Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, China.
J Phys Chem A. 2011 Jun 23;115(24):6551-8. doi: 10.1021/jp203352e. Epub 2011 May 23.
The reactions of titanium oxide molecules with dinitrogen have been studied by matrix isolation infrared spectroscopy. The titanium monoxide molecule reacts with dinitrogen to form the TiO(N(2))(x) (x = 1-4) complexes spontaneously on annealing in solid neon. The TiO(η(1)-NN) complex is end-on bonded and was predicted to have a (3)A'' ground state arising from the (3)Δ ground state of TiO. Argon doping experiments indicate that TiO(η(1)-NN) is able to form complexes with one or more argon atoms. Argon atom coordination induces a large red-shift of the N-N stretching frequency. The TiO(η(2)-N(2))(2) complex was characterized to have C(2v) symmetry, in which both the N(2) ligands are side-on bonded to the titanium metal center. The tridinitrogen complex TiO(η(1)-NN)(3) most likely has C(3v) symmetry with three end-on bonded N(2) ligands. The TiO(η(1)-NN)(4) complex was determined to have a C(4v) structure with four equivalent end-on bonded N(2) ligands. In addition, evidence is also presented for the formation of the TiO(2)(η(1)-NN)(x) (x = 1-4) complexes, which were predicted to be end-on bonded.
通过基质隔离红外光谱法研究了氧化钛分子与二氮的反应。在固态氖中退火时，一氧化钛分子与二氮自发反应，形成 TiO(N(2))(x) (x = 1-4) 配合物。TiO(η(1)-NN) 配合物为端接键合，预测其基态为 (3)A''，源于 TiO 的 (3)Δ 基态。氩掺杂实验表明，TiO(η(1)-NN) 能够与一个或多个氩原子形成配合物。氩原子配位诱导 N-N 伸缩振动频率的大幅红移。TiO(η(2)-N(2))(2) 配合物具有 C(2v) 对称性，其中两个 N(2)配体均以侧接键合于钛金属中心。三氮配合物 TiO(η(1)-NN)(3) 极有可能具有 C(3v) 对称性，其中三个 N(2)配体均为端接键合。TiO(η(1)-NN)(4) 配合物确定为 C(4v) 结构，其中四个 N(2)配体等价地以端接键合。此外，还提出了形成 TiO(2)(η(1)-NN)(x) (x = 1-4) 配合物的证据，预测其为端接键合。
