Organic compounds -- part of the class 532-570 series – Organic compounds – Boron containing
Reexamination Certificate
2000-10-31
2002-09-10
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Boron containing
C568S004000, C568S005000, C564S010000, C564S011000, C556S007000
Reexamination Certificate
active
06448447
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to weakly coordinating anion salts comprising a reactive cation and uses thereof. In particular, the present invention relates to fluoroborate salts comprising a reactive cation. Specifically, the present invention provides compounds of the formula M
x
Q
y
, where M, Q, x, and y are those defined herein.
BACKGROUND OF THE INVENTION
Weakly coordinating anion salts comprising a reactive cation are useful in variety of reactions including polymerization reactions, coupling reactions, and other chemical reactions which is facilitated by an appropriate cation. Useful reactive cations include silver cation, silylium cations, aluminum cations, ammonium cations, protonated arenes, triaryl carbocation, and other cations which can facilitate a chemical reaction such as a polymerization reaction, coupling reaction, and other catalytic reactions.
Currently, there are no methods to generate stable reactive cations, such as cation-like aluminum (i.e., pseudo aluminum-cation) species, e.g., AlMe
2
+1
, in the presence of weakly coordinating anions (WCA's). For example, when the AlMe
2
+1
was generated in situ, it caused the rapid decomposition of one of the most efficient WCA's known, viz. B(C
6
F
5
)
4
−1
(A
1
(C
6
F
5
)
3
was one of the reaction products). Other cationic aluminum complexes are based on the use of bulky nitrogen ligands to stabilize the positive charge on the aluminum atom. The synthesis and characterization of aluminum alkyl complexes containing guanidimates,
2
amidinates,
3
aminotroponimates,
4
and pyridyliminoamide
5
ligands have recently been reported. These complexes exhibited ethylene polymerization activity of 900-2,600 g PE/(mol·atm·h) in toluene at 80 to 100° C. and 1 to 5 atm of ethylene.
1,4
However, the steric or electronic properties of the nitrogen ligands may disfavor the coordination and activation of large organic molecules. The synthesis of &pgr;-stabilized (&eegr;
5
−Cp*)
2
Al
+1
has also been reported.
6
In addition, it is believed no examples of C—H activation by cationic aluminum complexes has been reported. However, &eegr;
1
-arene complex of Al(C
6
F
5
)
3
has recently been reported
7
, which may represent a model for the first step in C—H activation of aromatic molecules by aluminum cationic complexes. The catalytic activation of aromatic C—H bonds resulting in arene-olefin coupling is of considerable current interest for chemical and pharmaceutical industries.
8,9
Efficient palladium-catalyzed oxidative coupling of arenes with olefins has recently been reported.
8
Other methods of arene-olefin coupling include use of strong Lewis acids (e.g., AlCl
3
) and Bronsted acids (e.g., HF, BF
3
.HF, and AlCl
3
.HCl).
10
However these methods are usually accompanied by isomerization, disproportionation, and transalkylation. In addition, the use of WCA's other than fluorocarborate anions such as 1-R—CB
11
F
11
−1
to generate AlMe
2
+1
cation-like species has resulted in rapid decomposition of the aluminum cation as well as the WCA. Furthermore, it is believed that no other stable aluminum compound can catalyze C—H activation in the absence of a strong Bronsted acid.
Furthermore, many conventional co-catalysts for an &agr;-olefin (e.g., ethylene) polymerization, including methylalumoxane (MAO), have limited solubilities in aliphatic hydrocarbon solvents and are not stable when stored in solution.
11
Therefore, there is a need for stable weakly coordinating anion salts comprising a reactive cation that are useful in variety of organic reactions.
