Reactions of late lanthanide metal atoms with water molecules: a matrix isolation infrared spectroscopic and theoretical study.
The reactions of late lanthanide metal atoms (Gd-Lu) with water molecules have been investigated using matrix isolation infrared spectroscopy. The reaction intermediates and products were identified on the basis of isotopic substitution experiments and density functional theory calculations. All of the metal atoms except Lu react with water to form the M(H2O) complexes spontaneously upon annealing (M = Gd, Tb, Dy, Ho, Er, Tm, and Yb). The Dy(H2O) and Ho(H2O) complexes are able to coordinate a second water molecule to form the Dy(H2O)2 and Ho(H2O)2 complexes. The M(H2O) complexes isomerize to the inserted HMOH isomers under visible light irradiation, which further decompose to give the MO and/or HMO molecules upon UV light irradiation. The M(OH)2 molecules (M = Gd-Lu) were also produced. The results have been compared with our earlier work covering the early lanthanide metal atoms (Nd, Sm, Eu) to observe the existent trends for the lanthanide metal atom reactions.
Xu
Jia
J
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai 200433, People's Republic of China.
Jin
Xi
X
Zhou
Mingfei
M