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  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
  • C07F9/65688—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphonium compound
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C07F15/006—Palladium compounds
  • C07F15/0066—Palladium compounds without a metal-carbon linkage
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  • 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
  • C07F15/0086—Platinum compounds
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  • C07F17/00—Metallocenes
  • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
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  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/52—Halophosphines

Definitions

• the invention relates to bis (perfluoroalkyl) phosphine acids or bis (perfluoroalkyl) thiophosphinous acids, derivatives thereof, their
• Phosphine acids are of great interest for the synthesis of air-stable metal complexes for homogeneous catalysis.
• Palladium complexes with bis (tert-butyl) phosphine acid are known, which have high activity for the cross-coupling reactions, leading to the linking of new C-C, C-N or C-S bonds.
• the previously known phosphinous acids with alkyl or aryl groups are very unstable compounds and can not be isolated.
• the stabilization is usually carried out by complexation with a transition metal.
• Such transition metal complexes are marketed, for example, by COMBIPHOS CATALYSIS Inc. of Princeton, New Jersey, USA.
• the object of the invention was to prepare stable phosphine acids which are suitable for the preparation of transition metal complexes for homogeneous synthesis.
• phosphinous acids can be stabilized in the acid form by the introduction of perfluoroalkyl groups starting from two C atoms on the phosphorus atom.
• the known bis (trifluoromethyl) phosphine acid (CF 3 ) 2 POH is indeed isolable, but has a low stability, is pyrophoric in air and their complex
• the phosphinous acids of formula I as explained below, unlike the known bis (trifluoromethyl) phosphinous acid, can be synthesized starting from industrially available materials.
• salts of the phosphinous acid according to the invention have excellent properties and can be used in particular as ionic liquids.
• the thiophosphinous acids of the formula I can be prepared from the phosphinous chlorides.
• Ionic liquids or liquid salts are ionic species consisting of an organic cation and usually an inorganic or organic anion. They contain no neutral molecules and usually have melting points less than 373 K.
• ionic liquids e.g. Melting point, thermal and electrochemical stability, viscosity
• polarity and hydrophilicity or lipophilicity can be varied by the appropriate choice of the cation / anion pair.
• the invention therefore relates to compounds of the formula I or corresponding salts of the formula II in which
• R 1 and R 2 are each independently of one another straight-chain or branched perfluoroalkyl groups having 2 to 12 C atoms, Q A is O or S,
• X is H, straight-chain or branched alkyl groups having 1 to 18 C atoms, cycloalkyl having 3 to 7 C atoms, alkenyl having 2 to 12 C atoms, alkynyl having 2 to 12 C atoms, aryl, alkyl-aryl, Si (R °) 3 or Sn (R °) 3 when n is the integer 1, 5 X is H, halogen, N (R °) 2 when n is the integer 0, Y + for ammonium, phosphonium, tritylium, guanidinium, heterocyclic cations containing at least one nitrogen or phosphorus atom, Ag + , Li + , Na + , K + , Rb + or Cs + when n is the integer 1 and o R 0 represents a straight-chain or branched alkyl group having 1 to 8 C atoms.
• R 1 and R 2 may be different or the same. More preferably, R 1 and R 2 are the same. 5
• A is preferably O.
• R 1 and R 2 each independently represent pentafluoroethyl, heptafluoropropyl or linear or branched - A -
• R 1 and R 2 is pentafluoroethyl or nonafluorobutyl linear.
• a straight-chain or branched alkenyl preferably having 2 to 10 C atoms, is, for example, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hexenyl, octenyl or decenyl.
• a straight-chain or branched alkynyl preferably with 3 to 10 C
• Atoms for example, propargyl, 2- or 3-butynyl, further 4-pentynyl, hexynyl, octynyl or decynyl.
• Cycloalkyl having 3 to 7 C atoms means unsubstituted saturated or partially unsaturated cycloalkyl groups having 3-7 C atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl or cycloheptenyl, which is substituted by C r to C 6 - alkyl groups could be.
