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Issue 40, 2010
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Photochemical behavior of (bisphosphane)(η2-tolane)Pt0 complexes. Part B: An insight from DFT calculations

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Abstract

A series of various (bisphosphane)(η2-tolane)Pt0 complexes, exhibiting a manifold of substitution patterns of the tolane ligand (5a–g) and different rigid bisphosphanes defining various P–Pt–P bite angles at the Pt center (9a–b) have been theoretically investigated using time-dependent density functional theory (TD-DFT). UV/Vis absorption spectra have been calculated in order to rationalize the photochemistry of the complexes. Metal–ligand charge transfer (MLCT) transitions from the Pt atom to the alkyne are assigned as the photochemical “active” states responsible for promoting the CarylCethynyl bond activation. The steric, the electronic effects, as well as the P–Pt–P bite angle play an important role in determining the presence/absence of photochemical “active” states of d→π*alk character. Thus, electron-withdrawing substituted series and ortho-substituted complexes are best candidates to achieve CarylCethynyl bond activation. C–Br bond cleavage is also theoretically rationalized. The observed photochemical CarylCethynyl bond cleavage is, oppositely to C–Br bond activation, reversible under thermal conditions regaining the appropriate Pt0 complexes by reductive elimination (see T. Weisheit, D. Escudero, H. Petzold, H. Görls, L. González and W. Weigand, Photochemical behavior of (bisphosphane)(η2-tolane)Pt0 complexes in solution and in the solid state. Part A: Experimental considerations, Dalton Trans., 2010, 39, DOI: 10.1039/B925562a). In this part, we rationalize and clarify the thermal reductive elimination reactions via mechanistic DFT studies on the ground state.

Graphical abstract: Photochemical behavior of (bisphosphane)(η2-tolane)Pt0 complexes. Part B: An insight from DFT calculations

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Publication details

The article was received on 09 Dec 2009, accepted on 13 Aug 2010 and first published on 10 Sep 2010


Article type: Paper
DOI: 10.1039/B925928G
Citation: Dalton Trans., 2010,39, 9505-9513
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    Photochemical behavior of (bisphosphane)(η2-tolane)Pt0 complexes. Part B: An insight from DFT calculations

    D. Escudero, T. Weisheit, W. Weigand and L. González, Dalton Trans., 2010, 39, 9505
    DOI: 10.1039/B925928G

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