Synthesis, Structure, and Stability of Adducts between Phosphide and Amide Anions and the Lewis Acids Borane, Tris(pentafluorophenyl)borane, and Tris(pentafluorophenyl)alane

Anna-Marie Fuller, Andrew J. Mountford, Matthew L. Scott, Simon J. Coles, Peter N. Horton, David L. Hughes, Michael B. Hursthouse, Simon J. Lancaster

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Abstract

The phosphinoborane adduct H3P·B(C6F5)3 can be deprotonated using LiN(SiMe3)2 to give the phosphidoborate salt Li[H2PB(C6F5)3], which was converted to the phosphidodiborates Li[H2P{B(C6F5)3}2] and Li[H2P{B(C6F5)3}{BH3}] by treatment with an equivalent of B(C6F5)3 or Me2S·BH3, respectively. A series of anions of the form [RR'P{M(C6F5)3}{BH3}]-, where R = R' = Ph or R= tBu, R' = H, and M = B or Al, were prepared (through treatment of salts Li[RR'P(BH3)] with the corresponding Lewis acid) and characterized using multinuclear NMR, elemental analysis and X-ray crystallography. The solid state structures of [Li(Et2O)x][Ph2P{M(C6F5)3}{BH3}] exhibit ?2-bonding of the BH3 group to the cationic lithium center. The attempted preparation of an analogous series with amide cores of the form [R2N{B(C6F5)3}{BH3}]- proved unsuccessful; among the competing reaction pathways hydride abstraction occurred preferentially to yield Li[HB(C6F5)3] and dimers or higher oligomers with the composition (R2NBH2)n.
Original languageEnglish
Pages (from-to)11474-11482
Number of pages9
JournalInorganic Chemistry
Volume48
Issue number23
DOIs
Publication statusPublished - 28 Oct 2009

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