• Aryl is, for example, substituted or unsubstituted phenyl
• Aryl is particularly preferably unsubstituted or substituted phenyl. Phenyl substituted by C r to C 6 alkyl, C 2 - to C 6 alkenyl, NO 2, CN, F, Cl, Br, I, OH, non-fluorinated, partially fluorinated or perforated C 1 -C 6 -alkoxy , SCF 3, SO 2 CF 3 COOH, C (O) OR ", C (O) X 1, C (O) NR M 2l C (O) H, C (O) R ', SO 2 X 1, SO 2 NR " 2 or SO 3 H substituted phenyl, wherein X 1 F, Cl or Br and R" is a non, partially or perfluorinated
• C 1 to C 6 -alkyl or C 3 - to C 7 -cycloalkyl as defined, for example, o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o-, m- or p-iso-propylphenyl, o-, m- or p-tert-butylphenyl, o-, m- or p-nitrophenyl, o-, m- or p-hydroxyphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m-, p-
• perforated alkoxy groups correspondingly all H atoms of the abovementioned formula are replaced by F. For partially substituted by F alkoxy groups only some H are replaced by F.
• Alkyl-aryl is, for example, benzyl, phenylethyl, phenylpropyl,
• R 0 is a straight-chain or branched alkyl group having 1 to 8 C atoms, for example methyl, ethyl, propyl, n-butyl, s-butyl, tert-butyl, hexyl or octyl, particularly preferably methyl or butyl.
• Halogen is Cl 1 Br or I, preferably Cl or Br.
• Y + is either a metallic cation, for example
• Y + is preferably Ag + , Li + , Na + or K + , more preferably Li + .
• Lithium salts are particularly interesting salts for electrochemical applications, for example as conductive salts in electrochemical cells.
• the compounds of the formula II having the organic cations of the group ammonium, phosphonium, tritylium, guanidinium or a heterocyclic cation containing at least one nitrogen or phosphorus atom, when n 1, are used in particular as ionic liquids.
• ammonium Preferred for ammonium are ammonium cations of the formula (1),
• each R is independently H, OR ', NR' 2l with the proviso that at most one substituent R in formula (I) is OR 1 , NR ' 2 , straight-chain or branched alkyl with 1 -20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated or partially unsaturated cycloalkyl having 3-7 C -Atomen which may be substituted by alkyl groups having 1-6 C atoms, phenyl which may be substituted by alkyl groups having 1-6 C atoms, wherein one or more R partially or completely with halogens, in particular -F and / or -Cl, or partially with -OH, -OR ', -CN, -C (O) OH, -C (O) NR' 2 , -SO 2
• Preferred for phosphonium are phosphonium cations of the formula (2) [PR 3 4 ] + (2), where
• R 3 are each independently H, OR 1 , NR ' 2 , straight-chain or branched alkyl having 1 -20 C atoms, straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2 20 C atoms and one or more triple bonds, saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, phenyl substituted with alkyl groups having 1-6 C atoms may be one or more R 3 partially or completely halogens, especially -F and / or -Cl, or partially with -OH, -OR ', -CN, -C (O) OH, -C (O) NR ' 2 , -SO 2 NR' 2 , -C (O) X 1 , -SO 2 OH, -SO 2 X 1 , -NO 2
• R 8 to R 13 are each independently
• heterocyclic cation containing at least one nitrogen atom are heterocyclic cations of the formula (4), [HetN] + (4), wherein HetN + is a heterocyclic cation selected from the group
• Benzothiazolium Benzoxazolium means, wherein the substituents R 1 'to R 4 ' are each independently
• heterocyclic cation containing at least one phosphorus atom are heterocyclic cations of the formula (5),
• HetP is a heterocyclic cation selected from the group
• X 1 stands for P
• R 1 " , R 2 and R 3 are each independently H, straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl with 2-20 C atoms and one or more triple bonds, saturated or partially unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
• Phenyl which may be substituted by alkyl groups having 1-6 C atoms, saturated, partially or completely unsaturated heteroaryl,
• completely unsaturated substituents are also understood as meaning aromatic substituents.
• Preferred substituents R of the compounds of the formula (1) are H, straight-chain or branched alkyl groups having 1 to 20 C atoms, in particular C 1 to C 8 -alkyl groups, saturated or partially unsaturated C 3 - to C 7 -cycloalkyl groups which react with Cr can be up-C ⁇ alkyl substituted or phenyl which may be substituted with Cr to C 6 alkyl groups, especially unsubstituted phenyl.
