Ionic compounds with delocalized anionic charge, and their...

Details Ionic compounds with delocalized anionic charge, and their... Ionic compounds with delocalized anionic charge, and their...

1999-03-25

2002-01-22

Berman, Susan W. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

C522S066000, C522S057000, C564S082000, C252S519200, C429S314000, C429S315000, C429S188000

Reexamination Certificate

active

06340716

ABSTRACT:

BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to ionic compounds comprising a highly delocalized anionic charge, to a process for their preparation and to their uses.
It is well known that the salts of strong acids such as HClO
4
, HBF
4
, HPF
6
and HR
F
SO
3
(R
F
=perfluororadical) have properties in the field of electrochemistry and catalysis, but these properties are limited. The “superacids” obtained by adding a Lewis acid such as SbF
5
to the abovementioned compounds are moreover known. However, these compounds are not stable other than in protonated form and in non-solvating media such as aliphatic hydrocarbons. The salts are unstable in the usual polar solvents.
Perfluorosulfonimide derivatives H[R
F
SO
2
NSO
2
R
F
] (R
F
=perfluoroalkyl) have been studied since quite recently. They have advantageous stability properties in protonated form or in the form of salts and are used as solutes in electrochemistry and as catalysts. However, it is not possible to give these salts all of the properties required for all the applications, in particular in terms of acidity, dissociation or solubility, since the use of compounds containing perfluoro chains of several carbons only slightly increases the acidity or the dissociation of the salts, when compared with the simplest compound R
F
=CF
3
, and induces rigidity in the molecule to the detriment of the conductivity properties. Long fluoro chains are both hydrophobic and oleophobic and do not allow any appreciable increase in the solubility in organic media. Replacement of the groups R
F
in the simple imides with non-perfluoro or only partially fluorinated groups reduces the acidity and the solubility substantially.
The aim of the present invention is to provide novel ionic compounds derived from perfluorosulfonimides in which the delocalization of the anionic charge is improved, thus resulting in markedly better acidity and dissociation than those of the known compounds, while at the same time retaining good stability.
SUMMARY OF THE INVENTION
Accordingly, a subject of the present invention is ionic compounds, their uses and a process for preparing them.
One compound according to the invention is an ionic compound corresponding to the formula
in which:
M
m+
is a proton or a metal cation having the valency m, chosen from ions of alkali metals, of alkaline-earth metals, of transition metals or of rare-earth metals, or an organic onium cation or an organometallic cation, 1<m <3;
X
1
and X
2
, denoted below by X
i
, represent, independently of each other, S═Z
3
, S═Z
4
, P—R
3
or P—R
4
;
Q represents N, CR
5
, CCN or CSO
2
R
5
;
Z
1
, Z
2
, Z
3
and Z
4
, denoted below by Z
i
, represent, independently of each other, ═O, ═NC≡N, ═C(C≡N)
2
, ═NS(═Z)
2
R
6
or ═C[S(═Z)
2
R
6
]
2
, Z having the same meaning as Z
i
, it being understood that, in a segment —X
1
—Q—X
2
—, not more than 3 groups Z
i
represent ═O;
R
1
, R
2
, R
3
, R
4
, R
5
and R
6
, denoted below by R
i
, represent, independently of each other, Y, YO—, YS—, Y
2
N— or F;
Y represents a monovalent organic radical, preferably containing from 1 to 16 carbon atoms, chosen from alkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl, azaalkenyl, aryl, alkylaryl or perfluoroalkyl radicals, or from the radicals obtained from the abovementioned radicals by substitution, in the chains and/or the aromatic part, with hetero atoms such as halogens, oxygen, nitrogen, sulfur or phosphorus; it being understood that is sulfur or phosphorus are present, they can optionally be linked to substituted oxygen or nitrogen atoms, or alternatively Y is a repeating unit of a polymeric frame.
When M
m+