SUMMARY OF THE INVENTION
The present invention provides a compound of the formula:
M
x
Q
y
I
where each M is independently a cation, provided at least one M is a reactive cation. Preferably, M is selected from the group consisting of silver cation, aluminum cations, silylium cations, ammonium cations, protonated arenes, and triaryl carbocation. Q is a weakly coordinating anion (i.e., WCA). Preferably, Q is a polyhalogenated polyhedral borate or a fluorinated WCA, and more preferably a polyhalogenated polyhedral borate or a fluorinated polyhedral borate moiety selected from the group consisting of monoheteroborate and aminoborate. Preferably, when Q is a monoheteroborate then M is an aluminum cation. The variable x is an absolute value of the oxidation state of Q, i.e., when the oxidation state of Q is −1, then x is 1, and similarly when the oxidation state of Q is −2, then x is 2. Preferably, the oxidation state of Q is −1 or −2. And the variable y is an absolute value of the oxidation state of M. It should be appreciated that when there is more than one type of M is present in the Compound of Formula I, the variable y is the absolute value of the total oxidation states of all M's present. And similarly, when there is more than one type of Q is present in the Compound of Formula I, the variable x is the absolute value of the total oxidation states of all Q's present.
Preferably, the aluminum cation is a moiety of the formula (R
1
R
2
Al)
+1
, where each of R
1
and R
2
is independently selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, cycloalkalkyl, alkenyl, and halide. Preferably, each of R
1
and R
2
is independently selected from the group consisting of alkyl, aryl, and halide. And more preferably, each of R
1
and R
2
is independently selected from the group consisting of methyl, ethyl, iso-propyl, propyl, butyl, iso-butyl, t-butyl, pentyl, hexyl, and halide.
Preferably, the silylium cation is a moiety of the formula (R
3
R
4
R
5
Si)
+1
, where each of R
3
, R
4
, and R
5
is independently selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl, and halide. More preferably, each of R
3
, R
4
, and R
5
is independently selected from the group consisting of hydrogen, alkyl, and aryl. And most preferably, each of R
3
, R
4
, and R
5
is independently selected from the group consisting of alkyl and aryl.
Preferably, the ammonium cation is a moiety of the formula (R
16
R
17
R
18
NH)
+1
, where each of R
16
, R
17
, and R
18
is independently selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl, and silyl. Preferably, each of R
16
, R
17
, and R
18
is independently selected from the group consisting of alkyl, aryl, aralkyl, and cycloalkyl. More preferably, R
16
, R
17
, and R
18
are alkyl.
Preferably, the protonated arene is a moiety of the formula (Ar
1
H)
+1
, where Ar
1
is an optionally substituted aryl. In one embodiment of the present invention, Ar
1
is phenyl.
Preferably, the triaryl carbocation is a moiety of the formula (Ar
2
Ar
3
Ar
4
C)
+1
, where each of Ar
2
, Ar
3
, and Ar
3
is independently an optionally substituted aryl. In one embodiment of the present invention, Ar
2
, Ar
3
, and Ar
3
are phenyl (i.e., the triaryl carbocation is trityl cation).
Preferably, the monoheteroborate anion is of the formula ((R
6
)
a
ZB
b
H
c
F
d
X
e
(OR
7
)
f
)
−1
, where R
6
is bonded to Z, Z is bonded to B, and each of H, F, X, and OR
7
is bonded to a different boron atom. R
6
is selected from the group consisting of polymer, hydrogen, halide, alkyl, silyl, cycloalkyl, alkenyl, alkynyl, and aryl. Preferably, R
6
is selected from the group consisting of alkyl, aryl, and sily. More preferably R
6
is selected from the group consisting of methyl, ethyl, dodecyl, butyl, iso-butyl, t-butyl, silyl, propyl, iso-propyl, pentyl, hexyl, and a polymer. Z is selected from the group consisting of C, Si, Ge, Sn, Pb, N, P, As, Sb, and Bi. Preferably Z is C. Each X is independently halide. R
7
is selected from the group consisting of polymer, hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl. The variable “a” is 0 or, preferably, 1. The variable “b” is an integer from 5 to 13, preferably 11. The variable “c” is an integer from 0 to 12, preferably c” is 0. The variable “d” is an integer from 2 to 13, preferably 11. The variable “e” is an integer from
Ivanov Sergei V.
Strauss Steven H.
Colorado State University Research Foundation
Vollano Jean F.
LandOfFree
Fluoroborate salts comprising a reactive cation and uses... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Fluoroborate salts comprising a reactive cation and uses..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Fluoroborate salts comprising a reactive cation and uses... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2870535