Effect of ligand substituent coordination on the geometry and the electronic structure of Cu(II)-diradical complexes
| Autor: | Samir Ghorai, Soumava Biswas, Chandan Mukherjee, Richa Rakshit |
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| Rok vydání: | 2014 |
| Předmět: |
Models
Molecular Aniline Compounds Free Radicals Chemistry Diradical Ligand Stereochemistry Substituent Molecular Conformation Electrons Electronic structure Crystallography X-Ray Ligands Magnetic susceptibility law.invention Inorganic Chemistry Crystallography chemistry.chemical_compound Unpaired electron law Organometallic Compounds Moiety Physical and Theoretical Chemistry Electron paramagnetic resonance Copper |
| Zdroj: | Inorganic chemistry. 53(7) |
| ISSN: | 1520-510X |
| Popis: | Two organic moieties, known as ligands, having -OMe and -SePh as the ortho substituent attached to the aniline moiety of the parent 2-anilino-4,6-di-tert-butylphenol ligand, were synthesized. The ligands reacted with CuCl2·2H2O in a 2:1 ratio in CH3CN in the presence of Et3N and provided the corresponding mononuclear Cu(II)-diradical complexes 1 (-OMe) and 2 (-SePh). Complex 1 was square planar, while complex 2 was in distorted square planar geometry due to the secondary coordination between the Se atom and the central Cu(II) center. Both complexes were comprised of multi-paramagnetic centers and exhibited an St = 1/2 ground state as established by variable-temperature magnetic susceptibility measurements. X-band electron paramagnetic resonance measurements indicated the presence of an unpaired electron at the Cu(II) center in complex 1 and at the ligand center (π-radical) in complex 2. The extent of the secondary interaction was found to be dependent on the "softness" of the donor atom belonging to the ortho substituent. |
| Databáze: | OpenAIRE |
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