US20070293391A1 - Novel Strong Boron-Containing Acids, The Preparation And Use Thereof - Google Patents

Novel Strong Boron-Containing Acids, The Preparation And Use Thereof Download PDF

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US20070293391A1
US20070293391A1 US11/665,739 US66573905A US2007293391A1 US 20070293391 A1 US20070293391 A1 US 20070293391A1 US 66573905 A US66573905 A US 66573905A US 2007293391 A1 US2007293391 A1 US 2007293391A1
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atoms
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group
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alkyl
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Maik Finze
Eduard Bernhardt
Helge Willner
Nikolai Ignatyev
Urs Welz-Biermann
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the invention relates to boron-containing acids of the general formula (I) [B(R F ) 4-x-y (CN) x F y ] ⁇ H + (I)
  • x 0, 1, 2, 3 or 4,
  • the ligands R F may be identical or different and
  • R F stands for a perfluorinated or partially fluorinated C 1-12 -alkyl group
  • the present invention furthermore relates to processes for the preparation of the acids according to the invention, to salts comprising a cation and the anion of a selection of the acids according to the invention, and to processes for the preparation of the salts.
  • the invention furthermore relates to the use of the acids and salts according to the invention.
  • the present invention had the object of providing alternative strong acids which can be used, in particular, for the synthesis of salts which lead to ionic liquids or catalyst systems.
  • x 0, 1, 2, 3 or 4,
  • the ligands R F may be identical or different and
  • R F stands for a perfluorinated or partially fluorinated C 1-12 -alkyl group
  • CN group may be bonded to the B atom via the C atom
  • Fluorinated alkyl groups are, for example, difluoromethyl, trifluoromethyl, pentafluoroethyl, pentafluoropropyl, heptafluoropropyl, pentafluorobutyl, heptafluorobutyl, nonafluorobutyl, C 5 H 4 F 7 , C 5 H 2 F 9 , C 5 F 11 , C 6 H 4 F 9 , C 6 H 2 F 11 , C 6 F 13 , C 7 H 4 F 11 , C 7 H 2 F 13 , C 7 F 15 , C 8 H 4 F 13 , C 8 H 2 F 15 , C 8 F 17 , C 9 H 4 F 15 , C 9 H 2 F 17 , C 9 F 19 , C 10 H 4 F 17 , C 10 H 2 F 19 , C 10 F 21 , C 11 H 4 F 19 , C 11 H 2 F 21 , C 11 F 23 , C 12 H 4 F 21 , C 12 H 2 F
  • Perfluoroalkyl group means that all H atoms of the alkyl group, as described above, have been replaced by F atoms. Fluorinated means that 1 to 16 fluorine atoms in a perfluoroalkyl group have been replaced by hydrogen atoms.
  • R F is particularly preferably trifluoromethyl or pentafluoroethyl.
  • the present invention furthermore relates to processes for the preparation of the acids according to the invention.
  • the ligands R F may be identical or different and
  • R F stands for a perfluorinated or partially fluorinated C 1-12 -alkyl group
  • x 0, 1, 2, 3 or 4,
  • R F may be identical or different and
  • R F stands for a the ligands perfluorinated or partially fluorinated C 1-12 -alkyl group
  • M a+ is an alkali metal cation
  • an acid where conversion into the trialkylsilyl ether may optionally be carried out in advance, in particular in the case of later reaction with anhydrous HF.
  • the synthesis of the alkali metal compounds of the formula (II-1) containing at least one cyano group is carried out by isomerisation of corresponding isocyanoborate salts at temperatures between 150° and 300° C., preferably 200°-250° C.
  • x 0, 1, 2, 3 or 4,
  • R F may be identical or different and
  • R F stands for a the ligands perfluorinated or partially fluorinated C 1-12 -alkyl group
  • M a+ is an alkali metal cation, are formed by reaction of the corresponding isocyanoboric acid with a strong base.
  • Suitable bases are, for example, alkali metal amides, such as M[N(SiMe 3 )], where M may denote lithium, sodium or potassium.
  • the first step of this reaction is advantageously carried out in toluene, benzene, hexane or pentane, particularly preferably in toluene, at ⁇ 60° to 0° C., preferably at ⁇ 20° C.
