Electronic Structure of (β-Diketonato)trimethylplatinum(IV) Complexes from UV Photoelectron Spectra and SCF-MS-Xα Calculations

Dong Sheng Yang, G. Michael Bancroft, Richard J. Puddephatt

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8 Scopus citations


The UV photoelectron spectra of the (β-diketonato)trimethylplatinum(IV) complexes [PtMe3(acac)]2 (acac = acetylacetonate), [PtMe3(tfa)H2O] (tfa = trifluoroacetylacetonate), [PtMe3(hfa)H2O] (hfa = hexafluoroacetylacetonate), and [PtMe3(tfa)Me2S] are reported. The valence orbitals responsible for the ionizations have been assigned by using the MS-Xα result for the model compound [PtMe3(HC(O)CHCOH)] and the ionization shifts from the ligand substitutions. The valence molecular orbitals fall in the order of increasing binding energy π3 < n_. < Pt-n+ < Pt 5d, Pt-Me in the complexes [PtMe3(acac)], [PtMe3(tfa)H2O], and [PtMe3(hfa)H2O] and in the order Pt-S < π3 ‹ n_ < Pt-n+ < Pt 5d in the compound [PtMe3(tfa)Me2S]. Both photoelectron spectra and the MS-Xα calculation indicate that the Pt 5d electrons are extensively delocalized by interaction with the coordinated ligands.

Original languageEnglish
Pages (from-to)2118-2122
Number of pages5
JournalInorganic Chemistry
Issue number11
StatePublished - May 1 1990

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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