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{{chembox |
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| verifiedrevid = 291895967 |
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| verifiedrevid = 442369778 |
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| ImageFile = NaBPh4.png |
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| ImageFile = NaBPh4.png |
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| IUPACName = Sodium tetraphenylborate |
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| PIN = Sodium tetraphenylboranuide |
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| OtherNames = Tetraphenylboron sodium |
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| OtherNames = Tetraphenylboron sodium<br />Kalignost |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 143-66-8 |
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| CASNo = 143-66-8 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| PubChem = 2723787 }} |
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| UNII = 5A96KL5H1M |
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| Section2 = {{Chembox Properties |
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| PubChem = 2723787 |
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| InChI = 1S/C24H20B.Na/c1-5-13-21(14-6-1)25(22-15-7-2-8-16-22,23-17-9-3-10-18-23)24-19-11-4-12-20-24;/h1-20H;/q-1;+1 |
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| SMILES = (C1=CC=CC=C1)(C2=CC=CC=C2)(C3=CC=CC=C3)C4=CC=CC=C4. |
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}} |
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|Section2={{Chembox Properties |
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| Formula = (C<sub>6</sub>H<sub>5</sub>)<sub>4</sub>BNa |
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| Formula = (C<sub>6</sub>H<sub>5</sub>)<sub>4</sub>BNa |
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| MolarMass = 342.22 g/mol |
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| MolarMass = 342.216 g/mol |
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| Appearance = white solid |
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| Appearance = white solid |
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| Solubility = 47 g/100 g water |
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| Solubility = 47 g/100 mL |
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| SolubleOther = soluble in ] |
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| MeltingPt = >300 °C |
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| MeltingPt = > |
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| MeltingPtC = 310 |
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'''Sodium tetraphenylborate''' is the ] with the formula NaB(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub>. It is a salt, wherein the anion consists of four phenyl rings bonded to boron. This colourless crystalline solid is used to prepare other tetraphenylborate salts, which are often highly soluble in organic solvents. The compound is used in inorganic and organometallic chemistry as a ]. |
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'''Sodium tetraphenylborate''' is the ] with the formula NaB(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub>. It is a salt, wherein the anion consists of four phenyl rings bonded to boron. This white crystalline solid is used to prepare other tetraphenylborate salts, which are often highly soluble in organic solvents. The compound is used in inorganic and organometallic chemistry as a ] for ], ], ], and ] ions, and some organic nitrogen compounds. |
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==Synthesis and structure== |
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Sodium tetraphenylborate is synthesized by the reaction between ] and ]: |
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:NaBF<sub>4</sub> + 4 PhMgBr → 2 MgBr<sub>2</sub> + 2 MgF<sub>2</sub> + NaBPh<sub>4</sub> (where Ph = phenyl) |
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A related synthesis involves the use of ] in place of the ].<ref>R. M. Washburn, F. A. Billig, "Tetraarylboron Compounds"US Patent 3,311,662.</ref> |
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Unlike smaller counteranions, such as nitrate and the halides, tetraphenylborate confers lipophilicity to its salts. Many analogous tetraarylborates have been synthesized, containing both electron-rich and electron-deficient aryl groups. |
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The anhydrous salt adopts a polymeric structure in the solid state consisting of Na<sup>+</sup>-phenyl interactions. As such the salt could be classified as an ].<ref>Ulrich Behrens, Frank Hoffmann, and Falk Olbrich "Solid-State Structures of Base-Free Lithium and Sodium Tetraphenylborates at Room and Low Temperature: Comparison with the Higher Homologues MB(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> (M = K, Rb, Cs)" Organometallics 2012, volume 31, p. 905−913. {{doi|10.1021/om200943n}}</ref> |
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==Synthesis== |
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Sodium tetraphenylborate is synthesized by the reaction between ] and ]:<ref>{{cite journal | journal = Inorganic Syntheses| year = 2002 | pages = 83 | doi = 10.1002/0471224502.ch2 | title = Synthesis of <sup>2+</sup> (M = V, Cr, Mn, Fe, Co, Ni) Salts of Tetraborate | author = W. E. Buschman, J. S. Miller | volume = 33}}</ref> |
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:NaBF<sub>4</sub> + 4 ArMgBr → 2 MgBr<sub>2</sub> + 2 MgF<sub>2</sub> + NaBAr<sub>4</sub> (where Ar = ]) |
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Unlike smaller counteranions, such as nitrate and the halides, tetraphenylborate confers lipophilicity to its salts. Many analogues tetraarylborates have been synthesized, containing both electron rich and electron deficient aryl groups. |
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==Use in chemical synthesis== |
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==Use in chemical synthesis== |
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===Preparation of N-acylammonium salts=== |
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===Preparation of ''N''-acylammonium salts=== |
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Addition of sodium tetraphenylborate to a solution of a tertiary amine and an acid chloride in acetonitrile gives the acylonium salt by precipitating NaCl from the reaction mixture. This method has a broad scope:<ref>{{cite journal | journal = ] | year = 1992 | pages = 5136 | doi =10.1021/jo00045a025 | title = Preparation and characterization of crystalline N-acylammonium salts. | author = J. King and G. Bryant | volume = 57}}</ref> |