• R very particularly preferably represents straight-chain or branched alkyl groups having 1 to 4 C atoms.
• the substituents R in formula (1) may be the same or different. Particularly preferred are compounds in which three substituents R are the same and one substituent R is different or in which all four substituents are the same. Most preferably, three substituents R are the same and one substituent R is different.
• substituents R 3 of the compounds of formula (2) are preferably H, straight-chain or branched alkyl group having 1 to 20 C-atoms, in particular C 1 to C 8 alkyl groups, saturated or partially unsaturated, C 3 to C 7 cycloalkyl groups, which with C r to C 6 alkyl groups may be substituted, in particular cyclohexyl, or phenyl, which may be substituted with Cr to C ⁇ -alkyl groups, in particular unsubstituted phenyl.
• R 3 very particularly preferably represents straight-chain or branched alkyl groups having 1 to 4 C atoms.
• the substituents R 3 in formula (1) may be the same or different.
• substituents R 3 are the same and a substituent R 3 is different or in which all four substituents being the same. Most preferably, three substituents R 3 are the same and one substituent R 3 is different.
• the substituents R and R 3 are each, in each case independently of one another, preferably methyl, ethyl, isopropyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl or tetradecyl.
• Suitable substituents R 8 to R 13 of the compounds of formula (3) are each independently preferably H, straight-chain or branched alkyl group having 1 to 20 C atoms, in particular C 1 - to C 4 -alkyl groups, and saturated or unsaturated, ie also aromatic, C 3 - to C 7 - cycloalkyl groups which may be substituted by C r to C 6 alkyl groups, in particular phenyl.
• the substituents R 8 to R 10 and R 13 may have a previously given or particularly preferred meaning.
• the carbocyclic or heterocyclic rings of the above-mentioned guanidinium cations may by Cr to C 6 alkyl, d- to Ce alkenyl, NO 2, CN, F, Cl, Br, I, OH, C 1 -C 6 -alkoxy , SCF 3 , SO 2 CF 3 ,
• R 8 and R 9 , R 10 and R 11 and R 12 and R 13 in compounds of the formulas for guanidinium cations as described above may be the same or different. More preferably, R 8 to R 13 are each independently methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, i-butyl, phenyl or cyclohexyl, most preferably methyl, ethyl, n-propyl , iso-propyl or n-butyl.
• R 1 to R 4 of compounds of the formula (4) in addition to H according to the invention, preference is given in this case to: Cr to C 2 o, in particular Cr to C- 2 alkyl groups, and saturated or partially unsaturated C 3 - to C 7 cycloalkyl groups which may be substituted with Cr to C 6 alkyl groups, preferably cyclohexyl, or phenyl, which may be substituted with Cr to C ⁇ -alkyl groups.
• the substituents R 1 and R 4 are each, independently of one another, particularly preferably methyl, ethyl, isopropyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. They are very particularly preferably methyl, ethyl, n-butyl or n-hexyl. In pyrrolidinium, piperidinium or indolinium compounds, the two substituents R 1 and R 4 are preferably different.
• R 2 or R 3 is, in each case independently of one another, in particular H, methyl, ethyl, isopropyl, propyl, butyl, isobutyl, tert-butyl, cyclohexyl, phenyl or benzyl.
• R 2 is particularly preferably H, methyl, ethyl, isopropyl, propyl, butyl or isobutyl.
• Very particular preference is given to R 2 ' and R 3' H.
• R 1 to R 3 of compounds of the formula (5) in addition to H according to the invention, preference is given in this case to: Cr to C 2 o, in particular Cr to C- 2- alkyl groups, and saturated or partially unsaturated C 3 - to C 7 -cycloalkyl groups which may be substituted by Cr to C ⁇ -alkyl groups or phenyl which may be substituted by Cr to C 6 -alkyl groups.
• R 1 is particularly preferably methyl, ethyl, isopropyl, n-propyl, n-butyl or isobutyl.
• R 2 is particularly preferably methyl, ethyl, isopropyl, n-propyl, n-butyl or isobutyl.
• R 3 is particularly preferably methyl, ethyl, isopropyl, n-propyl, n-butyl or isobutyl.