  • the tetracyanoboric acid is synthesised, for example, under the conditions indicated in Example 4.
  • the acids of the formula (I) are formed from the reaction of the corresponding metal salts, in particular alkali metal salts, with strong acids, for example hydrochloric acid.
  • the metal salts of the acids of the formula (I) can be obtained, for example, by the following two-step reaction:
  • Potassium tetrafluoroborate can be reacted with NaCN in the presence of KCl to give the salts potassium tetracyanoborate as principal product, as described in WO 2004/07089, but with the salts K[B(CN) 3 F], K[B(CN) 2 F 2 ] and K[B(CN)F 3 ] also being formed in different amount ratios.
  • Stepwise replacement of the fluorine ligand by the CN ligand enables control of the ligand exchange and the amount ratios of the salts formed via the reaction time and does not present the person skilled in the art with any difficulties.
  • the subsequent reaction with ClF 3 , ClF or (CH 3 ) 2 NF as described in J. Am. Chem. Soc.
  • the acids of the formula (I) which contain at least one CN group can be isolated as solvent-free acids.
  • the acids according to the invention have high proton activity, as can be seen, for example, through deuterium exchange in C 6 D 6 .
  • the acids according to the invention can be used for the synthesis of further inorganic or organic salts, which can in turn be used as conductive salts for various electrochemical devices or as ionic liquids.
  • the conversion into their salts is carried out, for example, by neutralisation using an inorganic or organic base, for example the reaction of tetracyanoboric acid with tetra(butyl)ammonium hydroxide to give tetra(butyl)ammonium tetracyanoborate.
  • the acids according to the invention or the inorganic salts thereof, in particular alkali metal salts, are also good starting materials for cationic dyes containing the cyanoborate anions of the formula [B(R F ) 4-x-y (CN) x F y ] ⁇ , where x, y and R F have a meaning indicated above.
  • the present invention furthermore relates to a selection of salts of the acids of the formula (I) according to the invention, namely the salts of the general formula (II) [B(R F ) 4-x-y (CN) x F y ] a ⁇ M a+ (II)
  • the ligands R F may be identical or different and
  • R F stands for a perfluorinated or partially fluorinated C 1-12 -alkyl group
  • M a+ is an alkali metal cation, a silver, magnesium, copper(I), copper(II), zinc(II) or calcium(II) cation or an organic cation, where K[B(CF 3 ) 3 CN] and [NH 4 ][B(CF 3 ) 3 CN] are excluded.
  • cation M a+ is an alkali metal cation, preferably a lithium, sodium or potassium cation.
  • This group of compounds of the formula (II) is particularly suitable for the synthesis of ionic liquids containing the anion [B(R F ) 4-x-y (CN) x F y ] a ⁇ , where x, y, a and R F have a meaning indicated above, by metathesis with a salt MA, consisting of an organic cation, as defined below, and the counterion A, defined as F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , [HF 2 ] ⁇ , [CN] ⁇ , [SCN] ⁇ , [CH 3 COO] ⁇ , [CH 3 SO 3 ] ⁇ , [CF 3 COO] ⁇ , [CF 3 SO 3 ] ⁇ , [CH 3 OSO 3 ] ⁇ , [SiF 6 ] 2 ⁇ , [BF 4 ] ⁇ , [SO 4 ] 2 ⁇ , [HSO 4 ] 1 ⁇ , [NO 3 ]
  • the anion is preferably F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , [HF 2 ] ⁇ , [CH 3 SO 3 ] ⁇ [CH 3 OSO 3 ] ⁇ , [CF 3 COO] ⁇ , [CF 3 SO 3 ] ⁇ , [(C 2 F 5 ) 2 P(O)O] ⁇ or [CO 3 ] 2 ⁇ , particularly preferably Cl ⁇ , Br ⁇ , [CH 3 OSO 3 ] ⁇ , [CH 3 SO 3 ] ⁇ , [CF 3 SO 3 ] ⁇ or [(C 2 F 5 ) 2 P(O)O] ⁇ .
  • the lithium compounds in this group are particularly suitable as conductive salts in electrolytes, primary batteries, secondary batteries, capacitors, supercapacitors or electrochemical cells, optionally also in combination with further conductive salts and/or additives, as constituent of a polymer electrolyte or phase-transfer agent.
