Synthesis, Structure, and Characterization of Tris(1-ethyl-4-isopropyl-imidazolyl-κN)phosphine Nickel(II) Complexes
| Autor: | Reza Loloee, Jia Li, Ferman A. Chavez, Atanu Banerjee, Chanel R. Easley, William W. Brennessel |
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| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Chemistry Coordination number chemistry.chemical_element 010402 general chemistry 01 natural sciences Medicinal chemistry Magnetic susceptibility Article 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Nickel Tripodal ligand Materials Chemistry Physical and Theoretical Chemistry HOMO/LUMO Phosphine Isopropyl Dichloromethane |
| Zdroj: | Inorganica chimica acta. 489 |
| ISSN: | 0020-1693 |
| Popis: | In this work we report the synthesis of five new nickel(II) complexes all coordinated to the tripodal ligand tris(1-ethyl-4-(i)Pr-imidazolyl)phosphine (TlEt4iPrIP). They are [Ni(T1Et4iPrIP)(CH(3)CN)(2)(OTf)](OTf) (1), [Ni(T1Et4iPrIP)(OTf)(2)] (2), [Ni(T1Et4iPrIP)(H(2)O)(OTf)](OTf) (3), [Ni(T1Et4iPrIP)Cl](OTf) (4), and [Ni(T1Et4iPrIP)Cl(2)] (5). The complexes serve as bioinorganic structural model complexes for histidine-coordinated nickel proteins. The X-ray structures have been determine for all complexes which feature coordination numbers 4-6. We investigated the spectroscopic interconversions for these compound in dichloromethane solution and demonstrate interconversion between 1-3 and conversion of 2 to 4. Complex 5 can be spectroscopically converted to the cation of 4 by dissolving it in dichloromethane. Fits of variable temperature magnetic susceptibility data yielded the following parameters: g = 1.944, D = −0.327 cm(−1), E/D = 3.706 for 1; g = 2.280, D = −0.365 cm(−1), E/D = 22.178 for 2; g = 2.000, D = −7.402 cm(−1), E/D = −0.272 for 3; g = 2.176, D = −0.128 cm(−1), E/D = −0.783 for 4; g = 2.258, D = 14.288 cm(−1), E/D = 0.095 for 5. DFT structure optimizations afforded HOMO and LUMO energies indicating that complex 1 is the most stable. |
| Databáze: | OpenAIRE |
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