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From a consideration of odd-even intramolecular electron transfer processes in octahedrally co-ordinated transition metal complexes, two relationships have been derived. The first correlation describes π → γ 3  optical electron transfer bands of the complexes K 2 OsCl 6 , K 2 IrCl 6 , K 2 PtCl 6 , K 2 PtCl 4  as a function of the respective  35 Cl nuclear quadrupole coupling constants. The second relationship correlates π → γ 5  optical charge transfer transitions of the substances K 2 ReCl 6 , K 2 OsCl 6 , K 2 IrCl 6  with the  35 Cl nuclear quadrupole coupling constants of these compounds. By using this charge transfer model, a linear relationship has been verified between the optical electronegativity values of the quadrivalent transition metal ions W 4⨁ , Re 4⊖ , Os 4⨁ , Ir 4⨁ , Pt 4⨁  and the  35 Cl nuclear quadrupole coupling constants of their hexachloro complexes. The empirically established equation χMe n+  = 0.537which describes the  35 Cl n.q.r. frequencies of the hexachloro complexes of Re 4⨁ , Os 4⨁ , Ir 4⨁ , Pt 4⨁  and Pd 4⨁  as a function of the optical electronegativity values χ of these metal ions, has been used to estimate  35 Cl nuclear quadrupole resonance frequencies of chloro complexes as yet not probed by nuclear quadrupole resonance spectroscopy, e.g. Zeise's salt (KPtCl 3 C 2 H 4 ), K 3 IrCl 6 , K 2 RuCl 6 , K 3 RhCl 6  and K 3 MoCl 6 . Conversely, by the same procedure the optical electronegativity χ of W 4⨁  and Au 3⨁  has been estimated from the  35 Cl quadrupole resonance frequency of K 2 WCl 6  and KAuCl 4  (χ W 4⨁ = 1.71 and χ Au 3⨁ =2.80). In the case of analogous bromo complexes, the equation χ Me n+  = 0.19mol accounts for the dependence of the  79 Br nuclear quadrupole resonance frequencies upon the optical electronegativity of the metal ions. The assignment of electron transfer bands in other chloro complexes is discussed in the light of this “nuclear quadrupole resonance criterion“ of optical charge transfer bands.

zeitschrift für naturforschung b

On the Correlation of  35 Cl Nuclear Quadrupole Coupling Constants with π→γ 3  and π→γ 5  Optical Electron Transfer Bands of Transition Metal Complexes and its Significance in Pi-Bonding