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Updated: Nov 14, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Variable electronic structure and spin distribution in bis(2,2'-bipyridine)-metal complexes (M = Ru or Os) of
Madhumita Chatterjee1, Sudipta Mondal, Arijit Singha Hazari
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India. lahiri@chem.iitb.ac.in.
Abstract:
The odd-electron compounds [M(bpy)2(L1)](ClO4) M = Ru ([1](ClO4)) or Os ([2](ClO4)), and the even-electron species [M(bpy)2(H2L2)](ClO4)2, M = Ru ([3](ClO4)2) or Os ([4](ClO4)2) were obtained from pyrene-4,5-dione, L1, or 4,5-diaminopyrene, H4L2, and were characterised structurally, electrochemically and spectroscopically. Experimental and computational analysis (TD-DFT) revealed rather different electronic structures and spin distributions of the paramagnetic monocations 1+-4+. EPR investigations and electronic absorption studies exhibit increasing metal contributions to the singly occupied MO along the series 1+ < 3+ < 4+ < 2+, illustrated by g value and long-wavelength absorbance. In addition to variations of the metal (Ru,Os) and the donor atoms (O,NH) the extension of the π system of the semiquinone-type ligand has a large effect on the electronic structure of the paramagnetic cations.
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