• a straight-chain or branched alkenyl having 2 to 20 C atoms, wherein several double bonds may also be present, is, for example, ethenyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore
• Pentenyl iso-pentenyl, hexenyl, heptenyl, octenyl, -CgHi 7, -C- I oH 19 to - C 20 H 39; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferred is 4-pentenyl, iso-pentenyl or hexenyl.
• a straight-chain or branched alkynyl having 2 to 20 C atoms, wherein 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 Hi 5 , -CioH 17 -C 20 H 37 , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3 - Pentynyl or hexynyl.
• Aryl-C 1 -C 6 -alkyl is, for example, benzyl, phenylethyl, phenylpropyl,
• R 1 and X have the meanings given above.
• Unsubstituted saturated or partially unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl, cyclohexenyl,
• C 3 - to C 7 -cycloalkyl is, for example, preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
• R ' is substituted phenyl, by non-fluorinated, partially fluorinated or perfluorinated C r to C 6 alkyl, C 2 - to C 6 alkenyl, NO 2 , CN, F, Cl, Br, I, OH, non-fluorinated, partially fluorinated or perfluorinated Cr Ce alkoxy, SCF 3 , SO 2 CF 3 , COOH, SO 2 X ', SO 2 NR " 2 or SO 3 H substituted phenyl, where X' is F, Cl or Br and R" is not, partially or perfluorinated C 1 - to C 6 -alkyl or C 3 - to C 7 -cycloalkyl as defined for R ', for example, o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o-, m- or
• R 1 to R 4 or R 1 " to R 3 as heteroaryl is a saturated or unsaturated mono- or bicyclic heterocyclic radical having 5 to 13
• Understood ring members wherein 1, 2 or 3 N and / or 1 or 2 S or O atoms may be present and the heterocyclic radical one or more times by Cr to C 6 alkyl, C 1 to C 6 alkenyl, NO 2 , CN, F 1 Cl, Br 1 I, OH, C 1 -C 6 alkoxy, SCF 3 , SO 2 CF 3 , COOH, SO 2 X 1 , SO 2 NFT 2 or SO 3 H may be substituted, wherein X 'and R "have the meaning given above
• the heterocyclic radical is preferably substituted or unsubstituted 2- or 3-furyl, 2- or 3-thienyl , 1-, 2- or 3-pyrrolyl, 1-,
• Benzopyrazolyl 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, A-, 5-, 6- or 7- benzisoxazolyl, 2-, 4-, 5-, 6- or 7-benzthiazolyl, 2-, 4-, 5-, 6- or 7- benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1,3-oxadiazolyl, 1-, 2-, 3-, A-, 5 -, 6-, 7- or 8-quinolinyl, 1-, 3-, A-, 5-, 6-, 7- or 8-isoquinolinyl, 1-, 2-, 3-, 4- or 9-carbazolyl, 1-, 2-, 3-, A-, 5-, 6-, 7-, 8- or 9-acridinyl, 3-, A-, 5-, 6-, 7- or 8-cinnolinyl, 2-, A, 5-, 6-, 7- or 8-quinazolinyl or 1-, 2- or 3-pyrrolidinyl.
• Heteroaryl-C r C 6 -alkyl is now in analogy to aryl-CrC 6 -alkyl, for example, pyridinyl-methyl, pyridinyl-ethyl, pyridinyl-propyl, pyridinyl-butyl, pyridinyl-pentyl, pyridinyl-hexyl understood, wherein further heterocycles described in this way can be linked to the alkylene chain.
• HetN + is preferred Py ⁇ dinium Py ⁇ midinium
• HetN + is particularly preferably imidazolium, pyrrolidinium, morpholinium or pyridinium, as defined above, wherein the substituents R 1 to R 4 each independently have the same meaning as described above.
• HetN + is very particularly preferably imidazolium or pyrrolidinium, where the substituents R 1 to R 4 each independently of one another have the meaning described above.
