Wang Lichen, Wang Guanjun, Qu Hui, Wang Caixia, Zhou Mingfei
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University , Shanghai 200433, China.
J Phys Chem A. 2014 Mar 13;118(10):1841-9. doi: 10.1021/jp500152c. Epub 2014 Mar 4.
Infrared spectra of mass-selected mononuclear iron nitrosyl cations Fe(NO)n(+) with n = 1-5 and their argon tagged complexes are measured via infrared photodissociation spectroscopy in the nitrosyl stretching frequency region in the gas phase. The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations. Two IR active bands were observed for the argon-tagged Fe(NO)2(+) and Fe(NO)3(+) complexes, consistent with theoretical predictions that these complexes have bent C(2v) and nonplanar C(3v) symmetry, respectively. The Fe(NO)4(+) complex was characterized to have a completed coordination sphere with 17 electrons containing a bent one-electron NO ligand and three three-electron NO ligands. The Fe(NO)5(+) complex was determined to involve a Fe(NO)4(+) core ion that is solvated by an external NO molecule.
通过红外光解离光谱法在气相中的亚硝酰基伸缩频率区域测量了质量选择的单核铁亚硝酰阳离子Fe(NO)n(+)（n = 1 - 5）及其氩标记配合物的红外光谱。通过将实验光谱与密度泛函计算得出的模拟光谱进行比较来确定结构。对于氩标记的Fe(NO)2(+)和Fe(NO)3(+)配合物观察到两个红外活性带，这与理论预测一致，即这些配合物分别具有弯曲的C(2v)和非平面的C(3v)对称性。Fe(NO)4(+)配合物的特征是具有一个完整的配位球，包含17个电子，其中有一个弯曲的单电子NO配体和三个三电子NO配体。确定Fe(NO)5(+)配合物涉及一个由外部NO分子溶剂化的Fe(NO)4(+)核心离子。
