Boron Compounds 1

Boron Compounds
Robert J. Brotherton, U.S. Borax Research Corp., Anaheim, California 92801, United States (Chaps. 1 – 4,
6.4)
C. Joseph Weber, U.S. Borax Research Corp., Anaheim, California 92801, United States (Chaps. 1 – 4, 6.4)
Clarence R. Guibert, Callery Chemical Co., Callery, Pennsylvania 16024, United States (Chaps. 5, 6 – 6.3, 7)
John L. Little, Callery Chemical Co., Callery, Pennsylvania 16024, United States (Chaps. 5, 6 – 6.3, 7)

1. Boron Halides . . . . . . . . . . . . . . 1 2.5. Uses . . . . . . . . . . . . . . . . . . . . . 6

1.1. Physical Properties . . . . . . . . . . . 1 2.6. Pollution Control, Toxicology . . . . 7
1.2. Chemical Properties . . . . . . . . . . 1 3. Boron Subhalides . . . . . . . . . . . . 7
1.2.1. Exchange Reactions . . . . . . . . . . . 2 4. Boron Sulfide . . . . . . . . . . . . . . . 8
1.2.2. Halide Displacement Reactions . . . . 2 4.1. Physical and Chemical Properties . 8
1.2.3. Boron Trihalides as Lewis Acids . . . 3 4.2. Production . . . . . . . . . . . . . . . . 8
1.2.4. Reduction Reactions . . . . . . . . . . . 3 4.3. Uses . . . . . . . . . . . . . . . . . . . . . 8
1.3. Production . . . . . . . . . . . . . . . . 3 5. Boranes . . . . . . . . . . . . . . . . . . 8
1.4. Quality Specifications, Chemical 5.1. Diborane and Higher Boranes . . . 8
Analysis . . . . . . . . . . . . . . . . . . 4 5.1.1. Physical and Chemical Properties . . . 9
1.5. Sources, Handling, and Transporta- 5.1.2. Production . . . . . . . . . . . . . . . . . 10
tion . . . . . . . . . . . . . . . . . . . . . 4 5.1.3. Uses . . . . . . . . . . . . . . . . . . . . . 10
1.6. Uses of Boron Trihalides . . . . . . . 4 5.2. Amine Boranes . . . . . . . . . . . . . 11
1.7. Pollution Control, Toxicology, and 5.3. Borohydrides . . . . . . . . . . . . . . . 11
Occupational Health . . . . . . . . . . 5 5.4. Carbaboranes . . . . . . . . . . . . . . 12
2. Fluoroboric Acid and Fluoroborates 5 6. Organoboranes . . . . . . . . . . . . . 14
2.1. Physical and Chemical Properties . 5 6.1. Alkyl- and Arylboranes . . . . . . . . 14
2.2. Production . . . . . . . . . . . . . . . . 6 6.2. Borinic and Boronic Acids . . . . . . 15
2.3. Quality Specifications, Chemical 6.3. Borazines . . . . . . . . . . . . . . . . . 16
Analysis . . . . . . . . . . . . . . . . . . 6 6.4. Boric Acid Esters . . . . . . . . . . . . 16
2.4. Sources, Handling, and Transporta- 7. Toxicology and Occupational Health 18
tion . . . . . . . . . . . . . . . . . . . . . 6 8. References . . . . . . . . . . . . . . . . . 19

1. Boron Halides All four compounds have trigonal symmetry

1.1. Physical Properties
Boron forms trihalides, sometimes called
trihaloboranes, with fluorine, chlorine, bromine,
and iodine. The trifluoride [7637-07-2], BF3 , M r
67.80, and trichloride [10294-34-5], BCl3 , M r
117.19, are gases at room temperature. The tri-
bromide [10294-33-4], BBr3 , M r 250.54, is a
liquid, and the triiodide [13517-10-7], BI3 , M r
391.52, is a solid. All four trihalides are color-
less, but the tribromide and triiodide discolor on
exposure to light. A summary of some physical
properties of these compounds is given in Ta-
ble 1 (see next page).
with X−B−X angles of 120◦ . A crystal struc-
ture has been reported for a metastable phase of
BF3 at 142 K in which boron atoms are trigonal
prismatic with B−Xeq bond lengths of 0.126 –
0.131 nm and B−Xax bond lengths of 0.268 –
0.271 nm [10].
1.2. Chemical Properties
Trivalent boron halides are coordinatively unsat-
urated and their chemistry is dominated by the
unfilled boron pz orbital. The compounds are
Lewis acids and readily form adducts with a va-
riety of electron donors. Overlap of the unfilled
boron pz orbital with nonbonding filled orbitals

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a04 309
2 Boron Compounds
Table 1. Physical properties of boron halides [5], [6]

BF3 BCl3 BBr3 BI3

◦
mp, C − 127.1 − 107 − 46 49.9
bp, ◦ C − 99.9 12.5 91.3 210
Density, g/mL 1.57 ∗ 1.359 2.618 –
H ◦ fusion, kJ/mol (at 298 K) − 1136 [7] − 403 [8] − 240 [8] − 47 [8]
∆S ◦ , J mol−1 K−1 (at 298 K) 254 [7] 290 324 –
cp (v) , J mol−1 K−1 (at 298 K) 50.5 62.6 68.0 –
Electron affinity, J × 10−19 < 0 [9] 0.53 [9] 1.31 [9] 1.81 [9]
B−X Bond energy, kJ/mol 154.3 106.1 88.0 63.7
B−X Bond length, nm 0.129 0.175 0.187 0.210

∗ At −100 ◦ C.

