Chemistry:Boranes

From HandWiki
Decaborane(14), B
10H
14

A borane is a compound with the formula B
xH
y or a related anion. Many such boranes are known. Most common are those with 1 to 12 boron atoms. Although they have few practical applications, the boranes exhibit structures and bonding that differs strongly from the patterns seen in hydrocarbons. Hybrids of boranes and hydrocarbons, the carboranes are also well developed.[1]

History

The development of the chemistry of boranes led to innovations in synthetic methods as well as structure and bonding. First, new synthetic techniques were required to handle diborane and many of its derivatives, which are both pyrophoric and volatile. Alfred Stock invented the glass vacuum line for this purpose.[2]

The structure of diborane was correctly predicted in 1943 many years after its discovery.[3] The structures of the boron hydride clusters were determined beginning in 1948 with the characterization of decaborane. William Lipscomb was awarded the Nobel prize in Chemistry in 1976 for this and many subsequent crystallographic investigations. These investigations revealed the prevalence of deltahedral structures, i.e., networks of triangular arrays of BH centers.

The bonding of the clusters ushered in Polyhedral skeletal electron pair theory and Wade's rules, which can be used to predict the structures of boranes.[4] These rules were found to describe structures of many cluster compounds.

Interest in boranes increased during World War II due to the potential of uranium borohydride for enrichment of the uranium isotopes and as a source of hydrogen for inflating weather balloons. In the US, a team led by Schlesinger developed the basic chemistry of the anionic boron hydrides and the related aluminium hydrides. Schlesinger's work laid the foundation for a host of boron hydride reagents for organic synthesis, most of which were developed by his student Herbert C. Brown. Borane-based reagents are now widely used in organic synthesis. Brown was awarded the Nobel prize in Chemistry in 1979 for this work.[5]

Chemical formula and naming conventions

Borane clusters are classified as follows, where n is the number of boron atoms in a single cluster:[1][6][7]

Cluster type Chemical formula Example Notes
hypercloso- B
nH
n		 Unstable; derivatives are known[8]
closo- [B
nH
n]2−		 Caesium dodecaborate
nido- B
nH
n+4		 pentaborane(9)
arachno- B
nH
n+6		 pentaborane(11)
hypho- B
nH
n+8		 Only found in adducts

The International Union of Pure and Applied Chemistry rules for systematic naming is based on a prefix denoting a class of compound, followed by the number of boron atoms and finally the number of hydrogen atoms in parentheses. Various details can be omitted if there is no ambiguity about the meaning, for example, if only one structural type is possible. Some examples of the structures are shown below.

  • Hexaborate(6)
    [B
    6    H
    6    ]2−

  • Heptaborate(7)
    [B
    7    H
    7    ]2−

  • Octaborate(8)
    [B
    8    H
    8    ]2−

  • Nonaborate(9)
    [B
    9    H
    9    ]2−

  • Decaborate(10)
    [B
    10    H
    10    ]2−

  • Undecaborate(11)
    [B
    11    H
    11    ]2−

  • Dodecaborate(12)
    [B
    12    H
    12    ]2−

The naming of anions is illustrated by

octahydridopentaborate, [B
5H
8]−

The hydrogen count is specified first followed by the boron count. The -ate suffix is applied with anions. The ionic charge value is included in the chemical formula but not as part of the systematic name.

Bonding in boranes

Boranes are nonclassically–bonded compounds, that is, there are not enough electrons to form 2-centre, 2-electron bonds between all pairs of adjacent atoms in the molecule. A description of the bonding in the larger boranes was formulated by William Lipscomb. It involved:

  • 3-center 2-electron B-H-B hydrogen bridges
  • 3-center 2-electron B-B-B bonds
  • 2-center 2-electron bonds (in B-B, B-H and BH
    2    )

Lipscomb's methodology has largely been superseded by a molecular orbital approach. This allows the concept of multi-centre bonding to be extended. For example, in the icosahedral ion [B
12H
12]2−, the totally symmetric (Ag symmetry) molecular orbital is equally distributed among all 12 boron atoms. Wade's rules provide a powerful method that can be used to rationalize the structures in terms of the number of atoms and the connectivity between them.

