Phosphinotrihydroborate(1-), H2P.BH3-, the conjugate Broensted base of phosphine-borane. Synthesis, reactions, and stability of the lithium salt

Mayer, Erwin

doi:10.1021/ic50104a034

Cited by 10 publications

(4 citation statements)

References 2 publications

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“…In contrast to the apparent instability of dialkylamido- and dialkylphosphido-di(tris(pentafluorophenyl))borate anions, the adducts between dialkyl amide anions and trihydridroborane are well-known. Lithium dimethylamidoborate, LiMe 2 NBH 3 , is available commercially as a reducing agent, and the sodium salt of the dimethylamidodiborate anion, NaMe 2 N(BH 3 ) 2 was first reported in 1971. , Primary and secondary phosphine adducts of BH 3 react with n BuLi to give the corresponding salts, in which there is competing Li−P and LiHB bonding …”

Section: Introductionmentioning

confidence: 99%

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

et al. 2009

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The phosphinoborane adduct H(3)P x B(C(6)F(5))(3) can be deprotonated using LiN(SiMe(3))(2) to give the phosphidoborate salt Li[H(2)PB(C(6)F(5))(3)], which was converted to the phosphidodiborates Li[H(2)P{B(C(6)F(5))(3)}(2)] and Li[H(2)P{B(C(6)F(5))(3)}{BH(3)}] by treatment with an equivalent of B(C(6)F(5))(3) or Me(2)S.BH(3), respectively. A series of anions of the form [RR'P{M(C(6)F(5))(3)}{BH(3)}](-), where R = R' = Ph or R= (t)Bu, R' = H, and M = B or Al, were prepared (through treatment of salts Li[RR'P(BH(3))] with the corresponding Lewis acid) and characterized using multinuclear NMR, elemental analysis and X-ray crystallography. The solid state structures of [Li(Et(2)O)(x)][Ph(2)P{M(C(6)F(5))(3)}{BH(3)}] exhibit eta(2)-bonding of the BH(3) group to the cationic lithium center. The attempted preparation of an analogous series with amide cores of the form [R(2)N{B(C(6)F(5))(3)}{BH(3)}](-) proved unsuccessful; among the competing reaction pathways hydride abstraction occurred preferentially to yield Li[HB(C(6)F(5))(3)] and dimers or higher oligomers with the composition (R(2)NBH(2))(n).

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Section: Introductionmentioning

confidence: 99%

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

et al. 2009

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“…On the basis of literature precedent, another mechanism has been proposed to address the potential phosphine−borane adduct formation (Figure , pathway B). However, we believe pathway A is more likely due to the reported dissociation of this adduct at −30 °C.…”

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confidence: 99%

Improved Synthesis of Bis(borano)hypophosphite Salts

et al. 2010

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A synthesis of the bis(borano)hypophosphite anion with various counterions has been developed to make use of more benign and commercially available reagents. This method avoids the use of potentially dangerous reagents used by previous methods and gives the final products in good yield. Details of the crystal structure determination of the sodium salt in space group Ama2 are given using a novel computational technique combined with Rietveld refinement.

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“…Also, the 11 B{ 1 H} NMR spectrum shows a broad resonance at δ = -0.4 ppm for the BH 2 moiety, which splits into a broad triplet with a boron-hydrogen coupling constant of 1 J B,H = 133 Hz when the spectrum is measured with proton coupling. In comparison with the trigonal planar surrounded boron atom of free B(C 6 F 5 ) 3 , which can be detected in its 11 B NMR spectrum at δ = 59.6 ppm, the resonance of the boron atom of the LA in compound 1, which is in a tetrahedral environment, is shifted strongly upfield and appears at δ = -18.3 ppm as a broad singlet.…”

Section: Synthesis and Spectroscopic Characterisation Of The Lewis Acmentioning

confidence: 94%

Main Group Lewis Acid/Base‐Stabilised Phosphanylboranes

2007

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The parent compounds of phosphanylboranes of the type (LA)H2P–BH2(LB) (LA = Lewis acid, LB = Lewis base) stabilised by Lewis acid/Lewis base have been synthesised by using perfluorinated main‐group Lewis acids. The Lewis acid–phosphane adducts (C6F5)3BPH3, (C6F5)3BPPhH2 and (C6F5)3GaPPhH2 (3) were used as starting materials, which upon lithiation with nBuLi react with the chlorinated Lewis base borane adduct ClBH2NMe3. The LA/LB stabilisedphosphanylboranes (C6F5)3BPH2BH2NMe3 (1), (C6F5)3BPPhHBH2NMe3 (4) and (C6F5)3GaPPhHBH2NMe3 (5), were obtained via salt elimination reactions. (C6F5)3GaPH2BH2NMe3 (2) was not accessible using this method due to the unavailability of an efficient synthetic route to (C6F5)3GaPH3. The synthesis of 2 could be achieved quantitatively via reaction of PH2BH2NMe3 with (C6F5)3Ga·Et2O. All products were comprehensively characterised by spectroscopic methods and X‐ray crystallography. Additionally, the intermediate products (C6F5)3BPH2Li and (C6F5)3GaPPhH2 (3) were spectroscopically characterised.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Phosphinotrihydroborate(1-), H2P.BH3-, the conjugate Broensted base of phosphine-borane. Synthesis, reactions, and stability of the lithium salt

Cited by 10 publications

References 2 publications

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

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

Improved Synthesis of Bis(borano)hypophosphite Salts

Main Group Lewis Acid/Base‐Stabilised Phosphanylboranes

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