FB C-Anorganische Chemie, Bergische Universität Wuppertal, Gaussstrasse 20, 42097 Wuppertal, Germany.
Inorg Chem. 2010 Mar 15;49(6):3002-10. doi: 10.1021/ic902524u.
Difluorophosphoryl azide, F(2)P(O)N(3), was fully characterized by (19)F, (31)P, (14)N, and (15)N NMR, as well as by IR (gas, Ar-matrix), and Raman (liquid, solid) spectroscopy. For comparison the vibrational spectra of the isoelectronic difluorophosphoryl isocyanate, F(2)P(O)NCO was also studied. Both molecules were found to exist as single rotamers in the gas, liquid, and solid states. Their solid-state structures were determined by X-ray crystallography as the rotamers with the P=O bond being cis to the pseudohalide groups (with respect to the P-N bond). The F(2)P(O)N(3) molecule exhibits approximate C(s) symmetry (phi(O1P1-N1N2) = -0.7(3) degrees), while F(2)P(O)NCO is significantly distorted from C(s) symmetry (phi(O1P1-N1C1) = -18.9(5) degrees) because of intermolecular C...O contacts. The crystal structure of difluorophosphoric acid anhydride, F(2)(O)POP(O)F(2), was also determined, possessing crystallographic C(2) symmetry with the two F(2)PO groups slightly staggered by 10.66(7) degrees along the P...P vector, and a P-O-P angle of 140.89(10) degrees for the bridging oxygen atom. The experimental results are supported by quantum chemical calculations, and the conformational properties of F(2)P(O)N(3) and F(2)P(O)NCO are discussed.
二氟膦酰叠氮化物，F(2)P(O)N(3)，通过 (19)F、(31)P、(14)N 和 (15)N NMR 以及 IR（气体、Ar 基质）和拉曼（液体、固体）光谱学进行了全面表征。为了进行比较，还研究了等电子的二氟膦酰异氰酸酯，F(2)P(O)NCO 的振动光谱。在气体、液体和固体状态下，这两种分子都被发现仅以单一构象存在。它们的固态结构通过 X 射线晶体学确定为 P=O 键与拟卤化物基团（相对于 P-N 键）顺式的构象。F(2)P(O)N(3)分子表现出近似的 C(s)对称性（phi(O1P1-N1N2) = -0.7(3) 度），而 F(2)P(O)NCO 由于分子间 C...O 接触而明显偏离 C(s)对称性（phi(O1P1-N1C1) = -18.9(5) 度）。二氟磷酸酐，F(2)(O)POP(O)F(2) 的晶体结构也被确定，具有结晶 C(2)对称性，两个 F(2)PO 基团沿 P...P 矢量略微错开 10.66(7) 度，桥氧原子的 P-O-P 角为 140.89(10) 度。实验结果得到量子化学计算的支持，并讨论了 F(2)P(O)N(3)和 F(2)P(O)NCO 的构象性质。