is a metal cation, it can be an alkali et al (in particular Li
+
and K
+
) , an alkaline-earth metal (in particular Mg
++
, Ca
++
or Ba
++
) , a transition metal (in particular Cu
++
, Zn
++
or Fe
++
) or a rare-earth metal (in particular Re
+++
).
When M
m+
is an onium cation, it can be chosen from ammonium ions [N(Y
j
)
4
]
+
, amidinium ions RC[N(Y
j
)
2
]
2
+
, quanidinium ions C[N(Y
j
)
2
]
3
+
, pyridinium ions [C
5
N(Y
j
)
6
]
+
, imidpazolium ions C
3
N
2
(Y
j
)
5
+
nium ions C
3
N
2
(Y
j
)
7
+
, triazolium ions C
2
N
3
(Y
j
)
4
+
, carbonium ions C
5
(Y
j
)
5
C
+
, NO
+
(nitrosyl) or NO
2
+
ions, sulfonium ions [S(Y
j
)
3
]
+
, phosphonium ions [P(Y
j
)
4
]
+
and iodonium ions [I(Y
j
)
2
]
+
. In the various abovementioned onium ions, the substituents Y
j
on the same anion can be identical or different. They represent, independently of each other, H or one of the substituents indicated above for Y.
When M
m+
is an organometallic cation, it can be chosen from metalloceniums. For example, mention may be made of the cations derived from ferrocene, from titanocene, from zirconocene, from an indocenium or from an arene metallocenium. It can also be chosen from metal cations coordinated by atoms such as O, S, Se, N, P or As, borne by organic molecules, in particular in the form of carbonyl, phosphine or porphyrine ligands optionally containing chirality. M
m+
can also be a cation derived from the alkyl groups defined for Y above and limited to those containing from 1 to 10 carbon atoms, for example a trialkylsilyl, tetraalkylgermanyl or dialkylstannyl derivative; in this case, M is linked to the group [R
1
—X
1
(Z
1
)—Q
−
—X
2
(Z
2
)—R
2
] via a very labile covalent bond and the compound behaves like a salt. The cation M can also be the repeating unit of a conjugate polymer in cationic oxidized form. As specific examples, mention may be made of the methylzinc, phenylmercury, trialkyltin or trialkyllead, chloro[ethylenebis(indenyl)]zirconium(IV) or tetrakis-(acetonitrile)palladium(II) cations. The organometallic cation can form part of a polymer chain.
The compounds according to the invention in which at least one of the groups X
i
represents a phosphorous group are particularly advantageous for the great stability of the P—N and P—C bonds and for their flexibility. As a result, these compounds are more soluble and have a lower melting point than the sulfur-containing homologous compounds. Moreover, a large number of phosphorous compounds bearing two substituents R are commercially available or can readily be synthesized. For example, mention may be made of the compounds
Mention may be made in particular of the phosphorous compounds in which Q represents N.
The compounds in which the radicals Z
i
represent R
F
SO
2
N and those in which the radicals R
i
represent a perfluoro group or an alkyl group are particularly advantageous, especially for the high acidity and the dissociation of the corresponding salts.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Among the compounds of the present invention corresponding to formula (I), mention may be made of those in which the groups X
i
represent S—Z
i
, more particularly those in which Q is N, and which correspond, respectively, to the formulae:
One particular family of compounds according to the invention corresponds to formula (VII), given that if R
1
is CF
3
, R
2
is a phenyl optionally bearing a halogen or an NO
2
, three substituents Z
i
represent O and one substituent Z
i
represents ═NSO
2
CF
3
, then M is other than an alkali metal cation or a proton.
Another family of compounds according to the invention corresponds to formula (I) in which the radicals R
1
and R
2
are chosen, independently of each other, from perfluoroalkyl radicals preferably containing from 1 to 8 carbon atoms, alkyl radicals preferably containing from 1 to 8 carbon atoms, alkenyl radicals preferably containing from 2 to 18 carbon atoms, dialkylamino radicals in which the alkyl radicals preferably contain from 1 to 18 carbon atoms, and styre

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