• HetP + is particularly preferred 1-Methyl-1-ethyl-1-methyl-1-butyl-1-ethyl-1-propyl-1, 1-dipropyl-phospholanium phospholanium phospholanium phospholanium phospholanium phospholanium phospholanium
• Preferred compounds are 1-methyl-3-methylimidazolium [(C 2 Fs) 2 PO] " , 1-ethyl-3-methylimidazolium [(C 2 Fs) 2 PO] " , 1-propyl-3-methylimidazolium [(C 2 Fs) 2 PO] ", 1-butyl-3-methylimidazolium [(C 2 f) 2 PO]", 1-hexyl-3-methylimidazolium [(C 2 f) 2 PO] ", 1-octyl-3-methylimidazolium [(C 2 Fs) 2 PO] " ,
• N-butyl-3-methylpyridinium [(C 4 Fg) 2 PO] " N- (3-hydroxypropyl) pyridinium [(C 4 Fg) 2 PO] ", N-hexyl-4- (dimethylamino) pyridinium [(C 4 Fg) 2 PO]", N-ethyl-3-hydroxymethylpyridinium [(C 4 Fg) 2 PO], "N, N-dimethylpyrrolidinium [(C 4 Fg) 2 PO]" N-butyl-N-methylpyrrolidinium [(C 4 Fg) 2 PO] ",
• the tris (perfluoroalkyl) phosphine of the formula R 1 R 2 R F P is hydrolyzed alkaline.
• the alkaline hydrolysis takes place in the presence of an aqueous solution of a base, in particular of NaOH, KOH or NH 4 OH, in an organic solvent, preferably in diethyl ether, and subsequent reaction with a Br ⁇ nsted acid, preferably with HBr.
• the reaction is preferably carried out at room temperature.
• Tris (perfluoroalkyl) phosphines of the formula R 1 R 2 R F P can be synthesized, for example, by reduction of tris (perfluoroalkyl) difluorophosphoranes [(R 1 R 2 R F ) PF 2 ], as described, for example, in WO 03/087113, Merck Patent GmbH , described.
• a Bronsted acid from the group HCl, HBr or R 111 SOaH is preferably used, where R ' 1 ' corresponds to an alkyl group having 1 to 6 C atoms or aryl, HBr is particularly preferably used.
• a trialkyltin hydride (R 111 ⁇ SnH is used, wherein R " 1 a
• tin hydrides of the formula (R 11 ⁇ 2 SnH 2 may alternatively be used in this reaction, where each R " 1 independently corresponds to an alkyl group having 1 to 6 C atoms or aryl, where aryl is as defined above ,
• Suitable solvents are 1, 2-dimethoxyethane, diethyl ether, dichloromethane, chloroform, acetonitrile, tetrahydrofuran, toluene or mixtures of the solvents mentioned. Preference is given to using diethyl ether.
• the reaction preferably takes place at room temperature.
• the reaction of the compounds of the formula I * * R 1 R 2 PSH to give a salt of the formula II as described above can be carried out analogously as described above.
• Formula II as described above, can now be reacted to obtain the salts with organic cations, preferably in the presence of a salt KtZ, wherein Kt is selected from ammonium, phosphonium, tritylium, guanidinium or a heterocyclic cation containing at least one nitrogen or phosphorus atom, such as previously described, and Z corresponds to an anion.
• Kt is selected from ammonium, phosphonium, tritylium, guanidinium or a heterocyclic cation containing at least one nitrogen or phosphorus atom, such as previously described, and Z corresponds to an anion.
• reaction is carried out, for example, in an organic solvent with an excess of salt or acid R 1 R 2 POH, preferably with equivalent amounts of the reagents.
• Suitable solvents are 1, 2-dimethoxyethane, diethyl ether, dichloromethane, chloroform, acetonitrile, tetrahydrofuran or mixtures of said solvents. Preference is given to using diethyl ether or acetonitrile.
• the reaction preferably takes place at room temperature.
• the reaction takes place, for example, in an organic solvent.
• Suitable solvents are 1, 2-dimethoxyethane, diethyl ether, acetonitrile dichloromethane or mixtures of said solvents. Preference is given to using diethyl ether, acetonitrile or dichloromethane.
• the reaction preferably takes place at -30 ° C. to room temperature, more preferably at room temperature.