  • the cation M a+ is a silver, magnesium, copper(I), copper(II), zinc(II) or calcium(II) cation.
  • the magnesium, copper(II), zinc(II) or calcium(II) cations are preferably in solvated form.
  • This group of compounds is likewise suitable for the synthesis of ionic liquids containing the corresponding anion by metathesis with a salt MA, as described above for the compounds of the formula (II) containing alkali metal cations.
  • This group of compounds is particularly suitable for metal deposition or as phase-transfer agent.
  • the organic cation here can be selected from the group [NR 1 R 2 R 3 R 4 ] + , [PR 1 R 2 R 3 R 4 ] + , [P(NR 1 R 2 ) 2 (NR 3 R 4 ) 2 ] + , [C(NR 1 R 2 )(NR 3 R 4 )(NR 5 R 6 )] + , [(R 1 R 2 N)C( ⁇ OR 7 )(NR 3 R 4 )] + , [(R 1 R 2 N)C( ⁇ SR 7 )(NR 3 R 4 )] + or [(C 6 H 6 ) 3 C] + , where the phenyl groups of the tritylium may each be substituted, independently of one another, by R 1 to R 4 .
  • R 1 to R 7 each, independently of one another, denotes hydrogen or straight-chain or branched alkyl having 1 to 20 C atoms,
  • substituents R 1 to R 7 may be partially or fully substituted by halogens, in particular —F and/or —Cl, or partially by —CN or —NO 2
  • one or two non-adjacent carbon atoms which are not in the ⁇ -position may be replaced by atoms and/or atom groups selected from the group —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, —SO 2 —, —SO 2 O—, —C(O)NH—, —C(O)NR′—, —SO 2 NH—, —SO 2 NR′—, —N ⁇ , —N ⁇ N—, —NH—, —NR′—, —PR′—, —P(O)R′—, —P(O)R′—O—, —O—P(O)R′—O—, —P(O)(NR′ 2 )—NR′— and —PR′ 2 ⁇ N— or by the end groups —C(O)X′ or —SO 2 X′, where R′
  • An alkyl group having 1 to 20 C atoms is taken to mean, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, furthermore also pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethyl-propyl, hexyl, heptyl, octyl, nonyl, decyl, C 11 H 23 , C 12 H 25 , C 13 H 27 , C 14 H 29 , C 15 H 31 , C 16 H 33 , C 17 H 35 , C 18 H 37 , C 19 H 39 or C 20 H 41 .
  • alkyl groups may also be partially or fully substituted by halogens, in particular —F and/or —Cl.
  • Fluorinated alkyl groups are difluoromethyl, trifluoromethyl, pentafluoroethyl, pentafluoropropyl, heptafluoropropyl, heptafluorobutyl or nonafluorobutyl.
  • a straight-chain or branched alkenyl having 2 to 20 C atoms, where a plurality of double bonds may also be present, is, for example, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, —C 9 H 17 , —C 10 H 19 to —C 20 H 39 ; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, preference is furthermore given to 4-pentenyl, isopentenyl or hexenyl.
  • a straight-chain or branched alkynyl having 2 to 20 C atoms, where a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, heptynyl, octynyl, —C 9 H 15 , —C 10 H 17 to —C 20 H 37 , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.
  • Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl, cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, phenyl, cycloheptenyl, cyclohepta-1,3-dienyl, cyclohepta-1,4-dienyl or cyclohepta-1,5-dienyl, each of which may be substituted by C 1 — to C 6 -alkyl groups, where the cycloalkyl group or the cycloalkyl group which is substituted by C 1 — to C 6 -alkyl groups may in turn also be substituted by hal
  • the substituents R 1 to R 7 may be partially or fully substituted by halogen atoms, in particular by F and/or Cl, or partially by CN or NO 2 .
