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

doi:10.1021/ic901799q

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

School of Chemistry

Research output: Contribution to journal › Article › peer-review

22 Citations (Scopus)

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 language	English
Pages (from-to)	11474-11482
Number of pages	9
Journal	Inorganic Chemistry
Volume	48
Issue number	23
DOIs	https://doi.org/10.1021/ic901799q
Publication status	Published - 28 Oct 2009

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10.1021/ic901799q

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Fuller, A-M., Mountford, A. J., Scott, M. L., Coles, S. J., Horton, P. N., Hughes, D. L., Hursthouse, M. B., & Lancaster, S. J. (2009). Synthesis, Structure, and Stability of Adducts between Phosphide and Amide Anions and the Lewis Acids Borane, Tris(pentafluorophenyl)borane, and Tris(pentafluorophenyl)alane. Inorganic Chemistry, 48(23), 11474-11482. https://doi.org/10.1021/ic901799q

Fuller, Anna-Marie ; Mountford, Andrew J. ; Scott, Matthew L. ; Coles, Simon J. ; Horton, Peter N. ; Hughes, David L. ; Hursthouse, Michael B. ; Lancaster, Simon J. / Synthesis, Structure, and Stability of Adducts between Phosphide and Amide Anions and the Lewis Acids Borane, Tris(pentafluorophenyl)borane, and Tris(pentafluorophenyl)alane. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 23. pp. 11474-11482.

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

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.",

author = "Anna-Marie Fuller and Mountford, {Andrew J.} and Scott, {Matthew L.} and Coles, {Simon J.} and Horton, {Peter N.} and Hughes, {David L.} and Hursthouse, {Michael B.} and Lancaster, {Simon J.}",

year = "2009",

month = oct,

day = "28",

doi = "10.1021/ic901799q",

language = "English",

volume = "48",

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Fuller, A-M, Mountford, AJ, Scott, ML, Coles, SJ, Horton, PN, Hughes, DL, Hursthouse, MB & Lancaster, SJ 2009, 'Synthesis, Structure, and Stability of Adducts between Phosphide and Amide Anions and the Lewis Acids Borane, Tris(pentafluorophenyl)borane, and Tris(pentafluorophenyl)alane', Inorganic Chemistry, vol. 48, no. 23, pp. 11474-11482. https://doi.org/10.1021/ic901799q

Synthesis, Structure, and Stability of Adducts between Phosphide and Amide Anions and the Lewis Acids Borane, Tris(pentafluorophenyl)borane, and Tris(pentafluorophenyl)alane. / Fuller, Anna-Marie; Mountford, Andrew J.; Scott, Matthew L.; Coles, Simon J.; Horton, Peter N.; Hughes, David L.; Hursthouse, Michael B.; Lancaster, Simon J.

In: Inorganic Chemistry, Vol. 48, No. 23, 28.10.2009, p. 11474-11482.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis, Structure, and Stability of Adducts between Phosphide and Amide Anions and the Lewis Acids Borane, Tris(pentafluorophenyl)borane, and Tris(pentafluorophenyl)alane

AU - Fuller, Anna-Marie

AU - Mountford, Andrew J.

AU - Scott, Matthew L.

AU - Coles, Simon J.

AU - Horton, Peter N.

AU - Hughes, David L.

AU - Hursthouse, Michael B.

AU - Lancaster, Simon J.

PY - 2009/10/28

Y1 - 2009/10/28

N2 - 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.

AB - 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.

U2 - 10.1021/ic901799q

DO - 10.1021/ic901799q

M3 - Article

VL - 48

SP - 11474

EP - 11482

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 23

ER -