on the halides decreases the electron acceptor
ability of the molecule but increases the strength
of the B−X bonds. The B−F bond in BF3 is the
strongest single bond known. The boron – halide
pz overlap decreases with increasing size of
the halide. Thus, the acceptor strength in-
creases as BF3 < BCl3 < BBr3 < BI3 . However,
the strength of the B−X bond decreases from
BF3 to BI3 . Boron trifluoride chemistry is dom-
inated by Lewis acid – base reactions, whereas
BBr3 and BI3 adducts are relatively unstable and
halide displacement reactions predominate.
1.2.1. Exchange Reactions
All of the boron halides undergo halide exchange
reactions, but of the mixed halide species only
BBr2 I and BBrI2 have been isolated. Exchange
reactions are also known with trialkyl-, triaryl-,
trialkoxy-, and triaryloxyboranes:
BX3 + 2 BR3 −→ 3 BXR2
Exchange reactions between BF3 and metal
halides may be used to prepare other boron tri-
halides:
3 KCl + 4 BF3 −→ 3 KBF4 + BCl3
AlBr3 + BF3 −→ BBr3 + AlF3
Because of the strength of the boron – fluorine
bond, halide displacement reactions occur to a
lesser extent with BF3 than with other boron
halides. Boron trifluoride reacts with water to
give a number of partially hydrolyzed fluorob-
orate species including BF3 OH− , BF2 (OH)− 2,
and BF(OH)− 3 , in addition to boric acid and the
fluoroborate anion, BF− 4 . Two hydrated species,
BF3 · H2 O and BF3 · (H2 O)2 , can be isolated at
low temperature. The dihydrate is formulated as
BF3 OH2 · H2 O [11].
In contrast to the slow substitution reactions
of BF3 , other boron trihalides react vigorously
with water:
BX3 + 3 H2 O −→ B(OH)3 + 3 HX
The reaction of BBr3 or BI3 with water may be
explosive.
Most halide displacement reactions with BF3
require either elevated temperature or an active
nucleophile, such as a Grignard reagent:
2 BF3 + 6 RMgBr −→ 2 BR3 + 3 MgBr2 + 3 MgF2
Halide displacement reactions between other
boron halides and compounds with active hy-
drogen atoms are quite facile. The first step is
often the formation of an adduct, which may
be isolated at low temperature, followed by the
elimination of the hydrogen halide:

1.2.2. Halide Displacement Reactions

Boron halides, with the exception of boron tri-

fluoride, react readily with compounds that have
active hydrogen atoms, including water, alco- In general the reactivity of boron trihalides
hols, thiols, amines, phosphines, and arsines. toward compounds with active hydrogen atoms

increases with decreasing B−X bond energy,
in the order BF3 < BCl3 < BBr3 . Side reactions
leading to alkyl halides and boric acid rather than
simple halide displacement are more common
with the triiodide and sterically hindered alco-
hols.
1.2.3. Boron Trihalides as Lewis Acids
Boron trifluoride forms adducts with a large
number of electron donors including ethers, al-
cohols, ketones, amines, phosphines, arsines,
thiols, and selenides. Those complexes with
large electron donor atoms or sterically hindered
bases tend to be less stable. Boron trichloride
also forms many stable complexes with electron
donors, but these are more prone to halide dis-
placement reactions than are the BF3 adducts.
Few stable adducts are known with BBr3 or BI3 .
1.2.4. Reduction Reactions
Reaction of boron halides with hydrogen, hy-
drides, or alkali metals often yields boron sub-
halides or elemental boron. If hydrogen or a hy-
dride is used, boranes may result, e.g., in the
following convenient preparation of diborane:
6 LiH + 8 BF3 · O(C2 H5 )2 −→ B2 H6 + 6 LiBF4
+ 8 (C2 H5 )2 O
1.3. Production
Boron Trifluoride. Boron trifluoride was
first prepared by the reaction of boric acid and
fluorspar (CaF2 ) at red heat [12]. Commercially,
BF3 has been produced by the stepwise addition
of hydrofluoric acid and sulfuric acid to anhy-
drous borax (sodium tetraborate):
Na2 B4 O7 + 12 HF −→ Na2 O · (BF3 )4 + 6 H2 O
Na2 O · (BF3 )4 + 2 H2 SO4 −→ 4 BF3 + 2 NaHSO4 + H2 O
Another method involves addition of sulfuric
acid and fluorspar and a source of boron, such
as anhydrous borax or boric oxide (B2 O3 ).
A process was developed in which BF3 is ob-
tained by the reaction of HF and boric acid, using
oleum as a dehydrating agent [13].
Boron Compounds 3
H3 BO3 + 3 HF −→ BF3 + 3 H2 O
Boron trifluoride is made commercially in the
United States by a proprietary process from
boric acid and hydrofluoric acid.
A variety of synthetic routes are available
for the production of small quantities of BF3 ,
including thermal decomposition of diazonium
fluoroborate. The diethyl etherate adduct, BF3
· O(C2 H5 )2 [109-63-7], produced by bubbling
BF3 into diethyl ether, provides a convenient
source of BF3 for many synthetic applications.
Boron Trichloride. This compound can be
prepared by the reaction of boric oxide, a reduc-
ing agent, and chlorine in a melt at high temper-
atures, for example:
The product BCl3 is recovered by fractional con-
densation. Sodium tetraborate Na2 B4 O7 can be
used in place of B2 O3 . Molten sodium chloride,
formed as a byproduct, settles to the bottom
of the reactor [14]. A molten combination of
aluminum chloride and an alkali-metal chloride
has also been used as a medium for reductive
chlorination of borates [15].
Free-radical chlorination of borate esters also
yields BCl3 :
B(OCH3 )3 + 9 Cl2 −→ BCl3 + 3 COCl2 + 9 HCl
A modification of this process, in which a free-
radical initiator is used, has been reported [16],
[17]. A low reaction temperature, 40 – 90 ◦ C,
and the use of an initiator decrease the consump-
tion of Cl2 and prevent the formation of phos-
gene, COCl2 .
Commercially, boron trichloride is prepared
by the reaction of boron carbide with chlorine
in a borate melt. This reaction can also be done
with dry B4 C in a fluidized-bed reactor using a
transition-metal halide as a catalyst [18].
Contamination of BCl3 with COCl2 from the
chlorination of carbon oxides is a serious prob-
lem in BCl3 manufacturing. Because of similar
vapor pressure – temperature curves, BCl3 and
COCl2 cannot be separated by fractional distil-
lation. Thermal or photochemical conversion of
4 Boron Compounds
COCl2 to CO and Cl2 followed by fractional
distillation has been used to purify BCl3 .
Boron trichloride can be prepared in the lab-
oratory by the reaction of boron trifluoride and
aluminum chloride.
Boron Tribromide. This compound can be
prepared by the reaction of boric oxide, carbon,
and bromine, or from boron carbide and bromine
analogous to the chlorine reactions.
Small quantities of BBr3 can be made by the
reaction of boron trifluoride and aluminum tri-
bromide. A five-fold excess of AlBr3 increases
the yield of BBr3 .
Boron Triiodide. Boron triiodide can be
prepared by the reaction of a borohydride and
iodine:
3 MBH4 + 8 I2 −→ 3 BI3 + 3 MI + 4 HI + 4 H2
where M is lithium, sodium, or potassium.
The reaction between sodium borohydride
and iodine in dimethylformamide (DMF) results
in BI3 · 4 DMF [19]. Boron triiodide can also be
made by exchange reactions between AlI3 and
BF3 , or between LiI and LiBH4 . Contrary to an
earlier report, boron triiodide can be prepared
from the elements by the reaction of amorphous
boron with iodine at 870 ◦ C [20].
1.4. Quality Specifications, Chemical
Analysis
Boron trifluoride is available in quantity as a
99 % pure gas. Boron trichloride is typically sold
as a 99.9 % pure liquid. Boron tribromide is of-
fered in grades up to 99.9999 % for electronic
applications.
Common impurities in BF3 include air, sil-
icon tetrafluoride, and sulfur dioxide. The ma-
jor impurities in boron trichloride are phosgene
and chlorine. Boron tribromide typically con-
tains traces of bromine.
The boron halides may be analyzed by hy-
drolysis followed by analysis of B2 O3 and the
halide, or by base titration. The concentration
of phosgene (COCl2 ) in BCl3 may be deter-
mined by infrared spectroscopy. The trifluoride,
trichloride, and tribromide may be purified by
fractional distillation.
1.5. Sources, Handling, and
Transportation
Allied Corp. is the major producer of boron tri-
fluoride. Boron trifluoride complexes with mo-
noethylamine, phenol, and diethyl ether are also
available in large quantities from Allied. Com-
plexes of BF3 with water, dimethylamine, mo-
noethylamine, phosphoric acid, and piperidine
are available from Harshaw/Filtrol. Kerr-McGee
Corp. is the major producer of BCl3 and BBr3 .
Boron trifluoride and trichloride are available
in steel cylinders. Boron tribromide is avail-
able in glass bottles. Boron tribromide for use
in electronics is supplied by J. C. Schumacher
Co. in specially sealed glass vessels equipped
with teflon valves. Boron triiodide is available
in small quantities from the Ventron Division of
Morton-Thiokol Inc.
Boron trifluoride and boron trichloride
sold for $ 6.83/kg ($ 3.10/lb) and $ 8.38/kg
($ 3.80/lb) in bulk in 1984. The 1982 price for
BBr3 was $ 57/kg ($ 26/lb) in large quantities
from Kerr-McGee.
Boron trifluoride is the largest volume boron
halide. The total annual production of BF3 and
its adducts is about 2300 – 4500 t/a. The annual
production of BCl3 is about 225 – 450 t/a. The
annual production rate of BBr3 is significantly
less than that of BCl3 .
The boron trihalides are nonflammable. But
because they hydrolyze easily, care should be
taken to avoid exposure to moisture. The DOT
classification for BCl3 and BBr3 is corrosive liq-
uid; BF3 is classified as a nonflammable gas.
Equipment for conveying the compounds should
be flushed with dry air prior to use. Stainless steel
lines and valves are suitable for use with all dry
boron halides.
1.6. Uses of Boron Trihalides
Boron Trifluoride. Boron trifluoride is the
most widely used boron halide. Most applica-
tions take advantage of its strong Lewis acid-
ity. The most important uses are in organic syn-
theses. Boron trifluoride is commonly used as a
catalyst for Friedel-Crafts alkylation reactions.
It also is used to catalyze the cleavage of ethers
to alcohols, to catalyze esterification reactions,