• the anion Z is selected from Cl “ , Br ' , R 0 COO “ , CF 3 COO “ , [BF 4 ] “ , [PF ⁇ ] “ or R 11 SOa ' , wherein R 0 has a meaning given in claim 1 and R "is a straight-chain or branched alkyl group having 1 to 6 C atoms or a cycloalkyl group having 3 to 7 C atoms, which is not fluorinated, partially fluorinated or perfluorinated or unsubstituted or substituted phenyl.
• a trialkyltin hydride (R '") 3 SnH is preferably used, where R 1 " corresponds to an alkyl group having 1 to 6 C atoms or aryl, where aryl is as defined above, for example trimethyltin hydride, triethyltin hydride, tripropyltin hydride, tributyltin hydride, trihexyltin hydride,
• Triphenyltin Especially preferred is tributyltin hydride.
• tin hydrides of the formula (R "') 2 SnH 2 are used, wherein R"' corresponds each independently an alkyl group having 1 to 6 carbon atoms or aryl, wherein aryl is as defined above is.
• Aryltetrachlorophosphorane is selected, for example, from phenyltetrachlorophosphorane, tolyltetrachlorophosphorane, 1,2-phenylenephosphorotrichloridite.
• phenyltetrachlorophosphorane is used.
• reaction takes place, for example, in 1,6-dibromohexane with an excess of aryltetrachlorophosphorane.
• the reaction preferably takes place at room temperature.
• Tris (perfluoroalkyl) phosphines of the formula R 1 R 2 R F P can be prepared, for example, by reduction of tris (perfluoroalkyl) difluorophosphoranes [(R 1 R 2 R F ) PF 2 ] be synthesized, as described for example in WO 03/087113, Merck Patent GmbH.
• the inorganic base is, for example MeOH, Me 2 O or Me 2 CO 3 , reacted, wherein Me is selected from Ag, Li, Na, K, Rb or
• Cs. Me is preferably selected from Li, Na or K.
• the organic base is, for example, [NR 4 ] OH, where R has one of the meanings given above for the formula (1).
• the chlorinating agent is, for example, SOCl 2, SO 2 Cl 2, C (O) CIC (O) CI, PCI 3, PCl 5, or PhPCI. 4 Particularly preferably PhPCI 4 is used. Ph is phenyl.
• the reaction with a base is carried out, for example, in an organic solvent with an excess of base.
• Suitable solvents for the chlorination reaction are 1, 2-dimethoxyethane, diglyme, triglyme, 1, 2-dibromohexane or mixtures of said solvents. Preference is given to using diglyme or 1,2-dibromohexane.
• the reaction preferably takes place at -20 0 C to room temperature instead, particularly preferably at 0 0 C.
• R 1 R 2 PCI is reacted with a sulfide of the formula K ' 2 S, wherein K' is Li, Na, K, Rb, Cs or [NH 4 ] and wherein R 1 , R 2 have the meaning given in claim 1 ,
• the synthesis of the bis (perfluoroalkyl) phosphinous chlorides takes place according to the invention as described above.
• Sulfides of the formula K ' 2 S are commercially available or can be prepared by known methods, wherein K' has a meaning mentioned. Particularly preferred is Na 2 S or K 2 S, very particularly preferably Na 2 S is used.
• the reaction takes place, for example, in an organic solvent.
• Suitable solvents are 1, 2-dimethoxyethane, diethyl ether, acetonitrile dichloromethane or mixtures of said solvents. Preference is given to using diethyl ether, acetonitrile or dichloromethane, very particular preference is given to using dichloromethane.
• the reaction is preferably carried out at -30 0 C to room temperature, most preferably at room temperature.
• An object of the invention are also transition metal complexes containing at least one compound of formula I, as described above.
• metal P and metal O bonds or metal P or metal O bonds are formed.
• the position of the compound of formula I may be terminal, on the other hand, a quasi-chelate may be formed.
• M 1 and M 2 is a transition metal selected from the group consisting of Pt, Pd, Rh,
• L is an anionic, neutral or cationically charged ligand
• R 1 and R 2 each independently represent straight-chain or branched perfluoroalkyl groups having 2 to 12 C atoms and R 1 / R 2 in formula IV is R 1 or R 2 or R 2 / R 1 in formula IV is R 2 or R 1 and R 0 is a straight-chain or branched alkyl group having 1 to 8 C
• Atoms and n is the number of ligands needed to saturate the valences of M 1 or M 2 , and wherein in formula VII the sum n + m corresponds to the coordination number of the metal M 2 .
