Electronic Structure of Square-Planar cis-Bis(trifluoromethyl)platinum(II) Complexes from UV Photoelectron Spectra and SCF–MS–Xα Calculations

Dong Sheng Yang; G. Michael Bancroft; R. J. Puddephatt; John S. Tse

doi:10.1021/ic00338a021

Electronic Structure of Square-Planar cis-Bis(trifluoromethyl)platinum(II) Complexes from UV Photoelectron Spectra and SCF–MS–Xα Calculations

Dong Sheng Yang, G. Michael Bancroft, R. J. Puddephatt, John S. Tse

Research output: Contribution to journal › Article › peer-review

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Abstract

UV photoelectron spectra of cis-[Pt(CF₃)₂L₂] (L₂ = 1,5-cyclooctadiene (COD), Me₂NCH₂CH₂NMe₂ (TMED); L = PEt₃, AsMe₃) are reported, as well as MS–Xα calculations on the model compounds [Pt(CF₃)₂(Ć₂H₄)₂] and cis-[Pt(CF₃)₂(PH₃)₂]. The spectra are assigned by using MS–Xα calculations and by comparison with the spectra of the corresponding dimethylplatinum(II) complexes. The first two ionization bands (with lowest ionization energies) are assigned to platinum–ligand σ orbitals, followed by four bands due to the essentially nonbonding platinum 5d orbitals. The nature of the Pt-CF₃ σ bonding is discussed in terms of MS–Xα results. In contrast to the Pt–CH₃ σ bonds, the Pt–CF₃ σ bonds have a significant C 2s and C–F antibonding character.

Original language	English
Pages (from-to)	2496-2501
Number of pages	6
Journal	Inorganic Chemistry
Volume	29
Issue number	13
DOIs	https://doi.org/10.1021/ic00338a021
State	Published - Jun 1 1990

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{dfdd9562ee1d426ca37625852492e3df,

title = "Electronic Structure of Square-Planar cis-Bis(trifluoromethyl)platinum(II) Complexes from UV Photoelectron Spectra and SCF–MS–Xα Calculations",

abstract = "UV photoelectron spectra of cis-[Pt(CF3)2L2] (L2 = 1,5-cyclooctadiene (COD), Me2NCH2CH2NMe2 (TMED); L = PEt3, AsMe3) are reported, as well as MS–Xα calculations on the model compounds [Pt(CF3)2({\'C}2H4)2] and cis-[Pt(CF3)2(PH3)2]. The spectra are assigned by using MS–Xα calculations and by comparison with the spectra of the corresponding dimethylplatinum(II) complexes. The first two ionization bands (with lowest ionization energies) are assigned to platinum–ligand σ orbitals, followed by four bands due to the essentially nonbonding platinum 5d orbitals. The nature of the Pt-CF3 σ bonding is discussed in terms of MS–Xα results. In contrast to the Pt–CH3 σ bonds, the Pt–CF3 σ bonds have a significant C 2s and C–F antibonding character.",

author = "Yang, {Dong Sheng} and Bancroft, {G. Michael} and Puddephatt, {R. J.} and Tse, {John S.}",

year = "1990",

month = jun,

day = "1",

doi = "10.1021/ic00338a021",

language = "English",

volume = "29",

pages = "2496--2501",

number = "13",

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TY - JOUR

T1 - Electronic Structure of Square-Planar cis-Bis(trifluoromethyl)platinum(II) Complexes from UV Photoelectron Spectra and SCF–MS–Xα Calculations

AU - Yang, Dong Sheng

AU - Bancroft, G. Michael

AU - Puddephatt, R. J.

AU - Tse, John S.

PY - 1990/6/1

Y1 - 1990/6/1

N2 - UV photoelectron spectra of cis-[Pt(CF3)2L2] (L2 = 1,5-cyclooctadiene (COD), Me2NCH2CH2NMe2 (TMED); L = PEt3, AsMe3) are reported, as well as MS–Xα calculations on the model compounds [Pt(CF3)2(Ć2H4)2] and cis-[Pt(CF3)2(PH3)2]. The spectra are assigned by using MS–Xα calculations and by comparison with the spectra of the corresponding dimethylplatinum(II) complexes. The first two ionization bands (with lowest ionization energies) are assigned to platinum–ligand σ orbitals, followed by four bands due to the essentially nonbonding platinum 5d orbitals. The nature of the Pt-CF3 σ bonding is discussed in terms of MS–Xα results. In contrast to the Pt–CH3 σ bonds, the Pt–CF3 σ bonds have a significant C 2s and C–F antibonding character.

AB - UV photoelectron spectra of cis-[Pt(CF3)2L2] (L2 = 1,5-cyclooctadiene (COD), Me2NCH2CH2NMe2 (TMED); L = PEt3, AsMe3) are reported, as well as MS–Xα calculations on the model compounds [Pt(CF3)2(Ć2H4)2] and cis-[Pt(CF3)2(PH3)2]. The spectra are assigned by using MS–Xα calculations and by comparison with the spectra of the corresponding dimethylplatinum(II) complexes. The first two ionization bands (with lowest ionization energies) are assigned to platinum–ligand σ orbitals, followed by four bands due to the essentially nonbonding platinum 5d orbitals. The nature of the Pt-CF3 σ bonding is discussed in terms of MS–Xα results. In contrast to the Pt–CH3 σ bonds, the Pt–CF3 σ bonds have a significant C 2s and C–F antibonding character.

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DO - 10.1021/ic00338a021

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SN - 0020-1669

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SP - 2496

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 13

ER -

Electronic Structure of Square-Planar cis-Bis(trifluoromethyl)platinum(II) Complexes from UV Photoelectron Spectra and SCF–MS–Xα Calculations

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