and in the nitration and sulfonation of aromatic
compounds. Many olefin polymerization reac-
tions use BF3 as an initiator, in conjunction with
a proton donor, such as water. Also BF3 is used to
catalyze the isomerization of alkenes and alka-
nes and in petroleum cracking and desulfuriza-
tion. Amine complexes of BF3 are used as epoxy
curing agents.
Boron Trichloride. One of the most impor-
tant uses of BCl3 is in the preparation of boron
fibers (→ Fibers, 5. Synthetic Inorganic). Typi-
cally an electrically heated tungsten filament is
passed through a chamber containing BCl3 and
hydrogen. The BCl3 is reduced, and boron is de-
posited on the filament, producing a stiff, strong
boron fiber.
Boron trichloride, like the trifluoride, has
been used as a Lewis acid catalyst in organic
synthesis in the polymerization of olefins and
phosphazines, as well as in catalysis of other or-
ganic reactions. Boron trichloride is also used
in plasma etching of aluminum and silicon, in
semiconductor manufacturing, and as a source
of boron for chemical vapor deposition. Steel is
boronized by contacting it with a reactive mix-
ture of hydrogen, hydrocarbons, and BCl3 at
high temperatures.
Boron Tribromide. The primary use of
boron tribromide is as an initiator for the poly-
merization of olefins and as a catalyst in other or-
ganic reactions. It is also used in the electronics
industry as a source of bromine for ion implanta-
tion in semiconductors, and for plasma etching
in semiconductor device manufacturing.
Boron Triiodide. There are no important
commercial uses for boron triiodide.
1.7. Pollution Control, Toxicology, and
Occupational Health
Boron halides are not major pollution sources.
Fluoride, from the hydrolysis of BF3 , can be pre-
cipitated from waste water as CaF2 by the addi-
tion of a calcium salt [21–23]. Aqueous boron
(boric acid or borates) can be precipitated by the
addition of calcium salts at high pH.
Boron Compounds 5
Boron halides are quite toxic and contact
with skin or eyes should be avoided. A TLV
ceiling limit of 1.0 ppm, 3 mg/m3 (TWA), has
been set for BF3 by the ACGIH. The MAK val-
ues are the same. For BBr3 , the adopted TLVs
are 1 ppm, 10 mg/m3 (TWA); 3 ppm, 30 mg/m3
(STEL). The LCs in air for BF3 and BCl3 in male
rats (1 h exposure) are 387 and 2.54 ppm, respec-
tively [24]. These compounds are not known to
be carcinogenic.
2. Fluoroboric Acid and
Fluoroborates
2.1. Physical and Chemical Properties
In the older literature and in some commercial
usage, HBF4 and its salts are referred to as fluo-
boric acid and fluoborates. Nomenclature based
on fluoroboric and fluoroborates has now be-
come generally accepted in the literature and is
used throughout this chapter [29].
The fluoroborate anion, BF− 4 , is essentially
the adduct of BF3 and F− . The ion is tetrahe-
dral, with B−F bond lengths of about 0.140 –
0.145 nm compared to a B−F bond length of
0.129 nm in BF3 .
The fluoroborate anion hydrolyzes in water
in a stepwise manner to give first hydroxyfluo-
roborates, then boric acid:
BF− − +
4 + H2 O −→ (HO)BF3 + H + F
−
(HO)BF− − +
3 + H2 O −→ (HO)2 BF2 + H + F
−
(HO)2 BF− − +
2 + H2 O −→ (HO)3 BF + H + F
−
(HO)3 BF− −→ B(OH)3 + F−
Concentrated solutions of alkali-metal fluoro-
borates are stable toward hydrolysis; the an-
ion is more easily hydrolyzed in solutions
of transition-metal fluoroborates. Concentrated
aqueous solutions of fluoroboric acid, tetrafluo-
roboric acid, HBF4 [16872-11-0], can be made,
but HBF4 has not been isolated. Solvated species
have been crystallized, including H3 O · BF4 ,
H5 O2 · BF4 , and [H(CH3 OH)2 ] · BF4 [30]. The
term fluoroboric acid, as used commercially, al-
ways refers to an aqueous solution of HBF4 .
Many transition-metal fluoroborates are quite
soluble in water. Alkali-metal salts are less
soluble. Ammonium, sodium, and potassium
fluoroborate crystallize as anhydrous salts.
6 Boron Compounds