  • C 3 — to C 7 -cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
  • substituted phenyl denotes phenyl which is substituted by C 1 — to C 6 -alkyl, C 1 — to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C(O)O—C 1 -C 6 -alkyl, NH 2 , C 1 -C 6 -alkylamino or C 1 -C 6 -dialkylamino, COOH, C(O)NH 2 , C(O)NHR′′, C(O)NR′′ 2 , SO 2 OR′′, SO 2 X′, SO 2 NH 2 , SO 2 NHR′′, SO 2 NR′′ 2 , SO 3 H, NR′′C(O)R′′ or NHC(O)R′′, where X′ denotes F, Cl or Br and R′′ denotes a non-, partially or perfluor
  • heterocycle is taken to mean a saturated or unsaturated mono- or bicyclic heterocyclic radical having 5 to 13 ring members, in which 1, 2 or 3 N and/or 1 or 2 S or O atoms may be present and the heterocyclic radical may be mono- or polysubstituted by C 1 — to C 6 -alkyl, C 1 — to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C(O)O—C 1 -C 6 -alkyl, NH 2 , C 1 -C 6 -alkylamino or C 1 -C 6 -dialkylamino, COOH, C(O)NH 2 , C(O)NHR′′, C(O)NR′′ 2 , SO 2 OR′′, SO 2 X′, SO 2 NH 2 , SO 2 NHR′′, SO 2 NR′′
  • the heterocyclic radical is preferably substituted or unsubstituted 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, furthermore preferably 1,2,3-triazol-1-, -4- or -5-yl, 1,2,4-triazol-1-, -4- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl, 1,
  • the carbocycles or heterocycles of the above-mentioned guanidinium cations may optionally also be substituted by C 1 — to C 6 -alkyl, C 1 — to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C(O)O—C 1 -C 6 -alkyl, NH 2 , C 1 -C 6 -alkylamino or C 1 -C 6 -dialkylamino, COOH, C(O)NH 2 , C(O)NHR′′, C(O)NR′′ 2 , SO 2 OR′′, SO 2 NH 2 , SO 2 NHR′′, SO 2 NR′′ 2 , SO 2 X′, SO 3 H, NR′′C(O)R′′ or NHC(O)R′′, where X′ and R′′ have an above-mentioned meaning
  • substituents of the uronium cation [(R 1 R 2 N)—C( ⁇ OR 7 )(NR 3 R 4 )] + or of the thiouronium cation [(R 1 R 2 N)—C( ⁇ SR 7 )(NR 3 R 4 )] + may also be connected in pairs in such a way that mono-, bi- or polycyclic cations are formed. Without restricting generality, examples of such cations are indicated below, where X ⁇ O or S: where the substituents R 1 , R 3 and R 7 may have an above-mentioned or particularly preferred meaning.
  • the carbocycles or heterocycles of the above-mentioned cations may optionally also be substituted by C 1 — to C 6 -alkyl, C 1 — to C 6 -alkenyl, NO 2 , F, Cl, Br, I, OH, C 1 -C 6 -alkoxy, CN, SCN, SCF 3 , SO 2 CF 3 , C(O)O—C 1 -C 6 -alkyl, NH 2 , C 1 -C 6 -alkylamino or C 1 -C 6 -dialkylamino, COOH, C(O)NH 2 , C(O)NHR′′, C(O)NR′′ 2 , SO 2 OR′′, SO 2 NH 2 , SO 2 NHR′′, SO 2 NR′′ 2 , SO 2 X′, SO 3 H, NR′′C(O)R′′ or NHC(O)R′′ or substituted or unsubstituted phenyl or an unsubstituted
  • the organic cation is particularly preferably selected from the group of the ammonium, phosphonium or guanidinium salts.
  • the substituents R 1 to R 7 are each, independently of one another, preferably a straight-chain or branched alkyl group having 1 to 4 C atoms.
  • R 1 to R 7 are particularly preferably methyl, ethyl, propyl, i-propyl or butyl.
  • R 1 to R 4 in the formulae [NR 1 R 2 R 3 R 4 ] + or [PR 1 R 2 R 3 R 4 ] + are particularly preferably identical.
  • the organic cation can furthermore be selected from the group of the heterocyclic cations.
  • Heterocyclic cations are, for example,
  • R 1 ′ to R 4 ′ each, independently of one another, denotes hydrogen
  • substituents R 1 ′ to R 4 ′ may be partially or fully substituted by halogens, in particular —F and/or —Cl, or partially by —CN or —NO 2 ,
  • R 1 ′ and R 4 ′ cannot simultaneously be perfluorinated or perchlorinated.
