Heterogenization of Lanthanum and Neodymium Monophosphacyclopentadienyl Bis(tetramethylaluminate) Complexes onto Periodic Mesoporous Silica SBA-15

Abstract : The monophosphacyclopentadienyl bis(tetramethylaluminate) lanthanide complexes (η5-PC4Me4)Ln[(μ-Me)2AlMe2]2 and [η5-PC4Me2(SiMe3)2]Ln[(μ-Me)2AlMe2]2 (Ln = La, Nd) have been immobilized onto mesoporous silica SBA-15, which was dehydroxylated at 500 °C. Major reaction pathways comprise methane elimination, that is, silanolysis of Ln(μ-Me)Al moieties with surface silanol groups, and trimethylaluminum separation resulting from donor-induced tetramethylaluminate cleavage. The formation of bis- and monosiloxy surface species is discussed involving transient [(η5-PC4Me4)Ln[(μ-OSi≡)(μ-Me)AlMe2]x[(μ-Me)2AlMe2]2-x] and [{η5-PC4Me2(SiMe3)2}Ln[(μ-OSi≡)(μ-Me)AlMe2]x[(μ-Me)2AlMe2]2-x] (Ln = La, Nd, x = 1, 2) as well as more stable entities such as [(η5-PC4Me2R2)(≡SiO)Ln[(μ-Me)2AlMe2]] and/or [(η5-PC4Me2R2)[(μ-OSi≡)(μ-Me)AlMe2]Ln(Me)] and [(η5-PC4Me2R2)(≡SiO)Ln[(μ-OSi≡)(μ-Me)AlMe2]] and/or [(≡SiO)2Ln(η5-PC4Me2R2)]. Moreover, surface alumination via released trimethylaluminum and the formation of [(≡SiO)3-yAlMey] (with y = 1, 2) surface sites is observed. The organometallic/inorganic hybrid materials (η5-PC4Me2R2)Ln(AlMe4)2@SBA-15-500 have been characterized by DRIFT and solid-state NMR spectroscopy, elemental analysis, and nitrogen physisorption. The equimolar reaction of complex (η5-PC4Me4)Nd[(μ-Me)2AlMe2]2 with tris(tert-butoxy)silanol (HOSi(OtBu)3) produces the siloxide complex (η5-PC4Me4)Nd[{μ-OSi(OtBu)3}(μ-Me)AlMe2][(μ-Me)2AlMe2], which was crystallographically authenticated as a model of a potential monophosphacyclopentadienyl neodymium surface species. All of the mesoporous hybrid materials are moderately active initiators for isoprene polymerization, producing 1,4-cis polyisoprene PI (>99%), which is in contrast to the case for the borate-activated molecular precursors (η5-PC4Me2R2)Ln(AlMe4)2 giving preferentially 1,4-trans PI. The surface organometallic chemistry as well as the polymerization performance markedly depend on the thermal pretreatment of the SBA-15 silica, as shown for the corresponding hybrid materials obtained from SBA-15-200 and SBA-15-700.
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Submitted on : Monday, November 18, 2013 - 5:39:53 PM
Last modification on : Wednesday, March 20, 2019 - 12:12:31 PM

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Erwan Le Roux, Yucang Liang, Karl W Tornoos, François Nief, Reiner Anwnader. Heterogenization of Lanthanum and Neodymium Monophosphacyclopentadienyl Bis(tetramethylaluminate) Complexes onto Periodic Mesoporous Silica SBA-15. Organometallics, American Chemical Society, 2012, 31 (18), pp.6526-6537. ⟨10.1021/om300168s⟩. ⟨hal-00905875⟩

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