Transition-metal salts all crystallize with vari-
ous degrees of hydration. Many metal fluorob-
orates are also soluble in methanol and ethanol.
Silver and copper(II) fluoroborate are soluble in
diethyl ether and aromatic solvents.
Solid fluoroborate salts decompose upon
heating, evolving BF3 . The heat of dissociation
increases with cation size for the alkali-metal
fluoroborates [31]. The reaction has been used
as a convenient source of BF3 for laboratory ap-
plications:
NaBF4 −→ NaF + BF3
Solid alkali-metal fluoroborates may contain
some hydroxyfluoroborates and boric acid as
contaminants. Metal fluoroborate solutions may
contain free boric acid or fluoroboric acid as well
as trace amounts of metallic impurities.
Fluoroboric acid can be analyzed by hydrol-
ysis, followed by precipitation of fluoride with
calcium and titration for the borate. Metal fluo-
roborates have been analyzed by electrolytic re-
duction followed by mannitol titration for boric
acid [32]. A BF−4 ion selective electrode is avail-
able from Orion. The tetrafluoroborate ion can
also be analyzed by ion chromatography [33],
[34].

2.2. Production
2.4. Sources, Handling, and
Fluoroboric acid is usually made by the reaction Transportation
of hydrofluoric acid and boric acid in water:
Fluoroboric acid is available from Allied
4 HF + B(OH)3 −→ HBF4 + 3 H2 O Corp., Harshaw/Filtrol, C.P. Chemicals, Fidelity
Chemicals, Harstan, and Ozark-Mahoning. A
The reaction is exothermic.
variety of fluoroborate salts is produced by C.P.
Most of the commonly used fluoroborate salts
Chemicals, Harstan, Allied, Harshaw/Filtrol,
can be prepared by reacting metal oxides, hy-
and Fidelity Chemicals. Transition-metal fluo-
droxides, or carbonates with fluoroboric acid.
roborates are commonly sold as aqueous solu-
Ammonium fluoroborate can be made from am-
tions. They may contain a slight excess of boric
monia and fluoroboric acid. Fluoroborate salts
acid, added as a stabilizer. Information on com-
can also be prepared by the reaction of BF3 with
mercial fluoroborates is given in Table 3.
a metal fluoride in a nonaqueous, inert solvent,
Fluoroboric acid and solutions of fluorob-
such as HF, BrF3 , or SO2 .
orates are corrosive and are shipped in plas-
tic drums or polyethylene pails. Glass vessels
should not be used for containing these solu-
2.3. Quality Specifications, Chemical tions.
Analysis Solutions of fluoroboric acid and fluorobo-
rates are classified as corrosive materials for
Fluoroboric acid is available from Har- shipping.
shaw/Filtrol in two grades, Electropure and Flu-
opure, a lower purity material. Specifications for
Electropure fluoroboric acid are given in Table 2.
2.5. Uses
Table 2. Specifications for Harshaw/Filtrol Electropure fluoroboric The primary use of fluoroboric acid is in the
acid
preparation of other fluoroborate salts. Flu-
Component Specification Typical average oroboric acid is also used in electroplating
HBF4 48 – 50 % 48.5 % and in dipping solutions for surface treating
H3 BO3 0.5 –1.5 % 0.75 % of aluminum. It has been recommended as a
Fe 10 ppm max. 4 ppm
Cu 1 ppm max. < 1 ppm pickling agent for hot rolled steel [35], and
Pb 1 ppm max. < 1 ppm has been patented for use as an etchant for
Zn 1 ppm max. < 1 ppm silicon and glass in the electronics industry
Cl 3 ppm max. < 3 ppm
SO4 50 ppm max. < 50 ppm (→ Electrochemical and Chemical Deposition,
Ni 2 ppm max. < 1 ppm Chap. 4.) [36], [37].
 Boron Compounds 7
Table 3. Commercial fluoroborates

Compound CAS Formula Commercial form Price (1984),

registry no. $/kg

Fluoroboric acid [16872-11-0] HBF4 49 % solution 2.01

Alkali-metal salts
Ammonium [13826-83-0] NH4 BF4 crystalline solid 3.73
Potassium [14075-53-7] KBF4 crystalline solid 3.13
Sodium [13755-29-8] NaBF4 solid 3.09
Transition-metal salts
Antimony(III) [14486-20-5] Sb(BF4 )3 solution 6.66
Cadmium(II) >[144-86-19-2] Cd(BF4 )2 50 % solution 5.00
Cobalt(II) [26490-63-1] Co(BF4 )2 solid −
Copper(II) [38465-60-0] Cu(BF4 )2 45 % solution 2.31
Indium(III) [27765-48-6] In(BF4 )3 solution −
Iron(II) [15283-51-9] Fe(BF4 )2 41 % solution 1.06
Lead(II) [13814-96-5] Pb(BF4 )2 51 % solution 1.87
Nickel(II) [14708-14-6] Ni(BF4 )2 45 % solution 3.55
Silver(I) [14104-20-2] AgBF4 powder −
Tin(II) [13814-97-6] Sn(BF4 )2 50 % solution 7.69
Zinc(II) [13826-88-5] Zn(BF4 )2 40 % solution −

