Lithium Tetrakis(pentafluorophenyl)borate - Wikipedia

Lithium tetrakis(pentafluorophenyl)­borate

Names
Preferred IUPAC name Lithium tetrakis(pentafluorophenyl)boranuide
Identifiers
CAS Number	371162-53-7 (etherate) Y
3D model (JSmol)	Interactive image
ChemSpider	8071952 N 9160766 (etherate) N
ECHA InfoCard	100.155.284
PubChem CID	9896287
InChI InChI=1S/C24BF20.Li/c26-5-1(6(27)14(35)21(42)13(5)34)25(2-7(28)15(36)22(43)16(37)8(2)29,3-9(30)17(38)23(44)18(39)10(3)31)4-11(32)19(40)24(45)20(41)12(4)33;/q-1;+1 NKey: WTTFKRRTEAPVBI-UHFFFAOYSA-N N InChI=1/C24BF20.Li/c26-5-1(6(27)14(35)21(42)13(5)34)25(2-7(28)15(36)22(43)16(37)8(2)29,3-9(30)17(38)23(44)18(39)10(3)31)4-11(32)19(40)24(45)20(41)12(4)33;/q-1;+1Key: WTTFKRRTEAPVBI-UHFFFAOYAW
SMILES [Li+].Fc1c(c(F)c(F)c(F)c1F)[B-](c2c(F)c(F)c(F)c(F)c2F)(c3c(F)c(F)c(F)c(F)c3F)c4c(F)c(F)c(F)c(F)c4F
Properties
Chemical formula	C24BF20Li
Molar mass	685.98 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is YN ?) Infobox references

Chemical compound

Lithium tetrakis(pentafluorophenyl)borate is the lithium salt of the weakly coordinating anion (B(C6F5)4)−. Because of its weakly coordinating abilities, lithium tetrakis(pentafluorophenyl)borate makes it commercially valuable in the salt form in the catalyst composition for olefin polymerization reactions and in electrochemistry. It is a water-soluble compound. Its anion is closely related to the non-coordinating anion known as BARF. The tetrakis(pentafluorophenyl)borates have the advantage of operating on a one-to-one stoichiometric basis with Group IV transition metal polyolefin catalysts, unlike methylaluminoxane (MAO) which may be used in large excess.

Structure and properties

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The anion is tetrahedral with B-C bond lengths of approximately 1.65 Angstroms. The salt has only been obtained as the etherate, and the crystallography confirms that four ether (OEt2) molecules are bound to the lithium cation, with Li-O bond lengths of approximately 1.95 Å. The [Li(OEt2)4]+ complex is tetrahedral.

Preparation

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The salt was first produced in studies on tris(pentafluorophenyl)boron, a well known Lewis acidic compound. Combining equimolar ether solutions of pentafluorophenyllithium and tris(pentafluorophenyl)boron gives the lithium salt of tetrakis(pentafluorophenyl)borate, which precipitates the etherate as a white solid:[1]

(C6F5)3B + Li(C6F5) → [Li(OEt2)3][B(C6F5)4]

Since its discovery, many revised syntheses have been described.[2]

Reactions

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Lithium tetrakis(pentafluorophenyl)borate is primarily used to prepare cationic transition metal complexes:

LiB(C6F5)4) + MLnCl → LiCl + [MLn]B(C6F5)4

LiB(C6F5)4 is converted to the trityl reagent [Ph3C][B(C6F5)4], which is useful activator of Lewis-acid catalysts.[3][4]

Safety

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Lithium tetrakis(pentafluorophenyl)borate will deflagrate on melting (ca. 265 °C) giving thick black smoke, even under nitrogen.[5] The mechanism is unknown. Metal tetrakis(pentafluorophenyl)borates of K and Na decompose vigorously as well.[6][7]

See also

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• Tetraphenylborate

References

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1. ^ A.G. Massey, A.J. Park. "Perfluorophenyl derivatives of the elements : I. Tris(pentafluorophenyl)boron." Journal of Organometallic Chemistry, 1964, 2, 245-250. doi:10.1016/S0022-328X(00)80518-5
2. ^ Martin, Eddy, Hughes, David, and Lancaster, Simon. "The composition and structure of lithium tetrakis(pentafluorophenyl)borate diethyletherate." Inorganica Chimica Acta, 2010, 363, 275-278 doi:10.1016/j.ica.2009.09.013
3. ^ Cordoneanu, Adina, Drewitt, Mark, Bavarian, Neda, Baird, Michael. "Synthesis and Characterization of Weakly Coordinating Anion Salts of a New, Stable Carbocationic Reagent, the Dibenzosuberenyl (Dibenzotropylium) Ion." New Journal of Chemistry, 2008, 32, 1890-1898. doi:10.1039/b804868a
4. ^ Lancaster, Simon J.; Bochmann, Manfred (2002). "The Reaction of Cp*2ZrMe2 with [CPh3][B(C6F5)4]: Triphenylethane Does Not form ηn-Arene Complexes with [Cp*2ZrMe]+". Journal of Organometallic Chemistry. 654 (1–2): 221–223. doi:10.1016/S0022-328X(02)01319-0.
5. ^ Martin, Eddy; Hughes, David L.; Lancaster, Simon J. (2010-01-04). "The composition and structure of lithium tetrakis(pentafluorophenyl)borate diethyletherate". Inorganica Chimica Acta. 363 (1): 275–278. doi:10.1016/j.ica.2009.09.013. ISSN 0020-1693.
6. ^ Stockmann, Tom J.; Ding, Zhifeng (2012-10-25). "Tetraoctylphosphonium tetrakis(pentafluorophenyl)borate room temperature ionic liquid toward enhanced physicochemical properties for electrochemistry". The Journal of Physical Chemistry B. 116 (42): 12826–12834. doi:10.1021/jp3081832. ISSN 1520-5207. PMID 23009026.
7. ^ Lee, Hyun-Ju; Baek, Jun-Won; Seo, Yeong-Hyun; Lee, Hong-Cheol; Jeong, Sun-Mi; Lee, Junseong; Lee, Chong-Gu; Lee, Bun-Yeoul (2021-05-10). "Preparation of High-Purity Ammonium Tetrakis(pentafluorophenyl)borate for the Activation of Olefin Polymerization Catalysts". Molecules. 26 (9): 2827. doi:10.3390/molecules26092827. ISSN 1420-3049. PMC 8126221. PMID 34068755.

