Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
1998-09-11
2001-04-24
Cain, Edward J. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C556S040000
Reexamination Certificate
active
06221941
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a compound containing polyfluoroalkoxides and the use thereof, in particular, for use in batteries.
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
−
(A
f
=C
6
F
5
or 3,5-C
6
H
3
(CF
3
)
2
), CB
11
H
12−n
X
n
−
(X=H or I), CB
9
H
10−n
X
n
−
(X=H, Cl, Br or 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
and LiPF
6
, have low electrical conductivity in 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. Moreover, some lithium salts, such as LiPF
6
, are known to be unstable 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
6
, 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 U.S. patent application Ser. No. 09/049,420, filed Mar. 27, 1998.
Despite the recent advances in weakly coordinating anions, there still is a need for a new weakly coordinating anion. There is also a need for a weakly coordinating anion having a high electrical conductivity in an organic solvent.
SUMMARY OF THE INVENTION
The present invention is directed to a class of novel weakly coordinating anions containing at least one ligand having at least one fluorine atom.
More specifically, the present invention provides an anion of the formula [M
1
(XC(CF
a
(R
1
)
b
)(CF
c
(R
2
)
d
)R
3
)
m
(R
4
)
n
]
−p
, and the use thereof, where M
1
is a transition metal, or a Group III, IV or V element;
p is 1 or 2;
each X is independently O, S, or NR
5
R
6
;
each of R
1
and R
2
are independently H, halide or C
1
-C
4
alkyl;
each R
3
is independently H, C
1
-C
4
alkyl, or C
4
-C
20
aryl;
each R
4
is independently C
1
-C
10
alkyl, C
1
-C
10
alkoxide or C
4
-C
20
aryloxide;
each of R
5
and R
6
are independently H or C
1
-C
10
alkyl;
each of a and c are independently an integer from 0 to 3;
a+b=3;
c+d=3;
m is an integer from 2 to 8; and
n is an integer from 0 to 4;
provided at least one of a or c is not 0. In a preferred compound of the present invention, p is 1, each R
4
is independently C
1
-C
10
alkoxide or C
4
-C
20
aryloxide and when M
1
is Al and a and c are 3, R
3
is not phenyl or p-methylphenyl.
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.
REFERENCES:
patent: 5534370 (1996-07-01), Kita et al.
patent: 5660947 (1997-08-01), Wuhr
patent: WO 96/26967 (1996-09-01), None
patent: WO 00/20472 (2000-04-01), None
Labrize et al; “Sythesis, Characterization . . . ”, Polyhedron vol. 14; 1995; pp. 881-848.*
Barbarich, et al.; “Coordination of the new weakly coordinating anions A1(OCH(CF3)2)4-, and A1(OC(Ph)(CF3)2)4-to the monovalent metal ions Li+and T1−”;Journal of Molecular Catalysis A:Chemical; v. 128; 1998; pp. 289-331.
Rockwell, et al.; “Nb (OCH(CF3)2)6−: protype for a new class of weakly coordinating anions based on polyfluoroalkoxide substituents”,Inorg. Chemical Act. v. 263, 1997; pp. 195-200.
Samuels, et al.; “Organofluorine Binding to Sodium and Thallium (I) in Molecular Fluoroalkoxide Compounds”;J. Am. Chem. Soc. v. 115; 1993; pp. 5093-5104.
Perozzi, et al.; “Directed Dilithiation of Hexafluorocumyl Alcohol--Formation of a Reagent for the Facile Introduction of a Stabilizing Bidentate Ligand in Compounds of Hypervalent Sulfur (10-S-4), Phosphorus (10-P-5)) Silicon (10-Si-5), and Iodine (10-I-3)”;The Journal of Organic Chemistry; v. 46; 1981; pp. 1049-1053.
Denmark, et al.; “Synthesis, Structure, and Reactivity of an Organogermanium Lewis Acid”; Organometallics v. 9, 1990; pp. 3015-3019.
Akiba, et al.; “First Example of Thermally Stable Hypervalent Bismuth Ate Complex (12-Bi-6) with Two Bidentate Ligands: Synthesis and Structure”;Tet. Lett. v. 30; 1989; pp. 953-956.
Laurent, et al.; “Synthesis and Characterization of Volatile Sodium Yttrium Fluoroalkoxides. Structure of Na3Y(OCH(CF32)6(THF)3 and Na2Y(OCMe(CF3)2)5(THF)3”;Inorg. Chem. v. 34; 1995, 34 pp. 3980-3985.
Samuels, et al.; “Structure/Volatility Correlation of Sodium and Zirconium Fluoroalkoxides”;Chem. Mater. v. 6; 1995; pp. 929-935.
Yamamoto, et al.; “Synthesis and Structure of Six-Coordinated Organobismuth Compounds with Bidentate Ligands (12-Bi-6)”;Organometallics v. 12; 1993, 3297-3303.
Samuels, et al.; “Structure/Volatility Correlation of Sodium and Zirconium Fluoroalkoxides”;Chem. Mater. v. 7; 1995; pp. 929-935.
Allan, et al.; “Fully fluorinated alkoxides. Part IV. Derivatives of perfluoropinacol”;Canadian Journal of Chemistry, v. 46; 1968; pp. 3671-3677.
Barthel, et al.; “A New Class of Electrochemically and Thermally Stable Lithium Salts for Lithium Battery Electrolytes: II. Conductivity of Lithium Organoborates in Dimethoxye
Barbarich Thomas J.
Nolan Benjamin G.
Rockwell Juston J.
Strauss Steven H.
Cain Edward J.
Colorado State University Research Foundation
Townsend and Townsend / and Crew LLP
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