Tris(borane) adducts of diphosphanylmethanides: The [H3BCH(PPh2BH3)2]- anion and its alkali metal complexes

Jens Langer; Robert Geitner; Helmar Görls

doi:10.1002/ejic.201402845

Tris(borane) adducts of diphosphanylmethanides: The [H₃BCH(PPh₂BH₃)₂]^- anion and its alkali metal complexes

Jens Langer^*
, Robert Geitner
, Helmar Görls

^*Corresponding author for this work

Friedrich Schiller University Jena
Institute of Inorganic and Analytical Chemistry

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

Abstract

The reactivity of lithium complexes that contain the borane-modified diphoshanylmethanide ligand [CH(PPh₂BH₃)₂]^- towards different Lewis base adducts of BH₃ was studied to gain further insight into the mechanism of the isomerization of this derivative, which formally proceeds through a shift of one BH₃ group from the phosphorus atom to the carbon atom. Whereas the use of BH₃·THF in THF only resulted in the thf adduct of the starting material, [Li{CH(PPh₂BH₃)₂}(thf)₂] (1), the application of BH₃·SMe₂ in toluene resulted in the formation of the novel compound [(Li{H₃BCH(PPh₂BH₃)₂})_∞] (2). The subsequent addition of ethereal ligands led to the isolation of [Li{H₃BCH(PPh₂BH₃)₂}(Me₄thf)] (3) and [Li{H₃BCH(PPh₂BH₃)₂}(thf)₃] (4). Treatment of these complexes with stronger Lewis bases such as N,N,N',N'-tetramethylethane-1,2-diamine (tmeda) results in the removal of one phosphorus-bound BH₃ molecule and the formation of the [Ph₂PCH(BH₃)PPh₂BH₃]^- anion. These results indicate that the isomerization of [CH(PPh₂BH₃)₂]^- requires an additional BH₃ source and a rather strong Lewis base. Complexes 1-4 and the related derivatives [Li{CH(PPh₂BH₃)₂}(Me₄THF)] (5) and [K{H₃BCH(PPh₂BH₃)₂}(dme)₂] (6; dme = 1,2-dimethoxyethane) were characterized by multinuclear NMR spectroscopy and by single-crystal X-ray diffraction analysis.

Original language	English
Pages (from-to)	5940-5947
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	2014
Issue number	34
DOIs	https://doi.org/10.1002/ejic.201402845
Publication status	Published - 2014
Externally published	Yes

Keywords

Boranes
Lithium
Phosphanes
Potassium
X-ray diffraction

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10.1002/ejic.201402845

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title = "Tris(borane) adducts of diphosphanylmethanides: The [H3BCH(PPh2BH3)2]- anion and its alkali metal complexes",

abstract = "The reactivity of lithium complexes that contain the borane-modified diphoshanylmethanide ligand [CH(PPh2BH3)2]- towards different Lewis base adducts of BH3 was studied to gain further insight into the mechanism of the isomerization of this derivative, which formally proceeds through a shift of one BH3 group from the phosphorus atom to the carbon atom. Whereas the use of BH3·THF in THF only resulted in the thf adduct of the starting material, [Li\{CH(PPh2BH3)2\}(thf)2] (1), the application of BH3·SMe2 in toluene resulted in the formation of the novel compound [(Li\{H3BCH(PPh2BH3)2\})∞] (2). The subsequent addition of ethereal ligands led to the isolation of [Li\{H3BCH(PPh2BH3)2\}(Me4thf)] (3) and [Li\{H3BCH(PPh2BH3)2\}(thf)3] (4). Treatment of these complexes with stronger Lewis bases such as N,N,N',N'-tetramethylethane-1,2-diamine (tmeda) results in the removal of one phosphorus-bound BH3 molecule and the formation of the [Ph2PCH(BH3)PPh2BH3]- anion. These results indicate that the isomerization of [CH(PPh2BH3)2]- requires an additional BH3 source and a rather strong Lewis base. Complexes 1-4 and the related derivatives [Li\{CH(PPh2BH3)2\}(Me4THF)] (5) and [K\{H3BCH(PPh2BH3)2\}(dme)2] (6; dme = 1,2-dimethoxyethane) were characterized by multinuclear NMR spectroscopy and by single-crystal X-ray diffraction analysis.",

