Organic compounds -- part of the class 532-570 series – Organic compounds – Chalcogen in the nitrogen containing substituent
Reexamination Certificate
2000-07-25
2002-06-18
Shah, Mukund J. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Chalcogen in the nitrogen containing substituent
C544S003000, C544S005000, C544S006000, C544S064000, C544S065000, C544S097000, C549S030000, C549S210000
Reexamination Certificate
active
06407232
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to an ionic metal complex having a novel chemical structure and a process for synthesizing the ionic metal complex that is used as a supporting electrolyte for lithium batteries, lithium ion batteries, electrical double-layer capacitors and other electrochemical devices, a polymerization catalyst for polyolefins and so forth, or a catalyst for organic synthesis.
Ionic complexes, such as PF
6
−
, BF
4
−
and AsF
6
−
, formed by bonding of Lewis acids with F ion have been used in applications such as supporting electrolytes for electrochemical devices, polymerization catalysts for polyolefins and so forth or catalysts for organic synthesis due to their solubility and ion dissociation characteristics.
As the application range of these ionic complexes becomes increasingly diverse, efforts are being made to search for the optimum ionic complex for each application, and these ionic complexes are being required to have properties including heat resistance, hydrolysis resistance, low toxicity and recycleability.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a useful, novel, ionic metal complex and a process for synthesizing the same.
As a result of earnest studies, the inventors of the present invention found an ionic metal complex having a novel chemical structure and a process for synthesizing the same, thereby leading to completion of the present invention.
According to the present invention, there is provided an ionic metal complex represented by the general formula (1):
wherein M is a transition metal selected from the group consisting of elements of groups 3-11 of the periodic table, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; A
a+
represents a metal ion, onium ion or proton; provided that M is not B when A
a+
is Cs
+
; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X
1
represents O, S or NR
5
R
6
; each of R
1
and R
2
independently represents H, a halogen, a C
1
-C
10
alkyl group or C
1
-C
10
halogenated alkyl group; R
3
represents a C
1
-C
10
alkylene group, C
1
-C
10
halogenated alkylene group, C
4
-C
20
aryl group or C
4
-C
20
halogenated aryl group; R
4
represents a halogen, C
1
-C
10
alkyl group, C
1
-C
10
halogenated alkyl group, C
4
-C
20
aryl group, C
4
-C
20
halogenated aryl group or X
2
R
7
; X
2
represents O, S or NR
5
R
6
; each of R
5
and R
6
represents H or a C
1
-C
10
alkyl group; and R
7
represents a C
1
-C
10
alkyl group, C
1
-C
10
halogenated alkyl group, C
4
-C
20
aryl group or C
4
-C
20
halogenated aryl group.
According to the present invention, there is provided a first process for synthesizing the ionic metal complex. The first process comprises reacting a compound represented by the general formula (2) with a metal complex represented by the general formula (3). This compound contains at least two active hydrogens.
wherein X
1
, R
1
, R
2
, R
3
, R
4
, M, A
a+
, q, a, b, p, m, and n are defined as above, R
8
represents a halogen, hydroxyl group, hydrogen, C
1
-C
10
alkyl group, C
1
-C
10
halogenated alkyl group, C
4
-C
20
aryl group, C
4
-C
20
halogenated aryl group or X
3
R
9
; X
3
represents O, S or NR
5
R
6
where R
5
and R
6
are defined as above; and R
9
represents a C
1
-C
10
alkyl group, C
1
-C
10
halogenated alkyl group, C
4
-C
20
aryl group or C
4
-C
20
halogenated aryl group.
According to the present invention, there is provided a second process for synthesizing the ionic metal complex. The second process comprises (a) reacting a first compound represented by the general formula (2) with a metal complex represented by the general formula (4), thereby obtaining an intermediate; and (b) reacting the intermediate with a second compound, thereby obtaining the ionic metal complex. The first compound contains at least two active hydrogens. The second compound contains a cation represented by A
a+
defined as above and is selected from the group consisting of metal halides, metal alkoxides, metal carboxylates, metal hydroxides, metal oxides, metal carbonates, quaternary alkylonium halides, quaternary alkylonium hydroxides and quaternary alkylonium carboxylates.
wherein X
1
, R
1
, R
2
, R
3
, R
4
, R
8
, M, q, m, and n are defined as above.
According to the present invention, there is provided a third process for synthesizing the ionic metal complex. The third process comprises (a) reacting a first compound represented by the general formula (2) with a second compound containing an alkali metal or alkali-earth metal, thereby obtaining an intermediate; and (b) reacting the intermediate with a metal complex represented by the general formula (5),
wherein X
1
, R
1
, R
2
, R
3
, R
4
, M, A
a+
, q, a, b, p, m, and n are defined as above, R
10
represents a halogen or hydroxyl group.
The above-mentioned ionic metal complex has a novel chemical structure and can be used as a supporting electrolyte for lithium batteries, lithium ion batteries, electrical double-layer capacitors and other electrochemical devices, a polymerization catalyst for polyolefins and so forth, or a catalyst for organic synthesis. The ionic metal complex can be synthesized by each of the above-mentioned first, second and third processes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention, the alkyl groups, halogenated alkyl groups, aryl groups and halogenated aryl groups, which are contained in the ionic metal complex and the raw materials for synthesizing the same, may be branched and/or may have other functional groups such as hydroxyl groups and ether bonds.
The followings are specific nine examples of the ionic metal complex represented by the general formula (1) of the present
Here, although lithium ion is indicated as an example of A
a+
of the general formula (1), examples of other cations that can be used other than lithium ion include sodium ion, potassium ion, magnesium ion, calcium ion, barium ion, cesium ion, silver ion, zinc ion, copper ion, cobalt ion, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion, yttrium ion, lanthanoid ion, actinoid ion, tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium ion, triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, proton, tetraethylphosphonium ion, tetramethylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion and triphenylmethyl ion. In the case of considering the application of the ionic metal complex for electrochemical devices and the like, lithium ion, tetraalkylammonium ion and proton are preferable. In addition, in the case of the application of the ionic metal complex for catalyst, lithium ion, proton, triphenylmethyl ion, trialkylammonium ion and metallocenium ion are preferable. As shown in the general formula (1), the valency (valence) of the A
a+
cation is preferably from 1 to 3. If the valency is larger than 3, the problem occurs in which it becomes difficult to dissolve the ionic metal complex in solvent due to the increase in crystal lattice energy. Consequently, in the case of requiring solubility of the ionic metal complex, a valency of 1 is preferable. As shown in the general formula (1), the valency (b−) of the anion is similarly preferably from 1 to 3, and a valency of 1 is particularly preferable.
The constant p expresses the ratio of the valency of the anion to the valency of the cation, namely b/a.
In the general formula (1), M at the center of the ionic metal complex of the present invention is selected from elements of groups 3-15 of the periodic table. It is preferably Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb, and more preferably Al, B or P. Although it is possible to use various elements for the M other than these preferable examples, synthesis is relatively
Takahashi Mikihiro
Takase Hironari
Tsujioka Shoichi
Central Glass Company Limited
Crowell & Moring LLP
Shah Mukund J.
Truong Tamthom N.
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