Electronic Structure of cis-Dimethylplatinum(II) Complexes from UV Photoelectron Spectra and SCF–MS–Xα Calculations

Dong Sheng Yang, G. Michael Bancroft, Lisa Dignard-Bailey, Richard J. Puddephatt, John S. Tse

Research output: Contribution to journalArticlepeer-review

27 Scopus citations


UV photoelectron spectra of cis-[PtMe2L2] [L = PMe3, PMe2Ph, PMePh2, PEt3, P(NMe2)3, PMe(OEt)2, P(OMe)3, P(OEt)3, AsMe3, CNMe, CNPh; L2 = Me2NCH2CH2NMe2 (TMED), 1,5-cyclooctadiene (COD), norbornadiene (NBD)] are reported, as well as MS–Xα calculations on the model compounds cis-[PtMe2(EH3)2] (E = N, P, As), cis-[PtMe2(C2H4)2], and cis- [PtMe2(CNH)2], The results from these calculations and spectral information, such as resolved vibrational fine structures and ligand shift effects, have allowed the assignment of the lower energy ionizations to specific molecular orbitals. The two molecular orbitals with lowest ionization energies are assigned, in all cases, to Pt–ligand σ orbitals, and these are followed by four MO's that have mostly nonbonding Pt 5d character. The σ-donor ability of a ligand L is reflected in the first ionization energy and decreases in the order L = P(NMe2)3 > TMED > PMePh2 ~ PMe2Ph > PEt3 > AsMe3 ~ PMe3 > PMe(OEt)2 > P(OEt)3 > P(OMe)3 > COD > NBD. The π-acceptor ability is reflected by the energy separation of the Pt dxy and dxy (axes defined by C2v symmetry) and falls in the order PMePh2 ~ PMe2Ph ~ P(OMe)3 ~ P(OEt)3 ~ PMe(OEt)2 ~ P(NMe2)3 > AsMe3 ~ PMe3 ~ PEt3 ~ COD ~ NBD > TMED. Both isocyanide ligands CNMe and CNPh, which cannot be arranged into the above series, have comparable σ-donor ability, and the latter has stronger π-donor and π-acceptor properties. Some typical chemical processes are also discussed on the basis of the established σ/π series.

Original languageEnglish
Pages (from-to)2487-2495
Number of pages9
JournalInorganic Chemistry
Issue number13
StatePublished - Jun 1 1990

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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