  • one or two non-adjacent carbon atoms which are not in the ⁇ -position may to the heteroatom be replaced by atoms and/or atom groups selected from the group —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, —SO 2 —, —SO 2 O—, —C(O)NH—, —C(O)NR′—, —SO 2 NH—, —SO 2 NR′—, —N ⁇ , —N ⁇ N—, —NH—, —NR′—, —PR′—, —P(O)R′—, —P(O)R′—O—, —O—P(O)R′—O—, —P(O)(NR′ 2 )—NR′— and —PR′ 2 ⁇ N— or by the end groups —C(O)X′ or —SO 2
  • Aryl denotes unsubstituted or substituted phenyl or naphthyl, preferably phenyl.
  • Aryl-C 1 -C 6 -alkyl denotes, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl.
  • Fluorinated aryl-C 1 -C 6 -alkyl denotes, for example, pentafluorophenyldifluoromethyl, pentafluorophenyltetrafluoroethyl or pentafluorophenylethyl.
  • heteroaryl is identical with the term heterocyclic radical, as described above.
  • a substituent with the name heteroaryl-C 1 -C 6 -alkyl is composed of a heteroaryl, as described above, and an alkylene chain having 1 to 6 C atoms, as already described clearly in the case of the term aryl-C 1 -C 6 -alkyl.
  • the substituents R 1 ′ to R 4 ′ are particularly preferably a straight-chain or branched alkyl group having 1 to 20 C atoms, very particularly preferably having 1 to 12 C atoms.
  • the cations are particularly preferably selected from substituted imidazolium, substituted pyridinium, substituted pyrrolidinium, substituted piperidinium or substituted morpholinium, as defined above.
  • the salts of the formula (II) according to the invention containing organic cations, as described above, can be used as ionic liquids.
  • Ionic liquids can be employed, for example, as solvents for many synthetic or catalytic reactions, for example Friedel-Crafts acylation and alkylation, Diels-Alder cyclo-additions, hydrogenation and oxidation reactions, Michael-type reactions or Heck reactions, as non-aqueous electrolytes, which are optionally employed in combination with other conductive salts additives and solvents known to the person skilled in the art.
  • these ionic liquids can be used as nonaqueous polar substances in suitable reactions as phase-transfer catalyst, as surfactant (surface-active agent), as plasticiser or as medium for the heterogenisation of homogeneous catalysts.
  • They are furthermore suitable as desiccants, heat-transfer media and as separating agents for gases.
  • Salts of the formula (II) where M a+ is an alkali metal cation can in turn be prepared by neutralising an acid of the formula (Ia), a selection of the acids of the formula (I) according to the invention, [B(R F ) 4-x-y (CN) x F y ] ⁇ H a+ (Ia)
  • the ligands R F may be identical or different and
  • R F stands for a perfluorinated or partially fluorinated C 1-12 -alkyl group
  • inorganic bases such as alkali metal hydroxides, for example KOH
  • the reaction is carried out in water or organic solvents at temperatures of 0° to 100° C., preferably at room temperature.
  • the invention furthermore relates to a process for the preparation of a salt of the formula (II) in which M a+ denotes a silver, magnesium, copper(I), copper(II), zinc(II) or calcium(II) cation or an organic cation by a salt-exchange reaction, characterised in that an alkali metal salt of the formula (II), prepared as described above or the acid itself, is reacted with a compound of the formula (III) MA (III),
  • M denotes a silver, magnesium, copper(I), copper(II), zinc(II) or calcium(II) cation or an organic cation and
  • A OH ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , [HF 2 ] ⁇ , [CN] ⁇ , [SCN] ⁇ , [CH 3 COO] ⁇ , [CH 3 SO 3 ] ⁇ , [CF 3 COO] ⁇ , [CF 3 SO 3 ] ⁇ , [CH 3 OSO 3 ] ⁇ , [BF 4 ] ⁇ , [SO 4 ] 2 ⁇ , [HSO 4 ] 1 ⁇ , [NO 3 ] ⁇ , [C 2 H 5 OSO 3 ] ⁇ , [(C 2 F 5 ) 2 P(O)O] ⁇ , [C 2 F 5 P(O)O 2 ] 2 ⁇ , tosylates, malonates, substituted malonates or [CO 3 ] 2 ⁇ .