Molten alkali-metal and ammonium fluorob-
orates are good solvents for metal oxides and
are commonly used in fluxes for soldering and
brazing.
A mixture of LiF and NaBF4 has been studied
as a nuclear reactor coolant [38] and as a solvent
for fissionable materials. Mixtures of NH4 BF4
with nitro compounds are useful as explosives
[39].
Alkali metal fluoroborates and fluoroboric
acid have also been used as catalysts in organic
synthesis and in polymerization reactions.
Lithium fluoroborate is used as an electrolyte
in lithium – sulfur batteries.
The fluoroborate anion is similar to perchlo-
rate, ClO− 4 , in its size, shape, and lack of ability
to form coordinate bonds with transition metals.
Fluoroborates are often used in transition metal
chemistry where a noncoordinating anion is re-
quired.
The primary use of transition metal fluorobo-
rates is in electroplating. The fluoroborate ion is
electrochemically inert and solutions of fluorob-
orates are highly conductive. Metals plated from
fluoroborate solutions include cadmium, copper,
indium, iron, lead, nickel, silver, tin, and zinc.
2.6. Pollution Control, Toxicology
Aqueous solutions of fluoroborates can be hy-
drolyzed and treated with calcium compounds to
precipitate calcium fluoride for pollution control
[40–42]. Reverse osmosis has also been used to
purify waste streams containing potassium flu-
oroborate [43].
Protective equipment used with hydrofluoric
acid should also be used when handling solu-
tions of fluoroboric acid or fluoroborates.
Little information is available in the litera-
ture on the toxicity of fluoroborates. Fluorobo-
rate given intravenously to rats depressed levels
of l-thyroxine [44], and ammonium fluorobo-
rate was shown to be nontoxic to fresh water
minnows at concentrations less than 600 mg/L
[45].
3. Boron Subhalides
All of the compounds, B2 X4 , where X
is F [13965-73-6], Cl [13701-67-2], Br
[14355-29-4], or I [13703-80-5], are known. The
tetrafluoride is the most stable, but all four com-
pounds decompose at room temperature to BX3
and other boron halides. The compounds are
Lewis diacids and form 1 : 2 complexes with
amines and other Lewis bases. Boron tetrachlo-
ride, which is the most commonly used of these
tetrahalides, can be prepared by reduction of
BCl3 in an electrical discharge apparatus. The
most important use of B2 X4 compounds is in di-
boration reactions, i.e., the addition of B2 X4 to
unsaturated organic molecules. These reactions
are analogous to hydroboration reactions with
diborane. Some of the decomposition products
of B2 Cl4 have been characterized. They include
B4 Cl4 , B8 Cl8 , and B9 Cl9 .
8 Boron Compounds
4. Boron Sulfide
4.1. Physical and Chemical Properties
Boron sulfide [12007-33-9], B2 S3 , M r 117.81,
is a colorless compound normally obtained as
an amorphous glass. It is extremely difficult to
purify and often contains traces of silicon (from
glass vessels), oxygen, or sulfur, which may im-
part a yellow color to the material [46]. The
amorphous form does not have a well-defined
melting point but begins to sublime at about
300 ◦ C. Some of the physical properties are
given in Table 4.
Table 4. Physical properties of B2 S3
mp (crystalline form), ◦ C 563 [47]
Flow point (amorphous form), ◦ C 310 [46]
bp, ◦ C ≈ 300, sublimes [46]
Density, , g/cm3 1.92 [48]
B−S Bond energy, kJ/mol 360 [49]
Heat of fusion, kJ/mol 150 [46]
Heat of vaporization, kJ/mol 252 [50]
Average B−S bond length, nm 0.1808 [48]
An X-ray analysis of crystalline B2 S3 indi-
cates it is composed of (BS)3 and (BS)2 rings
linked through bridging sulfur atoms in a two-
dimensional lattice [48].
Boron sulfide reacts with a variety of protonic
reagents [51]:
B2 S3 + 6 H2 O −→ 2 B(OH)3 + 3 H2 S
B2 S3 + 6 ROH −→ 2 B(OR)3 + 3 H2 S
B2 S3 + 6 R2 NH −→ 2 B(NR2 )3 + 3 H2 S
The reaction with water is quite violent.
Boron sulfide inflames in chlorine, and is ox-
idized at high temperature by carbon dioxide or
by oxygen [51]. At high temperature it also read-
ily attacks quartz and silicate glass [46]. Boron
sulfide reacts with sulfur to give B8 S16 , a planar
molecule [52]. A variety of other higher molec-
ular mass boron sulfides is also known [53].
Boron sulfide can also act as a sulfidizing
agent [54] and can be used to replace a terminal
oxygen atom with a terminal sulfur atom in both
organic and inorganic systems [55], [56].
4.2. Production
Boron sulfide is difficult to prepare in a pure
form. The reaction of boron hydrides or metal
borides with sulfur or sulfur compounds yields
impure B2 S3 [46]. Higher purity product is ob-
tained by the reaction of amorphous boron with
H2 S or sulfur. Other preparative reactions that
have been reported [47], [48] are:
The recommended route for the synthesis
of pure B2 S3 is the decomposition of (XBS)3 ,
where X is Cl, Br, or I [46], [51]:
4.3. Uses
Boron sulfide has been used in organic synthesis
to reduce sulfoxides to thiols [57], and to con-
vert ketones to thioketones [55],[58]. The sul-
fide glasses, M2 S−B2 S3 , where M is Li or Na,
have electrical conductivities 103 times greater
than the corresponding oxide glasses [59]. Elec-
trically conducting boron sulfide glasses have
also been made incorporating LiI [60] and other
glass-forming sulfides [61], [62]. These glasses
have potential as electrolytes in batteries or fuel
cells.
Boron sulfide is available in research quanti-
ties from the Alfa-Ventron Division of Morton-
Thiokol (USA).
5. Boranes
5.1. Diborane and Higher Boranes
Introduction. Alfred Stock and co-workers
began working on the hydrides of boron in
1912 [63]. From then until 1936, he discov-
ered a series of boron hydrides of the compo-
sition Bn Hn+4 and Bn Hn+6 , which he named
boranes.
Research on boron hydrides was started in
the United States by H. I. Schlesinger, who
with A. Burg published a new preparation of
diborane in 1931 [64]. Impetus was added by