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Addition of sodium tetraphenylborate to a solution of a tertiary amine and an acid chloride in ] gives the acylonium salt by precipitating NaCl from the reaction mixture. This method has a broad scope:<ref>{{cite journal | journal = ] | year = 1992 | pages = 5136 | doi =10.1021/jo00045a025 | title = Preparation and characterization of crystalline N-acylammonium salts |author1=J. King |author2=G. Bryant |name-list-style=amp | volume = 57 | issue = 19}}</ref> |
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:RC(O)Cl + R'<sub>3</sub>N + NaB(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> → + NaCl |
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:RC(O)Cl + R'<sub>3</sub>N + NaB(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> → + NaCl |
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Sodium tetraphenylborate is also employed as a phenyl donor in palladium-catalyzed cross-coupling reactions involving vinyl and aryl triflates to give arylalkenes and biaryl compounds in good yields and under mild conditions, respectively.<ref>{{cite journal | journal = Tetrahedron Letters | year = 1992 | pages = 4815 | doi = 10.1016/S0040-4039(00)61293-5 | title = Palladium-catalyzed cross-coupling reactions of vinyl and aryl triflates with tetraarylborates. | author = P. Ciattini, E. Morera, G. Ortar | volume = 33}}</ref> |
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Sodium tetraphenylborate is also employed as a phenyl donor in palladium-catalyzed cross-coupling reactions involving vinyl and aryl triflates to give arylalkenes and biaryl compounds in good yields and under mild conditions, respectively.<ref>{{cite journal | journal = Tetrahedron Letters | year = 1992 | pages = 4815 | doi = 10.1016/S0040-4039(00)61293-5 | title = Palladium-catalyzed cross-coupling reactions of vinyl and aryl triflates with tetraarylborates |author1=P. Ciattini |author2=E. Morera |author3=G. Ortar | volume = 33 | issue = 33}}</ref> |
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===Use in coordination chemistry=== |
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===Use in coordination chemistry=== |
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Tetraphenylborates are often studied in organometallic chemistry because of their favorable solubility in nonpolar solvents and their crystallinity. For example, the homoleptic ] complexes {M<sub>5</sub>}<sup>2+</sup> (Ni, Pd, and Pt) have been prepared as their tetraphenylborate salts.<ref>{{cite journal | journal = Inorganic Syntheses| year = 2007 | pages = 76 | doi = 10.1002/9780470132517.ch22 | title = Pentakis(Trimethyl Phosphite) Complexes of the d<sup>8</sup> Transition Metals | author = J. P. Jesson, M. Cushing, ] | volume = 20}}</ref> Similarly, sodium tetraphenylborate has been used to isolate ].<ref>{{cite journal | journal = ] | volume = 15 | year = 1974 | pages = 21 | doi = 10.1002/9780470132463.ch6 | title = trans - (Dinitrogen) Bis Hydridoiron(II) Tetraphenylborate. | author =M. Mays and E. Prater}}</ref> In the reaction below, sodium tetraphenylborate allows N<sub>2</sub> to displace the chloride ligand, which is removed from solution as a precipitate of sodium chloride: |
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Tetraphenylborates are often studied in organometallic chemistry because of their good solubility in nonpolar solvents and their crystallinity. For example, the homoleptic ] complexes {M<sub>5</sub>}<sup>2+</sup> (Ni, Pd, and Pt) have been prepared as their tetraphenylborate salts.<ref>{{cite book | series = Inorganic Syntheses| year = 2007 | pages = 76–82 | author = J. P. Jesson, M. Cushing, ] | volume = 20 | title= Pentakis(Trimethylphosphite) Complexes of the d<sup>8</sup> Transition Metals | chapter = Pentakis(Trimethyl Phosphite) Complexes of the D8 Transition Metals | doi = 10.1002/9780470132517.ch22| isbn = 9780470132517 }}</ref> Similarly, sodium tetraphenylborate has been used to isolate ].<ref>{{cite book | journal = ] | volume = 15 | year = 1974 | pages = 21–25 |author1=M. Mays |author2=E. Prater | title = Inorganic Syntheses | chapter = ''trans'' -(dinitrogen)bis[ethylenebis-(diethylphosphine)]hydridoiron(II) Tetraphenylborate |name-list-style=amp | doi = 10.1002/9780470132463.ch6| isbn = 9780470132463 }}</ref> In the reaction below, sodium tetraphenylborate allows N<sub>2</sub> to displace the chloride ligand, which is removed from solution as a precipitate of sodium chloride: |
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:FeHCl(diphosphine)<sub>2</sub> + NaB(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> + N<sub>2</sub> → B(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> + NaCl |
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:FeHCl(diphosphine)<sub>2</sub> + NaB(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> + N<sub>2</sub> → B(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> + NaCl |
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The use of tetraphenylborate is limited to non-acidic cations, strong acids decompose this anion to ] and ]:<ref>Tianshu Li, Alan J. Lough, Cristiano Zuccaccia, Alceo Macchioni, and Robert H. Morris "An acidity scale of phosphonium tetraphenylborate salts and ruthenium dihydrogen complexes in dichloromethane" Can. J. Chem. 84(2): 164–175 (2006). {{doi|10.1139/V05-236}}.</ref> |
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The use of tetraphenylborate is limited to non-acidic cations. With strong acids, the anion undergoes ] to give ] and ]:<ref>Tianshu Li, Alan J. Lough, Cristiano Zuccaccia, Alceo Macchioni, and Robert H. Morris "An acidity scale of phosphonium tetraphenylborate salts and ruthenium dihydrogen complexes in dichloromethane" Can. J. Chem. 84(2): 164–175 (2006). {{doi|10.1139/V05-236}}.</ref> |
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:H<sup>+</sup> + B(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub><sup>-</sup> → B(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub> + C<sub>6</sub>H<sub>6</sub> |
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:H<sup>+</sup> + B(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub><sup>−</sup> → B(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub> + C<sub>6</sub>H<sub>6</sub> |
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==Related tetraorganoborates== |
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]s often are based on tetraarylborates, with electronegative substituents. Examples include B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub><sup>−</sup> and ] containing the borate]] anion. |
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==References== |
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==References== |
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