  • the reaction can also be carried out with metal oxides, for example oxides of the group 1, 2, 11 and 12 metals.
  • the anion of the formula (III) is preferably OH ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , [CH 3 SO 3 ] ⁇ [CH 3 OSO 3 ] ⁇ , [CF 3 COO] ⁇ , [CF 3 SO 3 ] ⁇ , [(C 2 F 5 ) 2 P(O)O] ⁇ or [CO 3 ] 2 ⁇ , particularly preferably OH ⁇ , Cl ⁇ , Br ⁇ , [CH 3 OSO 3 ] ⁇ , [CF 3 SO 3 ] ⁇ , [CH 3 SO 3 ] ⁇ or [(C 2 F 5 ) 2 P(O)O] ⁇ .
  • the reaction is advantageously carried out in water, where temperatures of 0°-100° C., preferably 15°-60° C., particularly preferably at room temperature, are suitable.
  • reaction may alternatively also be carried out in organic solvents at temperatures between ⁇ 30° and 100° C.
  • Suitable solvents are benzene, acetonitrile, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or alcohol, for example methanol, ethanol or isopropanol.
  • the invention furthermore relates to the use of an acid of the formula (I) or of the formula (Ia), as described above, or of a salt of the general formula (II), as described above, for the synthesis of catalysts containing rare earths.
  • Catalysts containing rare earths or (transition) metals such as, for example, rhodium, ruthenium, iridium, palladium, platinum, osmium, cobalt, nickel, iron, titanium, zirconium, hafnium, thorium, uranium, gold or tungsten, are important catalysts for reactions such as, for example, the catalytic hydrogenation of alkenes, hydroformylations, hydrosilylations, isomerisations of unsaturated compounds, carbonylations, C—C couplings, polymerisations or oligomerisations.
  • rare earths or (transition) metals such as, for example, rhodium, ruthenium, iridium, palladium, platinum, osmium, cobalt, nickel, iron, titanium, zirconium, hafnium, thorium, uranium, gold or tungsten.
  • the ligands R F may be identical or different and
  • R F stands for a perfluorinated or partially fluorinated C 1-12 -alkyl group
  • a ligand exchange of chloride by the corresponding borate anion takes place here.
  • the reaction is carried out in a polar solvent, preferably in an alcohol, such as ethanol or isopropanol, at temperatures between 0° C. and 100° C., preferably between 10° and 60° C., particularly preferably at room temperature.
  • a polar solvent preferably in an alcohol, such as ethanol or isopropanol
  • the rhodium catalysts formed can be purified by methods which are known to the person skilled in the art, such as, for example, by extraction and/or recrystallisation.
  • x 0, 1, 2, 3 or 4,
  • the ligands R F may be identical or different and
  • R F stands for a perfluorinated or partially fluorinated C 1-12 -alkyl group
  • the reaction is advantageously carried out in dichloromethane.
  • the starting materials are mixed at temperatures of ⁇ 60° C., the actual reaction is carried out at room temperature.
  • This type of catalyst is usually generated in situ.
  • the NMR spectra were measured on solutions in deuterated solvents at 20° C. in a Bruker Avance 300 spectrometer with a 5 mm 1 H/BB broadband head with deuterium lock, unless indicated in the examples.
  • the measurement frequencies of the various nuclei are: 1 H: 300.13 MHz, 11 B: 96.92 MHz, 19 F: 282.41 MHz and 31 P: 121.49 MHz.
  • the referencing method is indicated separately for each spectrum or each data set.
  • the reaction vessel is cooled to ⁇ 20° C., and the toluene/amide solution is added dropwise over the course of two hours with stirring. When the addition is complete, the reaction mixture is stirred at ⁇ 20° C. for a further 30 minutes. 20 ml of an aqueous KOH/K 2 CO 3 solution are subsequently added to the mixture. The toluene phase is separated off, and the solvent is removed in vacuo in a rotary evaporator. The residue is taken up in 50 ml of diethyl ether and added to the aqueous phase of the reaction. The reaction mixture is extracted with a further 100 and 50 ml of diethyl ether. The combined organic phases are dried using potassium carbonate, and the mixture is subsequently filtered. All volatile constituents are pumped off on a rotary evaporator, giving 1.08 g of potassium tris(trifluoromethyl)isocyanoborate, which corresponds to a yield of 83%.
