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Type: Artigo de periódico
Title: Pt L-2,L-3 - Edge X-ray Absorption Spectroscopy Investigation of Zerovalent [Pt(PPh3)(2)(eta(2)-L)] {L = C2H4, C-60 and C-2(CN)(4)} Compounds
Author: Dias, GHM
da Fonseca, NF
Herbst, MH
Abstract: X-ray absorption spectra at the Pt L-2,L-3-edges have been measured for three [Pt(PPh3)(2)(eta(2)-L)] {L = C2H4, C-60 and C-2(CN)(4)} compounds. The spectral features are effective for measuring the pi*-acid strength of ligands (L) coordinated to the Pt(PPh3)(2) fragment. The energies of the d(pi)-orbitals are quantitatively determined using the difference between the edge jumping and the edge maximum shifts of the L-2,L-3-white lines in the second derivatives of the spectra. The d(pi)-orbital energies follow the order [Pt(PPh3)(2)(eta(2)-C2H4)] < [Pt(PPh3)(2)(eta(2)-C-60)] < [Pt(PPh3)(2){eta(2)-C-2(CN)(4)}]. These d(pi)-orbital energies are in good agreement with the changes in the bound olefinic carbon bond lengths and the P-31 NMR chemical shifts of the coordinated phosphines. Furthermore, the experimental values are in good agreement with available d(pi)-orbital interaction energy terms calculated using density functional theory for model [Pt(PH3)(2)(eta(2)-L)] compounds.
Subject: Pt L-2,L-3-edge XAS
zerovalent platinum compounds
pi back-donation energy
spectral decomposition
Country: Brasil
Editor: Soc Brasileira Quimica
Rights: aberto
Date Issue: 2012
Appears in Collections:Unicamp - Artigos e Outros Documentos

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