Counterintuitive Mechanisms of the Addition of Hydrogen and Simple Olefins to Heavy Group 13 Alkene Analogues
Caputo, C., Koivistoinen, J., Moilanen, J., Boynton, J., Tuononen, H., & Power, P. (2013). Counterintuitive Mechanisms of the Addition of Hydrogen and Simple Olefins to Heavy Group 13 Alkene Analogues. Journal of the American Chemical Society, 135(5), 1952-1960. https://doi.org/10.1021/ja3116789
Julkaistu sarjassa
Journal of the American Chemical SocietyTekijät
Päivämäärä
2013Oppiaine
Epäorgaaninen ja analyyttinen kemiaFysikaalinen kemiaInorganic and Analytical ChemistryPhysical ChemistryTekijänoikeudet
© 2013 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
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The mechanism of the reaction of olefins and hydrogen with dimetallenes ArMMAr (Ar = aromatic group; M = Al or Ga) was studied by density functional theory calculations and experimental methods. The digallenes, for which the most experimental data are available, are extensively dissociated to gallanediyl monomers, :GaAr, in hydrocarbon solution, but the calculations and experimental data showed also that they react with simple olefins, such as ethylene, as intact ArGaGaAr dimers via stepwise [2 + 2 + 2] cycloadditions due to their considerably lower activation barriers vis-à-vis the gallanediyl monomers, :GaAr. This pathway was preferred over the [2 + 2] cycloaddition of olefin to monomeric :GaAr to form a gallacyclopropane ring with subsequent dimerization to yield the 1,2-digallacyclobutane intermediate and, subsequently, the 1,4-digallacyclohexane product. The calculations showed also that the addition of H2 to digallene proceeds by a different mechanism involving the initial addition of one equivalent of H2 to form a 1,2-dihydride intermediate. This reacts with a second equivalent of H2 to give two ArGaH2 fragments which recombine to give the observed product with terminal and bridging H-atoms, Ar(H)Ga(μ-H)2Ga(H)Ar. The computations agree with the experimental observation that the :GaAriPr8 (AriPr8 = C6H-2,6-(C6H3-2,4,6-iPr3)2-3,5-iPr2), which does not associate even in the solid state, does not react with ethylene or hydrogen. Calculations on the reaction of propene with ArAlAlAr show that, in contrast to the digallenes, addition involves an open-shell transition state consistent with the higher singlet diradical character of dialuminenes.
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American Chemical SocietyISSN Hae Julkaisufoorumista
0002-7863Julkaisu tutkimustietojärjestelmässä
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