# US 9,518,068 B2 · Compounds containing hydrido-tricyano-borate anions

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,518,068 B2
- Document ID: US9518068B2
- Status: Granted
- Kind: B2
- Application number: 14/119,893
- Filed: 2012-05-23
- Published: 2014-04-17
- Granted: 2016-12-13
- Earliest claimed: 2011-05-31
- Assignees: Merck Patent GmbH
- Applicants: Nikolai (Mykola) Ignatyev; Michael Schulte; Kentaro Kawata; Tomohisa Goto; Eduard Bernhardt; Vera Bernhardt-Pitchougina; Helge Willner
- Inventors: Nikolai (Mykola) Ignatyev; Michael Schulte; Kentaro Kawata; Tomohisa Goto; Eduard Bernhardt; Vera Bernhardt-Pitchougina; Helge Willner
- Web page: https://patentgrep.com/patent/US9518068B2

## CPC

- C07F 5/025: {Boronic and borinic acid compounds}
- C07F 1/00: Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F 5/00: Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F 5/02: Boron compounds
- C07F 5/022: {without C-boron linkages}
- C07F 5/027: {Organoboranes and organoborohydrides}
- H01M 10/0563: Liquid materials, e.g. for Li-SOCl2 cells
- Y02E 60/10: Energy storage using batteries
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to compounds containing hydrido-tricyano-borate anions, their preparation and their use, in particular as part of electrolyte formulations for electrochemical or optoelectronic devices.

## Claims

### Claim 1

Compounds of formula I
[Kt]z+z[BH(CN)3]− I
in which [Kt]z+ denotes an inorganic or organic cation and z is 1, 2, 3 or 4, where sodium hydrido-tricyano-borate, potassium hydrido-tricyano-borate, silver hydrido-tricyano-borate and PPN[HB(CN)3] are excluded.

### Claim 2 (depends on 1)

A compound according to claim 1, wherein [Kt]z+ is an organic cation selected from the group comprising iodonium, tritylium, sulfonium, oxonium, ammonium, phosphonium, uronium, thiouronium, guanidinium cations or heterocyclic cations.

### Claim 3 (depends on 1)

A compound according to claim 1, in which Ktz+ denotes
an inorganic cation selected from the group of H+, NO+, Li+, Mg2+, Cu+, Cu2+, Zn2+, Ca2+, Y+3, Yb+3, La+3, Sc+3, Ce+3, Nd+3, Tb+3, Sm+3 and complex (ligands containing) metal cations
an organic cation, which is a tritylium cation, in which the phenyl groups are optionally substituted by straight-chain or branched alkyl groups having 1 to 20 C atoms, straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds or straight-chain or branched alkynyl having 2 to 20 C atoms and one or more triple bonds,
an oxonium cation of formula (1) or a sulfonium cation of formula (2)
[(Ro)3O]+ (1)
[(Ro)3S]+ (2),
where
Ro each independently of one another denotes a straight-chain or branched alkyl group having 1-8 C atoms, non-substituted phenyl or phenyl which is substituted by R1*, OR′, N(R′)2, CN or halogen and in case of sulfonium cations of formula (2) additionally denotes each independently (R′″)2N,
R′ is independently of each other H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl,
R1* is independently of each other non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and
R′″ is independently of each other straight-chain or branched C1 to C6 alkyl;
an ammonium cation of formula (3)
[NR4]+ (3),
where
R in each case, independently of one another, denotes
H, OR′, N(R′)2, with the proviso that a maximum of one R in formula (3) is OR′ or N(R′)2,
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 having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which is optionally substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two R may be fully substituted by halogens, and one or more of R are optionally partially substituted by halogens, and/or by —OH, —OR′, —CN, —N(R′)2, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —NO2, —SR′, —S(O)R′, and/or —SO2R′ and where one or two non-adjacent carbon atoms in R which are not in the α-position are optionally replaced by atoms and/or atom groups selected from the group consisting of —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— and —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a phosphonium cation of formula (4)
[P(R2)4]+ (4),
where
R2 in each case, independently of one another, denotes
H, OR′ or N(R′)2,
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 having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which is optionally substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two R2 are optionally fully substituted by halogens, and one or more of R2 are optionally partially substituted by halogens, in particular and/or by —OH, —OR′, —CN, —N(R′)2, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —NO2, —SR′, —S(O)R′, —SO2R′ and where one or two non-adjacent carbon atoms in R2 which are not in the α-position may be replaced by atoms and/or atom groups selected from the group consisting of —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a uronium cation of formula (5)
[C(NR3R4)(OR5)(NR6R7)]+ (5),
where
R3 to R7 each, independently of one another, denote
H, where H is excluded for R5,
straight-chain or branched alkyl having 1 to 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, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which is optionally substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two of the substituents R3 to R7 are optionally fully substituted by halogens, and one or more of R3 to R7 are optionally partially substituted by halogens, and/or by —OH, —OR′, —N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, and/or —NO2 and where one or two non-adjacent carbon atoms in R3 to R7 which are not in the α-position are optionally replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— and —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a thiouronium cation of formula (6)
[C(NR3R4)(SR5)(NR6R7)]+ (6),
where
R3 to R7 each, independently of one another, denote
H, where H is excluded for R5,
straight-chain or branched alkyl having 1 to 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, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which is optionally substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two of R3 to R7 are optionally fully substituted by halogens, and one or more of the substituents R3 to R7 are optionally partially substituted by halogens, and/or by —OH, —OR′, —N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, and/or —NO2 and where one or two non-adjacent carbon atoms in R3 to R7 which are not in the α-position are optionally replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— and —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a guanidinium cation of formula (7)
[C(NR8R9)(NR10R11)(NR12R13)]+ (7),
where
R8 to R13 each, independently of one another, denote
H, —CN, N(R′)2, —OR′,
straight-chain or branched alkyl having 1 to 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, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which is optionally substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two of the substituents R8 to R13 are optionally fully substituted by halogens, and one or more of the substituents R8 to R13 are optionally partially substituted by halogens, and/or by —OH, —OR′, —N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, and/or —NO2 and where one or two non-adjacent carbon atoms in R8 to R13 which are not in the α-position are optionally replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— and —P(O)R′—, where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a heterocyclic cation of formula (8)
[HetN]z+ (8)
which
[HetN]z+ denotes a heterocyclic cation selected from the group consisting of
where
R1′ to R4′ each, independently of one another, denote
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 having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which is optionally substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
saturated, partially or fully unsaturated heteroaryl, heteroaryl-C1-C6-alkyl or aryl-C1-C6-alkyl and
R2′ denote additionally F, Cl, Br, I, —CN, —OR′, —N(R′)2, —P(O)(R′)2, —P(O)(OR′)2, —P(O)(N(R′)2)2, —C(O)R′, —C(O)OR′, —C(O)X, —C(O)N(R′)2, —SO2N(R′)2, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′ and/or NO2, with the proviso that R1′, R3′, R4′ are in this case independently of each other H and/or a straight-chain or branched alkyl having 1-20 C atoms, and/or a straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
where the substituents R1′, R2′, R3′ and/or R4′ together optionally form a ring system,
where one to three substituents R1′ to R4′ are optionally fully substituted by halogens, and one or more of R1′ to R4′ are optionally partially substituted by halogens, and/or by —OH, —OR′, N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, and/or —NO2, but where R1′ and R4′ cannot simultaneously be fully substituted by halogens and where, in the substituents R1′ to R4′, one or two non-adjacent carbon atoms which are not bonded to the heteroatom are optionally replaced by atoms and/or atom groups selected from the —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′—,
where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen
or
a iodonium cation of formula (9)
where
the aryl group Ar denotes each independently of each other aryl with 6 to 30 C atoms which is non-substituted or substituted with at least a straight-chain or branched alkyl group having 1 to 20 C atoms, a straight-chain or branched alkenyl group having 2 to 20 C atoms and one or more double bonds, a straight-chain or branched alkynyl group having 2 to 20 C atoms and one or more triple bonds, R1*, NO2, SR′′, N(R′)2, CN and/or halogen,
where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl,
where R1* each independently is non-fluorinated, partially fluorinated or Perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl, and
halogen is F, Cl, Br or I.

