期刊
RSC ADVANCES
卷 8, 期 6, 页码 3328-3342出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7ra11603a
关键词
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资金
- Korea Research Fellowship program - Ministry of Science, ICT and Future Planning through the National Research Foundation of Korea [NRF-2015H1D3A1062502, NRF-2015R1C1A1A02036670, NRF-2015R1A2A2A01006445]
- Basic Science Research Program - Ministry of Science, ICT and Future Planning through the National Research Foundation of Korea [NRF-2015H1D3A1062502, NRF-2015R1C1A1A02036670, NRF-2015R1A2A2A01006445]
Nitro-nitrito isomerization in Co(NH3)(5)NO22+ linkage isomers was investigated with a focus on the geometries, relative stabilities and chemical bonding using omega B97XD/6-31+G(d,p) to elucidate the photo salient effect in [Co(NH3)(5)NO2]NO3Cl. Different techniques like atoms in molecules (AIM), electron localization function (ELF) and natural bonding orbital (NBO) were used to gain insight into the chemical bonds of the isomers and to identify the key factors influencing their relative stabilities. The study of the ground-state potential energy surface of Co(NH3)(5)NO22+ reveals that the nitro/exo-nitrito isomerization reaction can proceed via the following two paths: (1) nitro -> TS1 (38.16 kcal mol(-1)) -> endo-nitrito -> TS2 (9.68 kcal mol(-1)) -> exo-nitrito and (2) nitro -> TS3 (41.76 kcal mol(-1)) -> exo-nitrito. Pathway (1) through endo-nitrito is the most likely isomerization mechanism because of a lower energy barrier than pathway (2). The intramolecular-resonance-assisted hydrogen bonds (N-H center dot center dot center dot O and N-H center dot center dot center dot N), the orientation of NO2, and the difference between Co-N and Co-O bond energies are identified as the key factors determining the relative stabilities of the linkage isomers. Co(NH3)(6)(3+) is less stable compared to Co(NH3)(5)NO22+ and undergoes a slight geometrical distortion from D-3d to either D-3 or S-6 characterized by a stabilization energy of similar to 750 cm(-1) at CCSD(T)/6-31+G(d,p).
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