Multicluster boranes

Structure of the conjuncto boron hydride cluster [B
19H
22]−
.[9]

Although relatively rare, several multi-cluster boranes have been characterized. For example, reaction of a borane cluster with B
2H
6 (as a source of BH
3) can lead to the formation of a conjuncto-borane species in which borane cluster sub-units are joined by the sharing of boron atoms.[10]

B
6H
10 + "BH
3" → B
7H
11 + H
2
B
7H
11 + B
6H
10 → B
13H
19 + H
2

Other conjuncto-boranes, where the sub-units are joined by a B-B bond, can be made by ultra violet irradiation of nido-boranes. Some B-B coupled conjuncto-boranes can be produced using PtBr
2 as catalyst.[11]

Analogous to Wade's Rules, electron counting scheme has been developed to predict or rationalize multicluster boranes.

Multi-cluster descriptors[12]
Prefix Meaning Example
klado- branched clusters
conjuncto- conjoined clusters
megalo- multiple conjoined clusters

Reactivity of boranes

The lowest borane, BH
3 exists only transiently, dimerizing instantly to form diborane, B
2H
6. Its adducts BH
3 · THF and BH
3 · DMSO are sufficiently stable to be used in hydroboration reactions. Reminiscent of the behavior of diborane, some lower boranes react with air very exothermically, even explosively. By contrast, many closo-borane cluster, such as [B
12H
12]2−, do not react with air.

The boron hydride clusters are so diverse that generalizations on their reactions are not possible.

Lewis acid/base behavior

Some function as electron donors owing to the relative basic character of the B–H
terminal groups. Boranes can function as ligands in coordination compounds.[13] Hapticities of η1 to η6 have been found, with electron donation involving bridging H atoms or donation from B-B bonds. For example, nido-B
6H
10 can replace ethene in Zeise's salt to produce trans-Pt(η2
-B
6H
10)Cl
2.[13]

They can also act as Lewis acids, with concomitant opening of the cluster. An example involving trimethylphosphine:

B
5H
9 + 2 P(CH
3)
3 → B
5H
9 · 2P(CH
3)
3

Brønsted acid/base behavior

Some higher boranes, especially those with bridging hydrogen atoms, can be deprotonated with a strong base. An example:

B
5H
9 + NaH → Na[B
5H
8] + H
2

Acidity increases with the size of the borane, with B
10H
14 having a pKa value of 2.7.[14][15]

[[Chemistry:Pentaborane(
9)|B
5H
9]] < [[Chemistry:Hexaborane(
10)|B
6H
10]] < B
10H
14 < B
16H
20 < B
18H
22

Aufbau reactions

Structure of [(CH
3)
4N+
]
2[Fe(C
2B
9H
11)
2]+
, showing only one Me
4N+
.[16]

For the boron hydride chemist, one of the most important reactions is the building up process by which smaller boron hydride clusters add borane to give larger clusters. This approach also applies to the synthesis of metallaboranes,

Hydroboration

Reminiscent of the behavior of diborane and its adducts, higher boranes participate in hydroboration. When boron hydrides add an alkyne, the carbon becomes incorporated into the cluster, producing carboranes, e.g. C
2B
10H
12.[17]

Applications

Diborane and its monomeric adducts borane–tetrahydrofuran or borane–dimethylsulfide are useful reagents. They are often used for hydroboration in organic synthesis. Some cobalt derivatives of carboranes have been commercialized for sequestering 137
Cs from radioactive waste.[18]

Boranes have a high specific energy of combustion compared to hydrocarbons, making them potentially attractive as fuels or igniters. Intense research was carried out in the 1950s into their use as jet fuel additives, but the effort did not lead to practical results.

