Issue 19, 1998

Electronic structure of radical anionic binuclear organoplatinum complexes. A multiple frequency EPR investigation

Abstract

The dinuclear organoplatinum compounds RnPt(µ-BL)PtRn (R = Me = methyl, n = 2,4; R = Mes = mesityl, n = 2; µ-BL = the bridging ligands 2,2′-bipyrimidine (bpym), 2,5-bis(1-phenyliminoethyl)pyrazine (bpip) or 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) undergo reversible one-electron reductions to yield the corresponding radical anions [RnPt(µ-BL)PtRn The chemically or electrochemically reduced species were studied by continuous wave EPR spectroscopy at various microwave frequencies (4–34 GHz). With one exception, only a single broad line is observed in fluid solution at ambient temperatures and X-band. Measurements on glassy frozen solutions at 110 K at S-, X-, K- or Q-band reveal not only all the three g-values for the rhombic spectra but also most of the hyperfine coupling constants to the 195Pt nuclei and also to two 1H nuclei of the bridging ligand when µ-BL = bpym. Density functional–Hartree–Fock (DFT–HF) molecular orbital calculations show the singly occupied molecular orbital in each case to be predominantly bridging-ligand based, in good agreement with the magnitudes of the observed 195Pt hyperfine coupling constants. The molecular structure of the free ligand 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) was determined by X-ray crystallography to serve as a basis for the calculations.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans., 1998,94, 2979-2984

Electronic structure of radical anionic binuclear organoplatinum complexes. A multiple frequency EPR investigation

A. Klein, E. J. L. McInnes, T. Scheiring and S. Zališ, J. Chem. Soc., Faraday Trans., 1998, 94, 2979 DOI: 10.1039/A803057J

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