Department of Chemistry, Zhejiang Sci-Tech University, Hanzhou, China.
J Phys Chem A. 2010 Aug 12;114(31):8083-9. doi: 10.1021/jp103866r.
The reaction of tantalum dioxide molecule with dinitrogen has been studied by matrix isolation infrared spectroscopy. The tantalum dioxide molecules produced from laser evaporation of bulk Ta(2)O(5) target reacted with dinitrogen to form the TaO(2)(eta(1)-NN)(x) (x = 1-3) complexes on annealing, in which the N(2) ligands are end-on bonded to the tantalum metal center. The TaO(2)(eta(1)-NN)(3) complex decomposed to TaO(2)(eta(1)-NN)(2) under infrared irradiation. The TaO(2)(eta(1)-NN)(2) and TaO(2)(eta(1)-NN)(3) complexes rearranged to the less stable TaO(2)(eta(1)-NN)(eta(2)-N(2)) and TaO(2)((eta(1)-NN)(2)(eta(2)-N(2)) isomers under visible light excitation. Both the mono- and bis-dinitrogen complexes were predicted to have (2)A' or (2)A(1) ground states arising from the (2)A(1) ground state of TaO(2), whereas the two tridinitrogen complexes were predicted to have (2)B(2) ground states with C(2v) symmetry, which are derived from the (2)B(1) excited state of TaO(2).
通过基质隔离红外光谱研究了二氧化钽分子与氮气的反应。用激光蒸发大块 Ta(2)O(5)靶产生的二氧化钽分子与氮气反应，在退火时形成 TaO(2)(eta(1)-NN)(x) (x = 1-3)配合物，其中 N(2)配体端接键合到钽金属中心。在红外辐照下，TaO(2)(eta(1)-NN)(3)配合物分解为 TaO(2)(eta(1)-NN)(2)。在可见光激发下，TaO(2)(eta(1)-NN)(2)和 TaO(2)(eta(1)-NN)(3)配合物重排为不太稳定的 TaO(2)(eta(1)-NN)(eta(2)-N(2))和 TaO(2)((eta(1)-NN)(2)(eta(2)-N(2)))异构体。单核和双核二氮配合物均预测具有源于 TaO(2)的(2)A'或(2)A(1)基态的(2)A'或(2)A(1)基态，而两个三氮配合物则预测具有 C(2v)对称的(2)B(2)基态，其源于 TaO(2)的(2)B(1)激发态。
