49 70

Theoretical investigation on the ground state properties of the hexaamminecobalt(III) and nitro-nitrito linkage isomerism in pentaamminecobalt(III) in vacuo

Title
Theoretical investigation on the ground state properties of the hexaamminecobalt(III) and nitro-nitrito linkage isomerism in pentaamminecobalt(III) in vacuo
Author
이상욱
Keywords
SOLID-STATE; ELECTRON LOCALIZATION; STRUCTURAL ISOMERISM; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURE; AQUEOUS-SOLUTION; SINGLE-CRYSTAL; ISOMERIZATION; COMPLEXES; ION
Issue Date
2018-01
Publisher
ROYAL SOC CHEMISTRY
Citation
RSC ADVANCES, v. 8, no. 6, page. 3328-3342
Abstract
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).
URI
https://pubs.rsc.org/en/content/articlelanding/2018/RA/C7RA11603A#!divAbstracthttps://repository.hanyang.ac.kr/handle/20.500.11754/117040
ISSN
2046-2069
DOI
10.1039/c7ra11603a
Appears in Collections:
GRADUATE SCHOOL[S](대학원) > BIONANOTECHNOLOGY(바이오나노학과) > Articles
Files in This Item:
Theoretical investigation on the ground state properties of the hexaamminecobalt(III) and nitro-nitrito linkage isomerism in pentaamminecobalt(III)...Download
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE