Weakly coordinating anions containing polyfluoroalkoxide...

Details Weakly coordinating anions containing polyfluoroalkoxide... Weakly coordinating anions containing polyfluoroalkoxide...

2000-03-10

2002-05-21

Cain, Edward J. (Department: 1714)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C524S176000

Reexamination Certificate

active

06392076

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a compound containing polyfluoroalkoxides and the use thereof, in particular, for use as an electrolyte in batteries and other electrochemical devices.
BACKGROUND OF THE INVENTION
A compound containing a weakly coordinating anion (i.e., an anion that coordinates only weakly with a cation) is useful in a variety of applications including as an electrolyte and a counter-ion for a catalyst in a variety of organic reactions. Some of the useful catalysts containing a weakly coordinating anion are described by Barbarich, et al. in “LiAl(OC(Ph)(CF
3
)
2
)
4
: A Hydrocarbon-Soluble Catalyst For Carbon-Carbon Bond-Forming Reactions”,
Organometallics,
1996, 15, 3776, which is incorporated herein in its entirety.
Investigations of very reactive metal and nonmetal cations continues to spur the development of new weakly coordinating anions. See, for example, Bochmann,
Angew. Chem., Int. Ed. Engl.
1992, 31 1181; Strauss,
Chem. Rev.
1993, 93, 927, Strauss,
Chemtracts-Inorganic Chem.
1994, 6,1; and Seppelt,
Angew. Chem., Int. Ed. Engl.
1993, 32, 1025. One of the most important uses of weakly coordinating anions is to enhance the catalytic activity of metal cations. Two examples that have received considerable attention recently are metallocene-catalyzed olefin polymerization, and lithium-catalyzed Diels-Alder reactions and 1,4-conjugate addition reactions. See Turner, European Patent Appl. No. 277,004, 1988; Pellecchia et al.,
Makromol. Chem., Rapid Commun.
1992, 13, 265; DuBay et al.,
J. Org. Chem.
1994, 59, 6898; Saidi et al.,
Chem. Ber.
1994, 127, 1761; Kobayashi et al.,
Chem. Lett.
1995, 307; and Arai et al.,
Angew. Chem., Int. Ed. Engl.
1996, 15, 3776.
Useful anions must not only be weakly coordinating, they must also be stable with respect to oxidation and/or fragmentation in the presence of highly electrophilic cations. In addition, an ideal weakly coordinating anion should have a single negative charge dispersed over a large surface composed of relatively nonpolar bonds to weakly basic atoms such as hydrogen or the halogens. Weakly coordinating anions which conform to many, but not all, of these criteria include B (Ar
f
)
4
−
(Ar
f
=C
6
F
5
or 3,5-C
6
H
3
(CF
3
)
2
), CB
11
H
12-n
X
n
−
(X=H, Me, Cl, Br, F or I), CB
9
H
10-n
X
n
−
(X=H, F, Cl, or Br), and M(OTeF
5
)
n
−
(n=4, M=B; n=6, M=Nb, Sb).
All of the anions mentioned above have limitations. Some are too strongly coordinating for specific applications. Some are unstable under the harsh chemical conditions where they would be employed. For example, the fluorinated derivatives of BPh
4
−
can react with strongly electrophilic cations, causing (i) cleavage of a C—F bond and formation of a bond between the fluorine atom and the cation or (ii) transfer of a fluoroaryl group to the cation. In either case, the cation is no longer reactive or catalytically active.
Other weakly coordinating anions, such as ClO
4
−
, BF
4
−
, PF
6
−
, SbF
6
−
, B(OTeF
5
)
4
−
, and Nb(OTeF
5
)
6
−
, are not thermally and/or hydrolytically stable. In addition, lithium salts of such anions, including LiCF
3
SO
3
, have low electrical conductivity in some organic solvents, especially organic solvents that are stable in the presence of strong reducing agents such as metallic lithium and related lithium-containing battery anode solutions. Furthermore, some lithium salts, such as lithium triflate (LiCF
3
SO
3
), cause corrosion of the aluminum current collectors in batteries, while some lithium salts, such as LiPF
6
, are known to be unstable at temperatures as low as 70° C. and decompose over time.
Still other anions containing boron atoms, and anions containing a carbon atom and a cluster of boron atoms, such as carboranes (e.g., CB
5
, CB
9
, CB
11