Aspirational uses

Because 10
B has a very high neutron-capture cross section, boron-hydride derivatives have often been investigated for applications in Neutron capture therapy of cancer.[19]

10
B + 1
n → (11
B*) → 4
He + 7
Li + γ (2.4 Mev)

See also

References

  1. ↑ 1.0 1.1 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.  pp 151-195
  2. ↑ Stock, Alfred (1933). The Hydrides of Boron and Silicon. New York: Cornell University Press. 
  3. ↑ Longuet-Higgins, H. C.; Bell, R. P. (1943). "64. The Structure of the Boron Hydrides". Journal of the Chemical Society (Resumed) 1943: 250–255. doi:10.1039/JR9430000250. 
  4. ↑ Fox, Mark A.; Wade, Ken (2003). "Evolving patterns in boron cluster chemistry". Pure Appl. Chem. 75 (9): 1315–1323. doi:10.1351/pac200375091315. http://dro.dur.ac.uk/12642/1/12642.pdf?DDD7+dcl0cim+d700tmt. 
  5. ↑ Brown, H. C. Organic Syntheses via Boranes John Wiley & Sons, Inc. New York: 1975. ISBN:0-471-11280-1.
  6. ↑ Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5 
  7. ↑ Lipscomb W. N. Boron Hydrides. Benjamin, New York (1963).
  8. ↑ Peymann, Toralf; Knobler, Carolyn B.; Khan, Saeed I.; Hawthorne, M. Frederick (2001). "Dodeca(benzyloxy)dodecaborane, B12(OCH2Ph)12: A Stable Derivative of hypercloso-B12H12". Angew. Chem. Int. Ed. 40 (9): 1664–1667. doi:10.1002/1521-3773(20010504)40:9<1664::AID-ANIE16640>3.0.CO;2-O. PMID 11353472. 
  9. ↑ Londesborough, Michael G. S.; Bould, Jonathan; Baše, Tomáš; Hnyk, Drahomír; Bakardjiev, Mario; Holub, Josef; Císařová, Ivana; Kennedy, John D. (2010). "An Experimental Solution to the "Missing Hydrogens" Question Surrounding the Macropolyhedral 19-Vertex Boron Hydride Monoanion [B19H22]−, a Simplification of its Synthesis, and its Use as an Intermediate in the First Example of syn-B18H22 to anti-B18H22 Isomer Conversion". Inorganic Chemistry 49 (9): 4092–4098. doi:10.1021/ic901976y. PMID 20349936. 
  10. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.  p. 162
  11. ↑ Sneddon, L.G. (2009). "Transition metal promoted reactions of polyhedral boranes and carboranes". Pure and Applied Chemistry 59 (7): 837–846. doi:10.1351/pac198759070837. 
  12. ↑ Bould, Jonathan; Clegg, William; Teat, Simon J.; Barton, Lawrence; Rath, Nigam P.; Thornton-Pett, Mark; Kennedy, John D. (1999). "An approach to megalo-boranes. Mixed and multiple cluster fusions involving iridaborane and platinaborane cluster compounds. Crystal structure determinations by conventional and synchrotron methods". Inorganica Chimica Acta 289 (1–2): 95–124. doi:10.1016/S0020-1693(99)00071-7. 
  13. ↑ 13.0 13.1 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 177, "The concept of boranes as ligands". ISBN 978-0-08-037941-8. 
  14. ↑ temperature not stated
  15. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.  p. 171
  16. ↑ Kang, H. C.; Lee, S. S.; Knobler, C. B.; Hawthorne, M. F. (1991). "Syntheses of Charge-Compensated Dicarbollide Ligand Precursors and Their Use in the Preparation of Novel Metallacarboranes". Inorganic Chemistry 30 (9): 2024–2031. doi:10.1021/ic00009a015. 
  17. ↑ Jemmis, E. D. (1982). "Overlap control and stability of polyhedral molecules. Closo-Carboranes". Journal of the American Chemical Society 104 (25): 7017–7020. doi:10.1021/ja00389a021. 
  18. ↑ Chaudhury, Sanhita; Bhattacharyya, Arunasis; Goswami, Asok (2014). "Electrodriven Selective Transport of Cs+ Using Chlorinated Cobalt Dicarbollide in Polymer Inclusion Membrane: A Novel Approach for Cesium Removal from Simulated Nuclear Waste Solution". Environmental Science & Technology 48 (21): 12994–13000. doi:10.1021/es503667j. PMID 25299942. Bibcode: 2014EnST...4812994C. 
  19. ↑ Sauerwein, Wolfgang; Wittig, Andrea; Moss, Raymond; Nakagawa, Yoshinobu (2012). Neutron Capture Therapy. Berlin: Springer. doi:10.1007/978-3-642-31334-9. ISBN 978-3-642-31333-2. 



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