First-row transition metal complexes of the strongly donating pentadentate ligand PY4Im |
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Authors: | Smith Jeremy M Long Jeffrey R |
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Institution: | Department of Chemistry and Biochemistry, MSC 3C, New Mexico State University, Las Cruces New Mexico 88003, United States. jesmith@nmsu.edu |
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Abstract: | The new ligand PY4Im, which incorporates an axial N-heterocyclic carbene and four equatorial pyridine donors, is readily prepared on a multigram scale. Six-coordinate first row transition metal complexes of the general formula (PY4Im)M(MeCN)](2+) (M = Fe, Co, Ni, Cu), where the PY4Im ligand coordinates in a square pyramidal pentadentate fashion, have been prepared. Structural, spectroscopic, and electrochemical characterization of these compounds provides evidence that PY4Im is a strongly donating ligand that favors the formation of low-spin complexes. Chemical oxidation of the iron(II) complex provides a low spin iron(III) complex, which has also been structurally and spectroscopically characterized. In the case of manganese(II), the PY4Im ligand is unable to either enforce a low-spin state or fully accommodate the metal ion. Rather, the ligand binds in a tridentate, face-capping mode. |
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