government sponsorship of various military pro-
grams to develop high-energy fuels for rockets
and aircraft during World War II. Boron fuels
(alkyl penta- and decaboranes) created great in-
terest because they possessed much higher heats
of combustion than conventional hydrocarbon
fuels. Large quantities of boron fuels were man-
ufactured under projects HEF (Olin Matheson
Chemical Corp.) and ZIP (Callery Chemical
Co.).
Attention has been expanded to other chem-
ical properties of the boranes since 1956, when
H. C. Brown discovered hydroboration proce-
dures [65] (1979 Nobel Prize). His work has
opened new avenues of research, one of which
was to obtain chiral and optically specific com-
pounds required in biological activity.
Progress in borane research was thwarted by
inconclusive theories of structure and reactiv-
ity until the second half of the century, when
W. Lipscomb and co-workers defined the struc-
tural and theoretical aspects of the boron hy-
drides through X-ray diffraction studies [66]
(1976 Nobel Prize). This breakthrough in bo-
rane chemistry gave new impetus to boron re-
search and to the discovery of the most thermo-
dynamically and kinetically stable class of bo-
ranes, the polyhedral anions, carbaboranes, and
metalloboranes.
Collectively, boranes are compounds of very
complex structure with B−Hµ −B and (open or
closed structured) B−Bµ −B tricentered bonds,
with Hµ equal to linking hydrogen atoms. Expla-
nation of structures and unusual bonding of these
compounds has furthered the theory of chemi-
cal bonding [67]. Nomenclature of these com-
pounds has been confusing, however, and rec-
ommendations to clarify their structures have
been made by IUPAC and ACS [68].
Table 5. Physical properties of boranes
Formula CAS Mr
registry no.
B2 H6 [19287-45-7] 27.69
B4 H10 [18283-93-7] 53.32
B5 H9 [19624-22-7] 63.17
B10 H14 [17702-41-9] 122.22
Boron Compounds 9
5.1.1. Physical and Chemical Properties
The lower boranes are very reactive to oxy-
gen and moisture. Diborane(6), B2 H6 , and air
mixtures containing 75 – 98 % diborane deto-
nate in air when sparked, and concentrations
over 0.5 vol % can lead to explosions in air or
oxygen even without an ignition source. For in-
vestigations of oxidation see [69–71]. Pentabo-
rane(9), B5 H9 , a volatile liquid, reacts readily
with air and moisture. Solid decaborane(14),
B10 H14 , should be handled in an inert atmo-
sphere; exposure should be avoided because of
the compound’s toxicity (see Table 8). Solutions
of B10 H14 and carbon tetrachloride are explo-
sive and more shock sensitive than nitroglycer-
ine [72]. Some physical properties of the most
commercially available boranes are given in Ta-
ble 5 (see below).
As a Lewis acid, the borane(3), BH3 , group
complexes with Lewis bases, analogous to co-
ordinate compounds of the Werner type; the lig-
ands NH3 , NH2 R, and NR3 are common to the
two cases [73]. The Lewis acid BH3 combines
with another borane (Lewis acid) to give the rel-
atively stable borane(6); hence borane groups
may be considered as operational “electron-de
ficient” bases as well as Lewis acids. How the na-
ture of the base or nucleophile affects the cleav-
age of diborane is controversial and has been dis-
cussed [74]. With neutral bases the two modes of
cleavage, symmetric or unsymmetric, may occur
to give molecular or ionic fragments as shown
in Figure 1 (see next page). Generally with large
bases or weaker donor atoms symmetric cleav-
age occurs. Base displacement reactions readily
occur and the relative stability of the complexes
is:
Group V: P > N
Group VI: S > O
Group V > Group VI
mp, ◦ C bp, ◦ C ∆H ◦ fusion,
(101.3 kPa) kJ/mol
−164.9 −92.6 35.5
−120 18 66.1
− 46.6 48 73.2
99.7 213 31.5
10 Boron Compounds
Figure 1. Cleavage of diborane
∗ L is any ligand. ∗∗ Modes of cleavage.
Lewis bases react with decaborane, with-
out deprotonation, evolving hydrogen with the
ligands coordinating at the 6,9 position. This
species, B10 H12 L2 , is a key intermediate in the
synthesis of the very stable and useful closo-
boranes, [B10 H10 ]2− , and carbaboranes (where
carbon is inserted in the 1,2 position of the poly-
hedron, i.e., 1,2-C2 B10 H12 ).
Bridge hydrogens of the boranes are acidic
as demonstrated by titration of B10 H14 and by
deuterium exchange [75], [76]. Abstraction of
a proton forms hydropolyborate anions, such
as B5 H−8 . They are useful intermediates in
the formation of higher boranes, heteroboranes,
and metalloboranes. These anions, containing a
B−B edge bond, can be reacted with diborane
to expand the polyhedron [77].
5.1.2. Production
Diborane(6) is available from Callery Chem-
ical Co., Callery, Pennsylvania (USA). The
method preferred for the commercial prepara-
tion is the addition of boron trifluoride to a stirred
solution of sodium borohydride in diethylene
glycol dimethyl ether (diglyme):
Diborane is shipped either as a compressed
gas (ambient) or as a liquid (cylinder over pack-
aged with dry ice). It is packaged as a hazardous
material regulated by the DOT [78].
Tetraborane(10), B4 H10 , can be obtained by
the action of acid on borides [79–81]. It has been
prepared from the decomposition of diborane
at 120 – 180 ◦ C [82] and under pressure [83].
Tetraborane can also be prepared from the re-
action of acid on commercially available B3 H− 8
salts, e.g., NaB3 H8 [12429-74-2].
Pentaborane is obtained by passing diborane
through a hot tube. Careful control of temper-
ature, pressure, and flow are required to obtain
good yields and avoid further pyrolysis to higher
hydrides.
Decaborane can be produced by several pro-
cedures, none of which give high yields; all re-
quire extensive preparatory time or equipment.
It is best produced by the pyrolysis of diborane
between 120 – 240 ◦ C. The solids thus produced
are removed from the reactor by dissolution and
further purified by sublimation.
5.1.3. Uses
Most of the boranes are highly reactive. This
property makes them useful and important
chemicals, but also necessitates special care in
their application.
Diborane serves as a strong but selective re-
ducing agent in organic chemistry. It is an elec-
trophilic reagent and reacts markedly different
from the nucleophilic alkali-metal boron and
aluminum hydrides. The rates of reduction with
diborane were found to decrease in the order:
carboxylic acids > olefins > ketones > nitriles
> epoxides > esters > acid chlorides [84]. Re-
ductions of several other organic substrates have
been studied, for example, oximes [85], perflu-
orinated olefins [86], diene polymers [87], and
organic acid amides [88].
Hydroboration, the addition of diborane or
borane to olefins, has found great significance
in preparative chemistry [65]. Hydroboration
is applicable to multiple bonds between C−C,
C−O, C−N, N−N, N−O. Diborane catalyzed
by the presence of an ether adds, in an anti-
Markovnikov mode, virtually quantitatively to
the carbon – carbon double bond of olefins,
forming an alkyl borane.
Other important derivatives of diborane are
Lewis base adducts, carbonyl adducts, and
oxygen-containing products. Further areas of
application for diborane are the doping of
semiconductor silicon and germanium. Dibo-
rane is readily decomposed at high temperature
(600 – 700 ◦ C) [89] to give fine-powder, high-
purity elemental boron. Copyrolysis of dibo-
rane with hydrocarbons yields boron carbide,