### Claim 4 (depends on 1)

A process for preparing a compound of formula I according to claim 1 in which [Kt]z+ is another cation than the alkali metal cation in the starting material and z denotes 1, 2, 3 or 4 in a salt-exchange reaction,
comprising
reacting an alkali metal salt of formula I-1
[Me]+[BH(CN)3]− I-1
in which [Me]+ is an alkali metal cation
or
reacting
H[BH(CN)3]
with a compound of formula V
KtA V,
in which
Kt has a meaning of an organic cation or inorganic cation other than the alkali metal cation of the compound of formula I-1 or H+ and
A denotes F−, Cl−, Br−, I−, OH−, [HF2]−, [CN]−, [SCN]−, [R1COO]−, [R1OC(O)O]−, [R1SO3]−, [R2COO]−, [R2SO3]−, [R1OSO3]−, [PF6]−, [BF4]−, [SO4]2−, [HSO4]1−, [NO3]−, [(R2)2P(O)O]−, [R2P(O)O2]2−, [(R1O)2P(O)O]−, [(R1O)P(O)O2]2−, [(R1O)R1P(O)O]−, tosylate, malonate which is optionally substituted by straight-chain or branched alkyl groups having 1 to 4 C atoms, [HOCO2]− or [CO3]2−, with the proviso that [SO4]2− and [CO3]2− are only for the synthesis of compounds of formula I having another metal cation than the alkali metal cation of the compound of formula I-1,
R1 is each independently of another a straight-chain or branched alkyl group having 1 to 12 C atoms and
R2 is each independently of one another a straight-chain or branched perfluorinated alkyl group having 1 to 12 C atoms.

### Claim 5 (depends on 1)

An electrolyte formulation comprising at least one compound of formula I according to claim 1.

### Claim 6 (depends on 5)

An electrochemical and/or optoelectronic device comprising an electrolyte formulation according to claim 5.

### Claim 7 (depends on 3)

A method for cationic polymerization or photo polymerization or for photo acid generative, comprising initiating said cationic polymerization or photo polymerization, or generating said photo acid by a compound of formula I according to claim 3 in which [Kt]z+ is a cation of formula (2), (5), (6), (9), tritylium, pyrylium, 1-benzopyrylium or 2-benzopyrylium which acts as a cationic polymerization initiator, photo-polymerization initiator or photo-acid generator.

### Claim 8 (depends on 1)

A media for a chemical reaction, a catalyst and/or a media in a catalytical process, a conducting salt, a component of electrolytes for the application in electrochemical cells, a component of supporting electrolytes for an electrochemical process, a surfactant, a phase-transfer catalyst, a trainer, an extractant; an antistatic additive, a plasticiser; a heat-transfer-medium, a modifier for a membrane or textile material; a lubricant, an additive to a lubricant composition or to an engineering fluid; a hydraulic fluid or an additive to a hydraulic fluid, comprising a compound of formula I according to claim 1 in which [Kt]z+ is an organic cation or H+ and z is 1, 2, 3 or 4.

### Claim 9 (depends on 1)

A compound according to claim 1, in which Ktz+ denotes an inorganic cation selected from the group consisting of H+, NO+,Li+, Mg2+, Cu+, Cu2+, Zn2+, Ca2+, Y+3, Yb+3, La+3, Sc+3, Ce+3, Nd+3, Tb+3, Sm+3 and xomplex (ligands containing) metal cations, wherein the metal is selected from the group consisting of rare-earths, transitions metals and noble metals.

### Claim 10 (depends on 1)

A compound according to claim 1, in which Ktz+ denotes an inorganic cation selected from the group consisting of H+, NO+, Li+, Mg 2+, Cu+, Cu2+, Zn2+, Ca2+, Y+3, Yb+3, La+3, Sc+3, Ce+3, Nd+3, Tb+3, Sm+3 and complex (ligands containing) metal cations, wherein the metal is selected from the group consisting of rhodium, ruthenium, iridium, palladium, platinum, osmium, cobalt, nickel, iron, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, hafnium, thorium, uranium and gold.

### Claim 11 (depends on 3)

A compound according to claim 3, in which Ktz+ denotes
a heterocyclic cation of formula (8)
[HetN]z+ (8)
which
[HetN]z+ denotes a heterocyclic cation selected from the group consisting of

### Claim 12 (depends on 3)

A compound according to claim 3, in which Ktz+ denotes
a heterocyclic cation of formula (8)
[HetN]z+ (8)
which
[HetN]z+ denotes a heterocyclic cation selected from the group consisting of

### Claim 13 (depends on 3)

A compound according to claim 3. in which Ktz+ denotes
a heterocyclic cation of formula (8)
[HetN]z+ (8)
which
[HetN]z+ denotes a heterocyclic cation selected from the group consisting of

### Claim 14 (depends on 3)

A compound according to claim 3, in which Ktz+ denotes
a heterocyclic cation of formula (8)
[HetN]z+ (8)
which
[HetN]z+ denotes a heterocyclic cation selected from the group consisting of