Chalcogenides of aluminium(III) and gallium(III) derived from Lewis base adducts of alane and gallane

Warren J. Grigsby, Colin L. Raston, Vicki Anne Tolhurst, Brian W. Skelton, Allan H. White

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17 Citations (Scopus)


Reductive cleavage of (ER)2 by [GaH3L], L = NMe3 or P(C6H11)3, afforded [Ga(TePh)3(NMe3)], [Ga(SeEt)3-(NMe3)] and [Ga(TePh)3{P(C6H11)3}]; the latter was also prepared by the reaction of [GaH2Cl{P(C6H11)3}] with LiTePh. They have slightly disordered tetrahedral metal centres, established in the solid for [Ga(TePh)3(NMe3)] and [Ga(TePh)3 {P(C6H11)3}], and in the structure of the aluminium analogue, [Al(SePh)3(NMe3)], which was also determined. Reaction of [GaH2Cl {P(C6H11)3}] with Li2Se afforded dinuclear trans-[{GaCl(μ-Se)[P(C6H11)3]}2] (minor product) which is centrosymmetric with distorted tetrahedral metal centres associated with a planar Ga2Se2 ring system. Treatment of trans-[{AlH(μ-Se)(NMe3)}2] with tmen (=N,N,N′,N′-tetramethylethane-1,2-diamine), or [{AlH3(tmen)}x] with elemental selenium, afforded polymeric [{[AlH(μ-Se)]2(tmen)}α]. Cleavage of (EPh)2 by trans-[{AlH(μ-Se)(NMe3)}2] gave trans-[{Al(μ-Se)(EPh)(NMe3)}2], E = S, Se or Te, also as centrosymmetric dinuclear species with planar Al2Se2 ring systems. Reaction of trans-[{AlH(μ-Se)(NMe3)}2] with 2 equivalents of NH(SiMe3)2 or 6-methyl-2-trimethylsilylaminopyridine gave the secondary amine metallated products trans-[{Al(μ-Se)[N(SiMe3)2](NMe3)} 2] (structurally authenticated as a centrosymmetric dinuclear species) and [{Al(μ-Se)(NC5H3NSiMe3-2-Me-6)} 2].

Original languageEnglish
Pages (from-to)2547-2556
Number of pages10
JournalJournal of the Chemical Society - Dalton Transactions
Issue number15
Publication statusPublished - 7 Aug 1998
Externally publishedYes


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