and with NH3 yields boron nitride. These mate-
rials, deposited on metal substrates as thin, hard
layers, are used in ceramics, tools, and wear-
resistant parts. Boron fibers are formed from
the decomposition of diborane on substrates and
used for light-weight structural components.
The large cross-sectional area of the 10 B iso-
tope for neutron capture makes these compounds
especially useful in nuclear applications. Bo-
rane is also supplied as stable liquid adducts
(CH3 )2 S · BH3 [13292-87-0] (Callery Chemi-
cal Co., Aldrich Chemical Co.), and as a 1 M
solution in tetrahydrofuran (THF) [14044-65-6]
(Aldrich Chemical Co., Ventron Div. of Morton-
Thiokol Inc.).
5.2. Amine Boranes
Most amine boranes are white solids, stable to
air and moisture. Primary and secondary amine
boranes are, however, thermally unstable above
70 ◦ C.
Aliphatic amine boranes are soluble in a vari-
ety of protic and nonprotic solvents, in contrast
to NaBH4 . Hydrolysis is slow under neutral con-
ditions and increases in rate as the pH is lowered.
Arylamine boranes are hydrolyzed much more
readily.
Production. Preparation may be by reaction
of diborane or dimethyl sulfide borane with an
amine, or by reacting an ammonium salt of the
desired amine with NaBH4 in an ether [90]. The
dimethyl sulfide borane route is the most con-
venient method of preparing small quantities of
amine boranes [91].
Both (CH3 )2 NH · BH3 [74-94-2] and tert-
C4 H9 NH2 · BH3 [7337-45-3] are available in up
to tonnage quantities, whereas smaller quantities
of (CH3 )3 N · BH3 [75-22-9], (C2 H5 )3 N · BH3
[1722-26-5], (C2 H5 )2 NH · BH3 [2670-68-0],
pyridine borane [110-51-0], and morpholine bo-
rane [4856-95-5] are commercially available
(Callery Chemical Co., Bayer AG).
Uses. The largest quantities of amine boranes
are consumed in the electroless plating of vari-
ous metals, primarily nickel. Dimethylamine bo-
rane is the preferred reductant in North America,
whereas diethylamine borane is used in Europe.
The nickel thus plated by chemical reduction
Boron Compounds 11
is amorphous and contains varying amounts of
boron depending on the bath formulation [92].
This plating mainly provides corrosion protec-
tion and high solderability to electrical parts.
Amine boranes have also been used to plate cop-
per, gold, palladium, cobalt, and other metals
[93].
Amine boranes are finding expanding use as
mild reducing agents, comparable to cyanoboro-
hydride in reducing power, but considerably
less toxic. Amines of greater base strength give
amine boranes of diminished reducing power;
for example, (CH3 )3 N · BH3 is a relatively weak
reducer, whereas NH3 · BH3 is a moderately
strong reducer.
It has been shown that NH3 · BH3 and pri-
mary and secondary amine boranes are efficient
stereoselective reducing agents for aldehydes
and ketones in a variety of solvents [94]. Ad-
ditionally, these reagents selectively reduce al-
dehydes in the presence of ketones or esters [95],
[96].
Chiral amine boranes have been useful in
the asymmetric reduction of prochiral ketones.
In the presence of BF3 etherate, borane com-
plexes of sodium salts of amino acids gave enan-
tiomeric excesses up to 62 % [97].
Pyridine borane in acidic media is a versatile
and powerful reducing agent. It reduces alde-
hydes, ketones, oximes, Schiff bases, tosylhy-
drazines, and aryl alcohols [98].
Polymer-bound amine boranes (Amboranes,
Alpha Ventron) have been proposed for the re-
covery of precious metals. They are effective,
if slow, reducing agents for imines, enamines,
aldehydes, and ketones [99].
Amine borane analogue of amino acids
showed anti-inflammatory activity in rodents
[100].
5.3. Borohydrides
Of the borohydrides or hydroboron ions, the
most common and most completely studied is
the tetrahydromonoborate(1−). The oxidation
state of the central atom in the higher hydroboron
ions is fractional in ions containing several boron
atoms and the charge is listed as a suffix in paren-
theses [101]. Generally, the borohydrides are
highly polarizable [102] and the bonding may
12 Boron Compounds
vary from essentially ionic to essentially cova-
lent.
All of the alkali-metal tetrahydroborates have
been prepared and are white crystalline solids
with markedly different solubilities. Sodium
tetrahydroborate(1−) [16940-66-2], NaBH4 ,
M r 37.83, is stable in dry air, reacting slowly
with moisture. Hydrolysis is catalyzed by acid,
but can be terminated with sufficient sodium hy-
droxide [103]. Salts of the ions B3 H− −
8 , B11 H14 ,
2− 2−
B10 H10 , and B12 H12 are all white crystalline
solids. The latter two salts are extremely sta-
ble thermally, especially their halo derivatives
B10 X2− 2−
10 , B12 X12 .
Production. Sodium tetrahydroborate is
made by the addition of methyl borate to hy-
drogenated sodium in mineral oil [104], [105]:
Separation of the sodium methoxide from
NaBH4 was accomplished by such methods
as extraction with amines [106], and extrac-
tion with water followed by a counterextraction
with a solvent, such as 2-aminopropane [107].
Sodium borohydride is produced commercially
by Ventron Div., Morton-Thiokol (USA) [108].
A simple preparation for B3 H− 8 , adaptable
to large scale, involves the addition of B2 H6 to
NaBH4 in diglyme at 100 ◦ C [109]. Further ad-
dition of B2 H6 to the B3 H−
8 at higher tempera-
ture yields B12 H2− [110].
12
Uses. A concentrated aqueous solution of
NaBH4 stabilized by NaOH is used to reduce
hydrogen sulfite to dithionite in the bleaching of
ground wood pulp [111]. Also, NaBH4 has ex-
tensive and important use as a reducing agent
in organic synthesis. Other hydroborates can
be obtained by reaction with NaBH4 to give
different reductive capabilities (e.g., NaBH3 CN
[25895-60-7] ) [112].
Additional applications are extensive, e.g.,
electroless plating [113], blowing agent for cel-
lular plastics [114], removal of heavy metals
from waste streams [115], polymerization cat-
alyst [116], and hydrogen source for fuel cells
[117]. The B3 H− 2− 2−
8 , B10 H10 , and B12 H12 may
also find use in the latter application. The qua-
ternary ammonium salt of B3 H−
8 [33055-82-2]
is used as a fogging agent in photographic
film [118]. Chloro derivatives of B10 H2− 10 and
B12 H2−
12 lithium salts have been used as battery
electrolytes [119]; B12 H11 SH2− [12448-23-6]
was useful in a study of neutron-capture therapy
in brain tumors [120].
5.4. Carbaboranes
Carbaboranes are boron hydrides with one to
four of the polyhedral sites occupied by car-
bon atoms. The carbon atom, like the cage boron
atoms, can bond singly to hydrogen, carbon, etc.
The number of known substituted carbaboranes
is very large [121], [122] and has grown rapidly.
The largest body of literature is based on 1,2-
dicarba-closo-dodecaborane(12) [16872-09-6],
o-carborane, 1,2-C2 B10 H12 , M r 144.23, mp
285 –287 ◦ C, and its derivatives (for cage num-
bering system see [121] ).
Production. 1,2-Dicarba-closo-dodeca-bo-
rane(12) is prepared from B10 H14 , a Lewis
base, such as dialkyl sulfide, and acetylene
[123]. C-Substituted derivatives can be read-
ily prepared from substituted acetylenes or from
lithio reagents, such as 1,2-Li2 -1,2-C2 B10 H10
[22220-85-5] [121].
Heating 1,2-C2 B10 H12 under inert condi-
tions at 450 – 500 ◦ C gives 1,7-C2 B10 H12 ; at
600 ◦ C it gives a mixture of 1,7-C2 B10 H12
and 1,12-C2 B10 H12 [20644-12-6], sometimes
called the meta and para isomers, respectively.
There is a large body of literature on the rest
of the C2 Bn Hn+2 family (n = 3 – 10) [124], but
the members having n < 10 are of little commer-
cial significance.
One boron atom may be removed from
1,2-C2 B10 H12 and 1,7-C2 B10 H12 to yield the
open-cage species nido-7,8-C2 B9 H− 12 and nido-
7,9-C2 B9 H−12 , respectively. Further degradation
yields arachno-boranes (e.g., C2 Bn Hn+6 ) as
well as nido and closo species [125].
The nido cages have been compared with cy-
clopentadienide ion as ligands for transition met-
als. Indeed, a rather large number of transition-
metal carbaborane complexes are known [126].
Complexes with two carbaborane cages sand-
wiching a transition metal are common, e.g.,
Co(B9 C2 H11 )− 2 , whereas cages containing two