• n can also be equal to zero.
• M 1 and M 2 are preferably selected from Pt, Pd, Rh, Ru and Ni, most preferably Pd and Pt or Pd or Pt.
• Ligands for metal complexes of the invention may be anionic, neutral or cationically charged ligands known to those skilled in the art of metal complexes.
• Pincer ligands are known, for example, from CJ. Moulton et al, J.
• Pincer complexes consist of a metal center and a tridentate ligand, which is connected to the metal center via at least one metal-carbon ⁇ bond. Examples are planar aryl compounds.
• the substituents R 1, R 2, R 0 have an above-mentioned or a previously specified preferred value.
• the metal complexes of the formulas III, IV, V, VI or VII according to the invention and mixtures thereof, as described above, are advantageous for the following reactions:
• Coupling reaction C-B coupling reaction, C-P coupling reaction, decarboxylating biaryl coupling, hydroformylation or C-H activation, polymerization, or oxidation and hydrogenation reactions.
• Solvents DMF, dioxane, DMA, NMP, toluene.
• Nickel catalyst [Ni (dppf) Cl 2 ] 18 - R benzylic phosphates -> cat: Pd (OAc) 2 / PPh 3 19
• Bases TBAF, K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaOH, KOH, K 3 PO 4 .
• Solvent DMF, MeCN, / -PrOH, EtOAc, DMA, THF. Temperature: reflux.
• Solvent - starting material 4-haloquinoline -> cat: POPd, POPdI, POPd2 2 '32 - one-pot synthesis of Stille and Heck reaction 33 Bases: R 3 N.
• Solvent dioxane, DMF, THF. Temperature: reflux. 32 C. Wolf, R. Lerebours, J. Org. Chem., 2003, 68, 7551-7554.
• Bases Amines, pyrolidine, NaOH, KOH, K 2 CO 3 , Cs 2 CO 3 , Na 2 CO 3 .
• Solvent dioxane, DMF, 1 - /> butyl-3-methylimidazolium tetrafluoroborate.
• Nickel catalyst [frans-haloarylbis (triphenylphosphine) nickel (I)] 40 Reaction at room temperature -> cat: Pd (OAc) 2 / phosphine ligand 39
• Bases NaOH, KOH, K 2 CO 3 , Cs 2 CO 3 , Na 2 CO 3 , K 3 PO 4 , R 3 N.
• Solvent dioxane, toluene, DMF, DME.
• Ar 1 2- (CF 3 ) C 6 H 4 -> cat: Pd (OAc) 2 / phosphine ligand 50
• Bases R 3 N, N-Me-piperidine, KOAc, NaOAc, DABCO, K 2 CO 3 , Cs 2 CO 3 ,
• Solvents toluene, DMF, DMA, acetonitrile, methanol, NMP.
• Solvent toluene, H 2 O. temperature: 60-120 0 C. Other Bed .: 20-60 bar CO 2 / H 2
• Bases K 2 CO 3 , Cs 2 CO 3 , Na 2 CO 3 , R 3 N, KOf-Bu, NaOf-Bu.
• Solvent toluene, DMF, DME, DMA, / -PrOAc, EtOAc. Temperature: reflux.
• the reaction takes place, for example, in an organic solvent.
• reaction can also be carried out without a solvent.
• Solvents are diethyl ether, 1, 2-dimethoxyethane, acetonitrile or
• Tetrahydrofuran Preference is given to using diethyl ether.
• the reaction takes place at -30 0 C to the boiling point of the solvent, preferably at 0 0 C to room temperature, more preferably at
• the reaction preferably takes place using dried solvents and under inert gas conditions, ie under inert gases such as argon or nitrogen.
• the invention also relates to the use of complexes of
• Formula III, IV, V, VI or VII and mixtures thereof as a catalyst, for the treatment of surfaces or for the production of nanoparticles of the corresponding metal M 1 or M 2 .
• nanoparticles takes place by the reduction, thermolysis, photolysis or electrolysis of complexes of the formula III, IV, V, VI or VII or salts of the formula II in solvents, for.