  • the dichloromethane solution is concentrated to a volume of about 2 ml in vacuo.
  • the trityl salt is precipitated as solid by slow addition of 25 ml of hexane with constant stirring. After one hour, the stirring is stopped, and the product settles. The liquid phase is removed.
  • the crude product is washed with hexane, giving 445 mg of triphenylmethyl tris(trifluoromethyl)cyanoborate, which corresponds to a yield of 82%.

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US20120018676A1 (en) * 2009-02-02 2012-01-26 Lonza Ltd. Novel Tricyanoborates
CN102712659A (zh) * 2010-01-18 2012-10-03 默克专利有限公司 电解质配制剂
CN102712660A (zh) * 2010-01-18 2012-10-03 默克专利有限公司 含有全氟烷基-氰基-烷氧基-硼酸根阴离子或全氟烷基-氰基-烷氧基-氟-硼酸根阴离子的化合物
CN102712661A (zh) * 2010-01-18 2012-10-03 默克专利有限公司 制备全氟烷基氰基硼酸盐或全氟烷基氰基氟硼酸盐的方法
CN103687863A (zh) * 2011-07-15 2014-03-26 默克专利有限公司 含有烷基-氰基-硼酸根或烷基-氰基-氟硼酸根阴离子的化合物
US9243013B2 (en) 2008-08-22 2016-01-26 Nippon Shokubai Co., Ltd. Ionic compound, method for producing the same, and ion-conductive material comprising the same

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KR20120120314A (ko) * 2010-01-18 2012-11-01 메르크 파텐트 게엠베하 전해질 조성물
DE102015006493A1 (de) 2015-05-22 2016-11-24 Julius-Maximilians-Universität Würzburg Polymere enthaltend polymerisierte ionische Flüssigkeiten und deren Anwendung in Membranen
DE102016009846A1 (de) 2016-08-16 2018-02-22 Julius-Maximilians-Universität Würzburg Fluoralkylhydrido- und Fluoralkylcyanohydridoborate

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US9243013B2 (en) 2008-08-22 2016-01-26 Nippon Shokubai Co., Ltd. Ionic compound, method for producing the same, and ion-conductive material comprising the same
KR101238570B1 (ko) 2009-02-02 2013-02-28 론자 아게 (론자 엘티디.) 신규한 트리시아노보레이트
TWI408142B (zh) * 2009-02-02 2013-09-11 Lonza Ag 新穎三氰硼酸鹽及新穎三氰硼酸鹽之用途和製備方法
US20120018676A1 (en) * 2009-02-02 2012-01-26 Lonza Ltd. Novel Tricyanoborates
US8283497B2 (en) * 2009-02-02 2012-10-09 Lonza Ltd. Tricyanoborates
CN102712661A (zh) * 2010-01-18 2012-10-03 默克专利有限公司 制备全氟烷基氰基硼酸盐或全氟烷基氰基氟硼酸盐的方法
CN102712660A (zh) * 2010-01-18 2012-10-03 默克专利有限公司 含有全氟烷基-氰基-烷氧基-硼酸根阴离子或全氟烷基-氰基-烷氧基-氟-硼酸根阴离子的化合物
US8835667B2 (en) 2010-01-18 2014-09-16 Merck Patent Gmbh Electrolyte formulations
US8901340B2 (en) 2010-01-18 2014-12-02 Merck Patent Gmbh Compounds containing perfluoroalkyl-cyano-alkoxy-borate anions or perfluoroalkyl-cyano-alkoxy-fluoro-borate anions
US8927757B2 (en) 2010-01-18 2015-01-06 Merck Patent Gmbh Process for the preparation of perfluoroalkylcyano- or perfluoroalkylcyanofluoroborates
US9175021B2 (en) 2010-01-18 2015-11-03 Merck Patent Gmbh Process for the preparation of perfluoroalkylcyano- or perfluoroalkylcyanofluoroborates
CN102712659A (zh) * 2010-01-18 2012-10-03 默克专利有限公司 电解质配制剂
CN103687863A (zh) * 2011-07-15 2014-03-26 默克专利有限公司 含有烷基-氰基-硼酸根或烷基-氰基-氟硼酸根阴离子的化合物

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