Synthesizing Polyhedral Ionic Borohydride Clusters to be Nano-Building Blocks

SURF Application: Kyle Hartman

Abstract Polyhedral boron clusters have a wide range of geometries and properties, including special

electronic properties with extremely high thermal stability as rare conductive refractory ceramics.

Conventional synthesis requires volatile boron compounds, but these compounds are volatile, pyrophoric

and extremely toxic. Reactions with sodium borohydride (NaBH4) with alkyl halides will be explored in

order to form three basic ionic borohydride clusters in a safe manner. These stable boron clusters can be

used as nano-building blocks for electrochemical and refractory thin-films.

 Synthesizing Polyhedral Ionic Borohydride Clusters to be Nano-Building Blocks
SURF Application: Kyle Hartman

Project Description

Introduction - The ability to use nano-scale structures as building blocks for larger and more practically

useful compounds is very valuable, and can help lead to some interesting discoveries. This form of

synthesis offers diverse and easily modified functionality, allowing many different types of materials to be

made from the nano-building blocks. Borohydride clusters are a very good example of this type of

molecule, with specific uses as refractory thin-films for high temperature applications and electrolytes for

fuel cells, batteries, and sensors.1

The most stable and well known boron cluster is the icosahedral B12H122- dianion. It has been

demonstrated to have stable and reversible two-electron reduction-oxidation characteristics, a key

property for electrochemical applications. Due to the ionic nature of these borohydride molecules, the

uses are quite varied. Compounds with these type of electrical characteristics are of interest for the

precise manipulation of electron spin in microelectronic devices for information processing, a field known

as spintronics. It has also been shown that boron clusters are unique and stable electrolyte materials with

high stabilities and ionic conductivities that lend themselves to applications for fuel cells and batteries.

These same properties have applications in the field of medicine as well, with electrochemical detection

of base pair matches in DNA possible via incorporation of borane clusters, with the possibility to simplify

genetic analysis. 1

Furthermore, these boron clusters have uses as refractory thin films in high temperature

applications, particularly leading edges of hypersonic vehicles or internal components of nuclear reactors.

Metal diborides have already been shown to have exceptional thermal stability and conductivity, as well

as impressive flexure strength. 3 Classically, highly volatile and pyrophoric transition metal borohydrides

produced by metatheses are more suited to chemical vapor deposition processes under high vacuum
 Synthesizing Polyhedral Ionic Borohydride Clusters to be Nano-Building Blocks
SURF Application: Kyle Hartman

conditions. However, some research has been done to explore the use of polyhedral borane clusters in

polymer precursors for refractory uses with success.

Unfortunately, High off-the-shelf prices (>$50 per gram) and the use of pyrophoric and toxic

reagents in reported syntheses have placed a

large barrier in the way of potential materials

research. The goal of this project is to explore

routes to different borohydride clusters starting

from low cost sodium borohydride and avoiding

the use of toxic boron compounds such as

diborane, pentaborane, decaborane, and boron

trihalides. In addition, the B11H14- is a key Scheme 1. Routes to Ionic Borohydride Clusters1

intermediate in synthesizing the carborane

anion, one of the least coordinating anions ever discovered, which makes it useful for making powerful

acids and catalysts. Unfortunately, currently its synthesis is complex, and commercially it is priced

upwards of $700 per gram.

Project Design This project will focus mainly on the synthesis of B3H8- and B11H14- via sodium borohydride

in a non-toxic manner in order to make nano-scale building blocks to form ionic borohydride clusters (B6H6-

, B10H10-, B12H12-). There is difficulty in this, however, as it is known to be complicated to isolate any single

species of borohydride cluster in solution because it also includes salts of B10H10- and B12H12-.2 Due to the

low cost and availability of sodium borohydride, and the fact that it is a stable solid at room temperature

and dissolves slowly in neutral water, this method is very appealing when trying to synthesize these

compounds on a per gram scale.

 Synthesizing Polyhedral Ionic Borohydride Clusters to be Nano-Building Blocks
SURF Application: Kyle Hartman

A primary goal to follow the isolating the

B11H14-1 anion is its use to synthesize the

monoanionic carborane shown in Scheme 2. The

combination of Schemes 1 and 2 may allow for a

simple, one-pot synthesis directly from NaBH4,

Scheme 2. Route to produce carborane anion.
which would open broad new opportunities for

exploration.