keywords = "Boranes, Lithium, Phosphanes, Potassium, X-ray diffraction",

author = "Jens Langer and Robert Geitner and Helmar G{\"o}rls",

year = "2014",

doi = "10.1002/ejic.201402845",

language = "English",

volume = "2014",

pages = "5940--5947",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley",

number = "34",

}

TY - JOUR

T1 - Tris(borane) adducts of diphosphanylmethanides

T2 - The [H3BCH(PPh2BH3)2]- anion and its alkali metal complexes

AU - Langer, Jens

AU - Geitner, Robert

AU - Görls, Helmar

PY - 2014

Y1 - 2014

N2 - The reactivity of lithium complexes that contain the borane-modified diphoshanylmethanide ligand [CH(PPh2BH3)2]- towards different Lewis base adducts of BH3 was studied to gain further insight into the mechanism of the isomerization of this derivative, which formally proceeds through a shift of one BH3 group from the phosphorus atom to the carbon atom. Whereas the use of BH3·THF in THF only resulted in the thf adduct of the starting material, [Li{CH(PPh2BH3)2}(thf)2] (1), the application of BH3·SMe2 in toluene resulted in the formation of the novel compound [(Li{H3BCH(PPh2BH3)2})∞] (2). The subsequent addition of ethereal ligands led to the isolation of [Li{H3BCH(PPh2BH3)2}(Me4thf)] (3) and [Li{H3BCH(PPh2BH3)2}(thf)3] (4). Treatment of these complexes with stronger Lewis bases such as N,N,N',N'-tetramethylethane-1,2-diamine (tmeda) results in the removal of one phosphorus-bound BH3 molecule and the formation of the [Ph2PCH(BH3)PPh2BH3]- anion. These results indicate that the isomerization of [CH(PPh2BH3)2]- requires an additional BH3 source and a rather strong Lewis base. Complexes 1-4 and the related derivatives [Li{CH(PPh2BH3)2}(Me4THF)] (5) and [K{H3BCH(PPh2BH3)2}(dme)2] (6; dme = 1,2-dimethoxyethane) were characterized by multinuclear NMR spectroscopy and by single-crystal X-ray diffraction analysis.

AB - The reactivity of lithium complexes that contain the borane-modified diphoshanylmethanide ligand [CH(PPh2BH3)2]- towards different Lewis base adducts of BH3 was studied to gain further insight into the mechanism of the isomerization of this derivative, which formally proceeds through a shift of one BH3 group from the phosphorus atom to the carbon atom. Whereas the use of BH3·THF in THF only resulted in the thf adduct of the starting material, [Li{CH(PPh2BH3)2}(thf)2] (1), the application of BH3·SMe2 in toluene resulted in the formation of the novel compound [(Li{H3BCH(PPh2BH3)2})∞] (2). The subsequent addition of ethereal ligands led to the isolation of [Li{H3BCH(PPh2BH3)2}(Me4thf)] (3) and [Li{H3BCH(PPh2BH3)2}(thf)3] (4). Treatment of these complexes with stronger Lewis bases such as N,N,N',N'-tetramethylethane-1,2-diamine (tmeda) results in the removal of one phosphorus-bound BH3 molecule and the formation of the [Ph2PCH(BH3)PPh2BH3]- anion. These results indicate that the isomerization of [CH(PPh2BH3)2]- requires an additional BH3 source and a rather strong Lewis base. Complexes 1-4 and the related derivatives [Li{CH(PPh2BH3)2}(Me4THF)] (5) and [K{H3BCH(PPh2BH3)2}(dme)2] (6; dme = 1,2-dimethoxyethane) were characterized by multinuclear NMR spectroscopy and by single-crystal X-ray diffraction analysis.

KW - Boranes

KW - Lithium

KW - Phosphanes

KW - Potassium

KW - X-ray diffraction

UR - https://www.scopus.com/pages/publications/84913580399

U2 - 10.1002/ejic.201402845

DO - 10.1002/ejic.201402845

M3 - Article

AN - SCOPUS:84913580399

SN - 1434-1948

VL - 2014

SP - 5940

EP - 5947

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 34

ER -

Tris(borane) adducts of diphosphanylmethanides: The [H₃BCH(PPh₂BH₃)₂]^- anion and its alkali metal complexes

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Keywords

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