), are not particularly weakly coordinating because the salts formed therefrom contain at most only one fluorine atom which is bonded to a boron atom.
Recently, polyfluorinated carborane anions that are weakly coordinating and are thermally and/or hydrolytically stable have been disclosed in commonly assigned U.S. patent application Ser. No. 09/049,420, filed Mar. 27, 1998. In addition, one particular class of compounds containing polyfluoroalkoxide ligands and the use thereof has been disclosed in commonly assigned PCT Patent Application No. PCT/US98/19268, filed Sep. 11, 1998, and commonly assigned U.S. patent application Ser. No. 09/151,852, filed Sep. 11, 1998, disclosures of which are incorporated herein by reference in their entirety.
Despite the recent advances in weakly coordinating anions, there still is a need for new weakly coordinating anions. There is also a need for weakly coordinating anions having a high electrical conductivity in an organic solvent. There is also a need for weakly coordinating anions that are stable in solution and in the solid state.
SUMMARY OF THE INVENTION
One embodiment of the present invention provides a compound comprising a monoanion of the formula:
and uses thereof,
where
M
1
is a transition metal, or a Group III, IV or V element;
each Z is independently O, S, or NR
6
R
7
;
each X is independently a halide;
each R
1
is independently a bond or C
1
-C
4
alkylene;
each of R
2
, R
3
and R
4
is independently H, F, fluorinated C
1
-C
10
alkyl, fluorinated C
4
-C
20
aryl, C
3
-C
10
cycloalkyl, fluorinated C
3
-C
10
cycloalkyl, C
1
-C
10
alkyl or C
4
-C
20
aryl, provided at least one of R
2
, R
3
and R
4
is F, fluorinated C
1
-C
10
alkyl, fluorinated C
3
-C
10
cycloalkyl, or fluorinated C
4
-C
20
aryl;
each R
5
is independently fluorinated C
1
-C
10
alkyl, fluorinated C
4
-C
20
aryl, C
4
-C
20
aryloxide, fluorinated C
4
-C
20
aryloxide, C
1
-C
10
alkoxide or fluorinated C
1
-C
10
alkoxide;
each of R
6
and R
7
is independently H or C
1
-C
10
alkyl;
each of a, b and c is independently an integer from 0 to 4,
provided the sum of a, b and c is an integer from 2 to 8; and n is 1 or 2; and
provided that when R
2
is a fluorinated C
1
-C
4
alkyl, R
1
is a bond, b, and c are 0, and R
3
is C
1
-C
10
alkyl or fluorinated C
4
-C
10
alkyl then R
4
is F, fluorinated C
1
-C
10
alkyl or fluorinated C
4
-C
20
aryl.
Another embodiment of the present invention provides a compound comprising an anion of the formula:
wherein
M
1
is a transition metal, or a Group III, IV or V element;
L is a halide, C
1
-C
10
alkyl, fluorinated C
1
-C
10
alkyl, C
4
-C
20
aryl, fluorinated C
1
-C
20
alkyl or a moiety of the formula −Z
3
-R
11
;
d is an integer from 0 to 4;
e is an integer from 1 to 3;
the sum of d and e is an integer from 1 to 6;
n is 1 or 2;
each of Z
1
, Z
2
and Z
3
is independently O, S, or NR
6
R
7
;
each of R
6
and R
7
is independently H or C
1
-C
10
alkyl;
each R
9
is independently C
1
-C
30
alkylene, fluorinated C
1
-C
30
alkylene, substituted C
1
-C
30
alkylene, C
3
-C
10
cycloalkylene, fluorinated C
3
-C
10
cycloalkylene, C
4
-C
20
arylene or fluorinated C
4
-C
20
arylene;
each of R
8
and R
10
is a bond, or a moiety of the formula —[C(R
12
R
13
)]
x
—;
each x is independently an integer from 1 to 4;
each of R
12
and R
13
is independently H, F, C
1
-C
4
alkyl or fluorinated C
1
-C
4
alkyl; and
each R
11
is independently C
1
-C
10
alkyl, fluorinated C
1
-C
10
alkyl, C
4
-C
20
aryl, or fluorinated C
4
-C
20
aryl;
provided at least one of R
8
and R
10
is a moiety of the formula —C(R
12
R
13
)— and at least one of R
12
and R
13
is F or fluorinated C
1
-C
4
alkyl.
The present invention also provides an electrolyte for an electrochemical device, comprising the anion of the above described formula having a counter cation M where M is a metal cation, a phosphonium cation, an ammonium cation or a sulfonium cation. Preferably M is Li cation.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a compound comprising an anion of the formula:
and uses thereof, where M
1
is a transition metal, or a Group III, IV

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