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

doi:10.1021/ic00336a017

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

Chemistry

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Abstract

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 language	English
Pages (from-to)	2118-2122
Number of pages	5
Journal	Inorganic Chemistry
Volume	29
Issue number	11
DOIs	https://doi.org/10.1021/ic00336a017
State	Published - May 1 1990

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{ba7e499f365d4978a0fe22fd741dddea,

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

abstract = "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.",

author = "Yang, {Dong Sheng} and Bancroft, {G. Michael} and Puddephatt, {Richard J.}",

year = "1990",

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doi = "10.1021/ic00336a017",

language = "English",

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T1 - Electronic Structure of (β-Diketonato)trimethylplatinum(IV) Complexes from UV Photoelectron Spectra and SCF-MS-Xα Calculations

AU - Yang, Dong Sheng

AU - Bancroft, G. Michael

AU - Puddephatt, Richard J.

PY - 1990/5/1

Y1 - 1990/5/1

N2 - 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.

AB - 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.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

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

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