dependent on the quantum‐chemical method used. This syn‐orientation of the isocyanate group is the only one found in the gas phase and contained likewise in the crystal. The overall molecular structure is very similar in gas and solid, despite in the solid state the molecules arrange through intramolecular O⋅⋅⋅F contacts into layers, which are further interconnected by S⋅⋅⋅N, S⋅⋅⋅C and C⋅⋅⋅F contacts. Additionally, the photodecomposition of F₂P(S)NCO to form CO, F₂P(S)N, and F₂PNCO is observed in the solid Ar‐matrix.

中文翻译：

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气相和固相二氟硫代磷酸异氰酸酯的光谱性质、构象和结构。

二氟硫代磷酰异氰酸酯 F ₂ P(S)NCO 用 UV/vis、NMR、IR（气体和 Ar 基质）和拉曼（液体）光谱进行了表征。其分子结构也分别通过气相和固态的气体电子衍射 (GED) 和单晶 X 射线衍射 (XRD) 建立。光谱数据和分子结构的分析得到了广泛的量子化学计算的补充。理论上，C _s对称顺式构象被预测为最稳定的构象。围绕 P-N 键的旋转需要大约 9 kJ mol ^-1并且反构象的预测存在取决于所使用的量子化学方法。这个异氰酸酯基团的同向取向是唯一在气相中发现的，并且同样包含在晶体中。整体分子结构在气体和固体中非常相似，尽管在固体状态下分子通过分子内 O⋅⋅⋅F 接触排列成层，这些层通过 S⋅⋅⋅N、S⋅⋅⋅C 和 C⋅ 进一步互连⋅⋅F接触。此外，在固体 Ar 基质中观察到 F ₂ P(S)NCO 光分解形成 CO、F ₂ P(S)N 和 F ₂ PNCO。