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Issue 14, 2013
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Contact and solvent-separated ion pair aluminium “ate” complexes on a titanium oxide molecular model

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Abstract

Treatment of [{Ti(η5-C5Me5)(μ-O)}33-CR)] [R = H (1), Me (2)] with AlPh3 or AlMe3 gives adducts [R′3Al(μ3-O)(μ-O)2{Ti(η5-C5Me5)}33-CR)] [R = H, R′ = Ph (3), Me (4); R = Me, R′ = Ph (5), Me (6)] that react with LiNMe2 to give the contact ion pair complexes [Ph3Al(μ-NMe2)Li(μ3-O)3{Ti(η5-C5Me5)}33-CR)] [R = H (7), Me (8)] or the solvent-separated ion pair compounds [Li{(μ3-O)3Ti35-C5Me5)33-CR)}2][(Me3Al)2(μ-NMe2)] [R = H (9), Me (10)]. Reactions of 1 or 2 with a mixture of AlPh3 and LiCH2SiMe3 lead to the solvent-separated ion pair complexes [Li{(μ3-O)3Ti35-C5Me5)33-CR)}2][Al(CH2SiMe3)Ph3] [R = H (11), Me (12)], presumably by evolution of redistribution intermediates containing the lithium dicubane cation [Li{(μ3-O)3Ti35-C5Me5)33-CR)}2]+ and [Li{Al(μ-Ph)2Ph(CH2SiMe3)}2] anionic units. Surprisingly, reaction of 4 with p-tolyl lithium gives the complex [{Me2Al(μ-Me)Li(p-MeC6H4)}{(μ3-O)2(μ-O)Ti35-C5Me5)33-CH)}] 13 in which the aryl lithium species is incorporated showing interactions with both the trialkyl aluminium unit and the organometallic oxide 1. X-ray diffraction studies were performed on 8, 12 and 13.

Graphical abstract: Contact and solvent-separated ion pair aluminium “ate” complexes on a titanium oxide molecular model

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Publication details

The article was received on 14 Nov 2012, accepted on 19 Jan 2013 and first published on 23 Jan 2013


Article type: Paper
DOI: 10.1039/C3DT32725F
Citation: Dalton Trans., 2013,42, 5076-5084
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    Contact and solvent-separated ion pair aluminium “ate” complexes on a titanium oxide molecular model

    A. Hernán-Gómez, A. Martín, M. Mena and C. Santamaría, Dalton Trans., 2013, 42, 5076
    DOI: 10.1039/C3DT32725F

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