Microsolvation of cobalt, nickel, and copper atoms with ammonia: a theoretical study of the solvated electron precursors.

ABSTRACT

CONTEXT The s-block metals dissolved in ammonia form metal-ammonia complexes with diffuse electrons which could be used for redox catalysis. In this theoretical paper, we investigated the possibility of the d-bloc transition metals (Mn, Fe, Co, Ni, and Cu) solvated by ammonia. It has been demonstrated that both Mn and Fe atoms undergo into an oxidative reaction with NH3 forming an inserted species, HMNH2. On the contrary, the Co, Ni, and Cu atoms can accommodate four NH3, via the coordination bond, to form the first solvation sphere within C2v, D2d, and Td point groups, respectively. Addition of a fifth NH3 constitute the second solvation shell by forming hydrogen bond with the other NH3s. Interestingly, M(NH3)4 (M = Co, Ni, and Cu) is a so-called solvated electron precursor and should be considered as a monocation M(NH3)4+ kernel in tight contact with one electron distributed over its periphery. This nearly free electron could be used to capture a CO2 molecule and engages in a reduction reaction. METHODS: Geometry optimization of the stationary points on the potential energy surface was performed using density functional theory - CAM-B3LYP functional including the GD3BJ dispersion contribution - in combination with the 6-311 + + G(2d, 2p) basis set for all the atoms. All first-principles calculations were performed using the Gaussian 09 quantum chemical packages. The natural electron configuration of transition atom engaged in the compounds has been found using the natural bond orbital (NBO) method. We used the EDR (electron delocalization range) approach to analyze the structure of solvated electrons in real space. We also used the electron localization function (ELF) to measure the degree of electronic localization within a chemical compound. The EDR and ELF analyses are done using the TopMod and Multiwfn packages, respectively.