The synthesis of B11H14- with NaBH4 and amyl Bromide is one of the first steps, and has been

demonstrated previously. A flask fitted with a mechanical stirrer, thermometer, addition funnel, and gas-

exit tube is charged with 6.0 g of NaBH4 and 100 mL of diglyme. It is then heated to 105 C and 128 mL of

neat n-amyl bromide is added over 5 hours. After cooling, the slurry is filtered and the solids are washed

with ethyl ether and the washings combined with the diglyme fraction. The combined solutions are

evaporated to an oil with use of a rotary evaporator, then the oil is dissolved in 200 mL of water and 12 g

of (CH3)4NCl is added. The precipitate is then filtered and recrystallized as (CH3)4NB11H14. 4

Another goal is the synthesis of B3H8- using different organic halides. The organic halide is added

with stirring to a solution of NaBH4 in diglyme heated to 100 C. The solution is kept under these conditions

for several hours and then the mixture if filtered off, diglyme is distilled off on a rotary evaporator, and

the resulting precipitate is dissolved in distilled water. The product [(n-C4H9)4N)[B3H8] is precipitated by a

solution of ((n-C4H9)4N)Br in water, filtered off, and then dried in air. The product is then precipitated from

dichloromethane with equal volume of diethyl ether. [(n-C4H9)4N)[B3H8] is filtered off and dried at room

temperature. 2

The Me3NH+ salt of Carborane (CB11H12-) can be synthesized from the Me3NH+ salt of B11H14-. The

Me3NH+ salt of B11H14- is dissolved in THF under an argon atmosphere. The solution is cooled to 0 C and
 Synthesizing Polyhedral Ionic Borohydride Clusters to be Nano-Building Blocks
SURF Application: Kyle Hartman

NaH is added. After stirring at room temperature for 30 minutes, the mixture is evaporated to dryness

and THF and CHCl3 are added. The reaction mixture is stirred for 2 hours at room temperature. EtOH is

added at 0 C and stirred for 4 hours at room temperature. Water is added and THF is evaporated under

reduced pressure. The solution is then acidified by addition of 10% HCl. Residual THF and EtOH are

removed under reduced pressure. After addition of Me3NH+Cl- a white solid precipitates. It is then

separated and dried under reduced pressure to yield the Me3NH+ salt of CB11H12-. 5

Timeline

Month 1 During the first month the primary goal is the synthesis of B11H14- via C5H11Br with the goal of

finding a repeatable, efficient, and high yield process with little to no toxic byproducts.

Month 2 The second month will focus on creating octahydrotriborate (B3H8-) for use as a building block

to create other ionic boron clusters.

Month 3 During the las month the goal will be to create and explore the applications of different

borohydride clusters (B6H6-, B10H10-, B12H12-).

Conclusion

This proposal has outlined a basic approach to synthesizing fundamental borohydride building

blocks as a first step to producing functional materials, and the demonstration of a one-pot process for

synthesizing the carborane anion would be a groundbreaking advance. This, along with the nature of the

greener syntheses that will be explored, will help lead to new discoveries regarding the chemistry of boron

clusters. With the wide variety of applications for these materials, this work is educational as well as

critical for furthering this field of materials research.

 Synthesizing Polyhedral Ionic Borohydride Clusters to be Nano-Building Blocks
SURF Application: Kyle Hartman

References

1. M. F. Roll. 2016. Ionic Borohydride Clusters for the Next Generation of Boron Thin-Films: Nano-Building

Blocks for Electrochemical and Refractory Materials. In revision.

2. A. Yu. Bykov, N. N. Maltseva, N. B. Generalova, K. Yu. Zhizhin, N. T. Kuznetsov. 2013. Reactions of

Sodium Tetrahydroborate with Alkyl and Aryl Halides: A New Approach to the Synthesis of B3H8- and

B12H122-. Russian Journal of Inorganic Chemistry: 1321-1323.

3. W. G. Fahrenholtz, G. E. Hilmas, I. G. Talmy, J. A. Zaykoski. 2007. Refractory Diborides of Zirconium and

Hafnium. Journal of the American Ceramic Society: 1348-1364

4. G. B. Dunks, K. Barker, E. Hedaya, C. Hefner, K. Palmer-Ordonez, P. Remec. 1981. Simplified Synthesis

of B10H14- Ion. Journal of Inorganic Chemistry: 1692-1697.

5. A. Franken, B. T. King, J. Rudolph, P. Rao, B. C. Noll, J. Michl. 2001. Preparation of [closo-CB11H12](-)

by dichlorocarbene insertion into [nido-B11H14](-). Collection of Czechoslovak Chemical
Communications: 1238-1249.
 Synthesizing Polyhedral Ionic Borohydride Clusters to be Nano-Building Blocks
SURF Application: Kyle Hartman

Budget:
The following outline basic consumable supplies for the proposal described. Any residual costs
will be covered by Dr. Rolls returned overhead, including $75 for poster printing.