v t e Lithium compounds (list)
Compounds with noble gases	LiHe HLiHe+ (hypothetical) LiFHeO(hypothetical) LiHe2 (hypothetical) (HeO)(LiF)2 (hypothetical) La2/3−xLi3xTiO3He (hypothetical)
Compounds with halogens	FLiBe FLiNaK LiAt (hypothetical) LiBr LiBrO LiBrO2 LiBrO3 LiBrO4 LiCl LiClO LiClO2 LiClO3 LiClO4 LiF Li2F LiFO LiI LiIO LiIO2 LiIO3 LiIO4
Oxides and hydroxides	LiO− LiO2 LiO3 Li2O Li2O2 LiOH
Compounds with chalcogens	LiCF3SO3 LiHSO3 LiHSO4 Li2Po Li2S Li2Se Li2SeO3 Li2SeO4 Li2Te LiTe3 Li2TeO3 Li2TeO4
Compounds with pnictogens	Li1+xAlxGe2−x(PO4)3 LiAl1+xTi2−x(PO4)3 LiAs LiAsF6 Li3AsO4 LiFePO4 LiGe2(PO4)3 LiH2AsO4 Li2HAsO4 Li2HPO3 Li2HPO4 Li3PO3 Li3PO4 LiH2PO3 LiH2PO4 LiN3 Li3N LiNH2 Li2NH LiNO2 LiNO3 Li2N2O2 Li2NaPO3 LiNaNO2 Li3P LiPF6 Li3PO4 Li[SbF6] LiTi2(PO4)3 LiZr2(PO4)3
Compounds with group 14 elements	Li2C2 Li2CO3 Li2GeF6 Li2GeO3 LiHCO3 Li3H(CO3)2 LiSi Li2SiF6 Li2SiO3 Li2Si2O5 Li4SiO4 Li2SnF6
Compounds with group 13 elements	CsLiB6O10 LiAlCl4 LiAlF4 Li3AlF6 LiAlH4 LiAlO2 LiB(C2O4)2 LiB(C6F5)4 LiBF4 LiBH4 LiBO2 LiB3O5 Li2B4O7 LiBSi2 LiGaH4
Compounds with transition metals	Li[AuCl4] LiCoO2 Li2CrO4 Li2Cr2O7 Li2IrO3 Li7La3Zr2O12 LiMn2O4 Li2MoO4 Li0.9Mo6O17 LiNbO3 Li2NbO3 Li2PtO3 Li2RuO3 LiTaO3 Li2TiF6 Li2TiO3 Li4Ti5O12 LiVO3 Li3V2(PO4)3 LiWF6 Li2WO4 Li2ZrF6 Li2ZrO3
Organic (soaps)	Hemolithin (extraterrestrial protein) Organolithium reagents Gilman reagent CH3COOLi C4H6LiNO4 LiC2F6NO4S2 LiN(SiMe3)2 Li3C6H5O7 C5H5Li LiN(C3H7)2 (C6H5)2PLi C18H35LiO3 C6H13Li C4H9Li CH3CHLiCH2CH3 (CH3)3CLi C12H28BLi CH3Li Li+C10H−8 C5H11Li C5H3LiN2O4 C6H5Li LiC2CH3 LiO2C(CH2)16CH3 C4H5LiO4 LiEt3BH LiOC(CH3)3 C9H18LiN LiC2H3 Vinyllithium LiC11H23COO CH3CH(OH)COOLi LiC2H2ClO2 LiC2H3IO2 Li(CH3)2N LiCHO2 LiCH3O LiC2H5O Li2C2O4
Other compounds	Li2 LixBey (hypothetical) LiCN Li2CN2 LiCNO LiH LiNa LiSCN LiYF4 Neodymium-doped
Minerals	Amblygonite Berezanskite Brannockite Cryolithionite Darapiosite Darrellhenryite Elbaite Fluorine Elbaite Fluor-liddicoatite Emeleusite Eucryptite Faizievite Hectorite Hsianghualite Jadarite Kunzite Lavinskyite Lepidolite Lithiophilite Lithiophosphate Manandonite Manganoneptunite Nambulite Neptunite Olympite Petalite Pezzottaite Rossmanite Saliotite Sogdianite Spodumene Sugilite Tiptopite Tourmaline Triphylite Zabuyelite Zektzerite Zinnwaldite
Other Li-related	Aluminium–lithium alloys Heteroatom-promoted lateral lithiation LB buffer Lithium atom Lithium medication LiNixCoyAlzO2 LiNixMnyCozO2 Lithium soap Lithium Triangle Lucifer yellow Magnesium–lithium alloys NASICON Environmentally friendly red light flare