Vibrational spectra of PT(II) complexes—I. The Raman and infrared spectra of the [Pt(CO)Cl3] and [Pt(NH3)Cl3] ions

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Abstract

The Raman spectra of Pt(CO)Cl3 and Pt(NH3)Cl3 in aqueous solution have been recorded, together with the infrared spectra (280–4000 cm−1) of solid salts of these ions. Assignments are made on the basis of point group C2ν for the square-planar molecular skeleton, and the metal—ligand vibration frequencies are discussed in relation to previous assignments for similar molecules. As the oxidation state of the metal in a carbonyl increases, the relative positions of ν(MC) and δ(MCO) may become inverted. Thus, in Pt(CO)Cl3, ν(MC) > δ(MCO), in contrast to the order usually found. Compared with NH3, the ligand CO has a profound effect on the vibrations of the PtCl3 moiety: it appears that a cis-strengthening effect is at least as significant as the more widely recognised trans-weakening effect in differentiating the two types of PtCl bond.

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    Present addresses: (R. G. D.) Department of Chemistry, University of Illinois, Urbana 61801, U.S.A. (M. J. W.) Department of Chemistry, University of Manchester, Manchester 13.

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