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

Education Research & Practice

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

24 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

@article{05f2849709b94db8a6638a4e06a5194e,

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",

pages = "11474--11482",

journal = "Inorganic Chemistry",

publisher = "American Chemical Society",

number = "23",

}

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. et al.
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

IS - 23

ER -