Synthesis of perhydroxydodecaborate salts and related species

Details Synthesis of perhydroxydodecaborate salts and related species Synthesis of perhydroxydodecaborate salts and related species

2000-04-10

2001-11-27

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Boron containing

C568S004000

Reexamination Certificate

active

06323372

ABSTRACT:

The present invention relates to unique three-dimensional hydoxylated icosahedral boron cage compounds.
BACKGROUND
Scientists have formed numerous different polyhydroxylated molecules. Carbon-based systems are well-known. For example, carbohydrates are ubiquitous in nature and serve as a source for chemical energy (glucose), the backbone for genetic information (ribose), and the organic constituents of plants (cellulose) or insects (chitin) (D. Voet, J. G. Voet,
Biochemistry,
2nd ed., Wiley, N.Y., 1995, pp. 251-276. The three-dimensional network of silica and its derived minerals (F. Liebau,
Structural Chemistry of Silicates,
Springer, N.Y., 1985, p. 4) results from the condensation of polyhydroxylated silicates.
However, very few polyhydroxylated boron compounds are known. The most prominent polyhydroxylated boron compound is boric acid, B(OH)
3
. Alkaline solutions of B(OH)
3
deposit Na
2
[B
4
O
5
(OH)
4
].nH
2
O, which constitutes two abundant boron minerals, kernite (n=2) and borax (n=8) (F. A. Cotton, G. Wilkinson,
Advanced Inorganic Chemistry,
5th ed., Wiley, N.Y., 1988, pp. 164-169.). Other common boron structures include the trigonal and tetrahedral boron-oxygen units common to borate minerals, (G. A. Heller,
Top. Curr. Chem.
1986, 131, 39-98), and the icosahedron. The allotropes of elemental boron, (J. Donohue,
The Structures of the Elements,
Wiley, N.Y., 1974, pp. 48-82) boron-rich solids (H. Hubert, B. Devouard, L. A. J. Garvie, M. O'Keeffe, P. R. Buseck, W. T. Petuskey, P. F. McMillan,
Nature
1998, 391, 376-378) and the parent anion of the polyhedral boranes, [closo-B
12
H
12
]
2−
First reported by Hawthorne et al (A. R. Pitochalli and M. F. Hawthorne
J. Am.Chem. Soc.,
1960, 82, 3228 followed by J. A. Wunderlich, W. N. Lipscomb,
J. Am. Chem. Soc.
1960, 82, 4427-4428) all contain B
12
icosahedral
The charge-delocalized icosahedral ion [closo-B
12
H
12
]
2−
, may be considered as the parent aromatic species for borane chemistry in a manner similar to that served by the benzene ring in organic (carbon) chemistry (M. F. Hawthorne,
Advances in Boron Chemistry,
Special Publication No. 201, Royal Society of Chemistry, London, 1997, pp. 261-272). However, while certain benzene and other aromatic compounds are known,(ie., phenol, hydroquinone, naphthol) fully hydroxylated aromatic compounds (all —H replaced by —OH) are not known or readily prepared. However, contrary to the process described herein for manufacturing the new hydoxylated borates, no reaction occurs when benzene is refluxed with boiling hydrogen peroxide. Isoelectronic substitution of one or two: B—H vertices in [closo-B
12
H
12
]
2
by: C—H
+
provides the aromatic derivatives [closo-1-CB
11
H
12
]
−
, and a set of three isomeric dicarbacarboranes (1,2- or ortho; 1,7- or meta; and 1,12- or para) closo-C
2
B
10
H
12
R (N. Grimes,
Carboranes,
Academic Press, New York, 1970, p. 8). Each of these isoelectronic derivatives of [closo-B
12
H
12
]
2−
, undergoes characteristic hydrogen-substitution reactions at their B—H vertices resulting in a huge number of known icosahedral species.
Of special interest are derivatives in which every available B—H vertex has been substituted. Thus, hydrophobic derivatives of [closo-B
12
H
12
]
2
and [closo-1-CB
11
H
12
]
−
, and the three isomeric dicarboboranes, such as [closo-B
12
Cl
12
]
2−
(W. H. Knoth, H. C. Miller, J. C. Sauer, J. H. Balthis, Y. T. Chia, E. L. Muetterties,
Inorg, Chem,
1964, 3, 159-167), [closo-CB
11
(CH
3
)
12
]
−
, (King, B. T.; Janousek, Z.; Grüner, B.; Trammell, M.; Noll, B. C.; Michl, J.
J. Am. Chem. Soc.
1996, 118, 10902-10903), closo-1,12-C
2
B
10
(CH
3
)
12
, (W. Jiang, C. B. Knobler, M. D. Mortimer, M. F. Hawthorne,
Angew. Chem.
1995, 107, 1470-1473;
Angew. Chem. Int. Ed. Engl.
1995, 34, 1332-1334.) and, [closo-B
12
(CH
3
)
12
]
2−
(T. Peymann, C. B. Knobler, M. F. Hawthorne,
J.Am. Chem. Soc.,
1999, 121, 5601) have been synthesized. However, the existence or formulation of similar highly substituted polyhedral borane derivatives having hydrophilic substituents, such as hydroxyl have not been demonstrated.
SUMMARY
It has now been found that per-B-hydroxylated icosahedral borane derivatives, which may be considered to be derivatives of a new type of polyhedral sub-boric acid, can be readily synthesized. Described herein are the per-B-hydroxylated icosahedral Cs
2
[closo-B
12
(OH)
12
],; Cs[closo-1-H-1-CB
11
(OH)
11
]; and closo-1,12-H
2
-1,12-C
2
B
10
(OH)
10
. These new borohydrate compounds are prepared by the oxidation of the icosahedral boranes [closo-B
12
H
12
]
2−
, [closo-1-CB
11
H
12
]
−
and closo-1,12-CH
2
OH)
2
-1,12-C
2
B
10
H
10
, respectively, with 30%
w
hydrogen peroxide at the reflux temperature (from about 100° C. to 50° C.)


REFERENCES:
patent: 3390966 (1968-07-01), Knoth, Jr.
patent: 3551120 (1970-12-01), Millet et al.
CA:131:19038 abs of Angew. Chem. Int. Ed. 38(8) pp 1062-1064 by Peymann et al, 1999.*
CA:77:126475 abs of Recl. Trav. Chim. Pays-Bas by Elferink et al 91(8) pp 989-1001, 1972.*
Kenneth Shelly, Carolyn B. Knobler, and M. Frederick Hawthorne,Synthesis of Monosubstituted derivatives of Closo-Decahydrodecabonate (2-) . X-Ray Crystal Structures of [Closo-2-B10H9NCO]2-, Inorganic Chemistry, vol. 31 No. 13, 1992. pp. 28892892.
M. Frederick Hawthorne, Richard L. Pilling, and Philip M. Garrett,A Study of the Reaction of Hydroxide Ion With B20H18-2, Journal of the American Chemical Society 87: Nov. 21, 1965, pp. 4740-4745.

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