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A study of some potassium hexachlorometallate complexes using electron spectroscopy
Authors:Lawrence E Cox  David M Hercules
Institution:Department of Chemistry, University of Georgia, Athens, Ga. 30601 U.S.A.
Abstract:X-ray photoelectron (ESCA) spectra of the core (Cl 2p K 2p and metal 4f, if present) and valence orbitals are reported for K2ReCl6, K2OsCl6, K2IrCl6· 3 H2O, K2PtCl6, K3MoCl6, and K2SnCl6. The K 2p32 binding energy was found to be nearly constant (292.7 eV) and that of Cl to increase very slightly with increasing atomic number for the third row transition metals. The chemical shifts of Re(IV), Os(IV), Ir(IV), and Pt(IV) relative to the metals were in qualitative agreement with atomic calculations utilizing configurations obtained from extended Hückel calculations. The valence spectra of the transition metal complexes exhibit a three-band structure. On the basis of MO results and intensity considerations the high binding energy band is assigned as a composite of the a1g, eg, 1t2g MO's. The middle band represents the t2u, 2t1g MO's; and the low binding energy band the 2t2g MO. Calculated nd orbital photoionization cross sections correlate reasonably well with the relative intensifies of the valence manifolds. Comparison of band separations and charge-transfer transition energies suggests that interelectronic repulsion and MO energy separation contribute about equally to the overall charge-transfer energy.
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