1995 Fiscal Year Final Research Report Summary
Synthesis and design of paramagnetic metal complexes containing stable radicals and their spectroscopic study
| Project/Area Number |
06453049
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Inorganic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
KAIZAKI Sumio Osaka University, Dept.Chem., PROFESSOR, 理学部, 教授 (20089874)
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| Co-Investigator(Kenkyū-buntansha) |
FUYUHIRO Akira Osaka University, Dept.Chem.RESEARCH ASSISTANT, 理学部, 助手 (90156951)
YAMANARI Kazuaki Osaka University, Dept.Chem.ASSOCIATE PROFESSOR, 理学部, 助教授 (40116124)
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| Project Period (FY) |
1994 – 1995
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| Keywords | Stable Radical / Radical Complexes / Spin-Forbidden Transition / Radical-metal Interaction |
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| Research Abstract |
This research aims at versatility and fine-tuning of the exchange coupling between metal complexes and radical ligands together with electronic and magnetic interaction between the ligand field and radicals as well as the reactivity of radical complexes in solutions for the primary purpose of synthesis and design of paramagnetic metal complexes containing radical ligands.
Firstly, we have revealed the behavior or the d electron state due to the subtle change of the ligand field such as the solvent effects as observed for the NMR and solvatochromism as well as anomalous trigonal field splitting due to anisotropic pi bonding. Furthermore, we explored the steric effect due to weak intramolecular interactions such as hydrogen bond and CH/pi interaction. These studies are the important and basic information to examine the coordination bond between the metal and radical, especially between the d orbital and pi^* orbital (SOMO)
Secondarily, radical complexes of paramagnetic Cr(III) and Ni(II) metal such as [Cr(acac)_2(NIT2-py)]+or[Ni(dbm)_2(NIT2-py)](dbm=dibenzoylmethane) and those of diamagnetic Co(III) metal such as trans-[Co(acac)_2(X)(NIT4+py)]^n(X=PPh_3 : n=1+ ; NO_<-2> : n=0)) and trans-[Co(acac)_2(P(Ph_3))(4-NH_2tempo)]+have been prepared. Their stability and magneto-optic properties such as the intensity enhancement of the spin-forbidden transitions were examined. The X-ray structure analysis of trans-[Co(acac)_2(PPh_3)(NIT4-py)]+confirmed the pyridine coordination mode. These data will be an important clue to accomplish the present purpose and valuable for the chemistry for radical complexes.
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