• organic solvents or ionic liquids or in an inert liquid or gaseous phase, or without solvent
• J. Krämer et al. Ionic liquids as a template for nanosyntheses, GIT Laboratory Journal, No. 4, 2008, p. 400 -403
• E. Redel et al. First Correlation of Nanoparticles Size-Dependent Formation with Lonic Liquid Anion Molecular Volume, Inorganic Chemistry, 47, 2008, p.14-16).
• salts of the formula II, as described above, wherein for Y + Ag + , Li + , Na + , K + , Rb + or Cs + is excluded, preferably an ionic liquid.
• Areas of use of the ionic liquids are, for example, the use as solvent or solvent additive, as
• Phase transfer catalyst as an extractant, as a heat transfer medium, as a surfactant, as a plasticizer, as an antistatic agent, as a flame retardant or as a conductive salt or as an additive for electrochemical and photo-electrochemical cells.
• the subject of the present invention is therefore the use of salts of the formula II, as described above, wherein for Y + Ag + , Li + , Na + , K + , Rb + or Cs + is excluded, as a solvent or solvent additive, as a phase transfer catalyst, as an extraction agent, as a heat carrier, as a surface-active substance, as a plasticizer, as an antistatic agent, as a flame retardant or as a conductive salt or as an additive for electrochemical and photo-electrochemical cells.
• reaction When used as a solvent, they are useful in any type of reaction known to those skilled in the art, e.g. for transition metal- or enzyme-catalyzed reactions, such as hydroformylation reactions, oligomerization reactions,
• the ionic liquid for the separation of reaction products but also for the separation of
• the ionic liquids can also serve as release agents in the separation of several components, for example in the distillative separation of several components of a mixture.
• plasticizers in polymeric materials, as flame retardants for a variety of materials or applications, and as a conductive salt or additive in various electrochemical cells and applications, e.g. in galvanic cells, in capacitors or in fuel cells.
• salts of the formula II are the use as solvents for solids containing carbohydrates, in particular biopolymers and derivatives or decomposition products thereof.
• some preferred salts of formula II as a lubricant, working fluids for Machines, such as compressors, pumps or hydraulic devices.
• some preferred salts of formula II may also be suitable for electro-optical cells, for example in sensors.
• the referencing method is used on each spectrum or each
• an undyed liquid is obtained and identified as bis (pentafluoroethyl) phosphine acid.
• the compound is stable at room temperature under inert gas conditions.
• Example 2 bis (pentafluoroethyl) phosphinous chloride or synonymous
• Three cold traps are used: -30 0 C, -78 ° C and -196 ° C contains The trap at -196 ° C, colorless liquid, identified as Bis (pentafluoroethyl) phosphinous chloride, (C 2 Fs) 2 PCI.
• the compound is stable at room temperature under inert gas conditions.
• Tributyltin chloride which is obtainable from the description of Example 1 or 4, is an excess of trimethylsilyl chloride, (CH 3 ) 3 SiCl, added. You get
• Example 7 Sodium bis (pentafluoroethyl) phosphinite
• the product is characterized by NMR spectroscopy.
• the spectrum corresponds to the values given in Example 2.
• Example 9 Chlorobis (pentafluoroethyl) phosphine (C 2 F 5 ) 3 P + NaOH (C 2 F 5 J 2 PCl
• the product is characterized by NMR spectroscopy.
• the spectrum corresponds to the values given in Example 1.
• Example 12 Platinum complex with bis (pentafluoroethyl) phosphinous acid
• Example 13 Palladium complex with bis (pentafluoroethyl) phosphinous acid
• a mixture of 0.858 g (3 mmol) of bis (pentafluoroethyl) phosphinous acid, obtainable according to Example 1, and 0.241 g (1.36 mmol) of palladium chloride is stirred in 25 ml of dry diethyl ether at room temperature for five days. The mixture turns yellow. After removal of diethyl ether, the palladium complex is isolated as a solid.
• the product, biphenyl, is characterized spectroscopically.
• Example 19 Synthesis of bis (pentafluoroethyl) thiophosphinous acid (C 2 F) 2 PCI + Na 2 S - ⁇ ⁇ * (C 2 F 5) 2 P-Na + _ ⁇ > (C 2 F 5) 2 PSH

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