transition metals, usually also bonded to cy-
clopentadienide, are also known. Some smaller
carbaboranes form multidecker complexes with
transition-metal cyclopentadienyls [127].
Carbaboranes, like polyhedral boranes, un-
dergo Friedel-Crafts halogenation, although
halogenation is complete only for the chlorine
derivative [121].
Uses. The early development of carbaborane
substitution chemistry was propelled by the
search for polymers that would be heat stable
at very high temperatures. Polyesters, siloxanes,
chains linked with Si, Ge, S, and others were in-
vestigated [121].
A short review of structure – property corre-
lations for linear polycarborane – siloxanes has
been published [128]. Much of the original work
on poly-1,7-carboranylsiloxanes was done at
Olin Corp., which formed a company (Dexsil
Chemical Corp.) to market the materials under
the trade name Dexsil. Early hopes were that
markets would grow for high-temperature seals,
gaskets, O-rings, and coatings. However, costs
and therefore prices have remained too high to
justify most such uses.
One application that may remain eco-
nomically viable is the use of poly-1,7-
carboranylsiloxanes as stationary phases for
high-temperature gas chromatography. For ex-
ample, Dexsil 300 GC is a low-melting solid that
can be used up to 450 ◦ C and even at 500 ◦ C for
short times. A bibliography of their use in gas
chromatography is available [129].
Carbaboranes have been attached to halo-
substituted cyclotriphosphazines. A heat-
resistant linear polymer is formed when the
monomer is heated [130].
If the residual Cl atoms are replaced with
hydrocarbyloxy groups in the polymer, boron
atoms can be removed by piperidine to form
nido cages, which can complex with transition
metals, such as Rh. These polymeric metal com-
plexes might be useful as immobilized catalysts
with high temperature stability [131].
A series of rhodacarborane complexes that
exhibit high activity as hydrogenation or alkene
isomerization catalysts has been developed
[132]. One of the most active homogeneous hy-
drogenation catalysts ever reported is closo-1,3-
[µ(η 2 -3-CH2 =CHCH2 CH2 )-3H-3-P(C6 H5 )3 -
3,1,2-RhC2 B9 H10 [76166-14-87], containing
Boron Compounds 13
a chelating 3-butenyl side chain attached to
the carborane cage. Hydrogenation produces
a noncoordinating butyl group, freeing up an
uncoordinated site on the rhodium [133]. The
alkene – metalloborane catalyst may be bound
to a suitable polymer for use as a heterogeneous
catalyst [134].
Thermal reaction of 1,3-dicyanobenzene in
the presence of 1,2-dicarba-closo-dodecabor-
ane(12) produced s-triazines [135].
1-Alkyl-1,2-dicarba-closo-dodecabor-
anes(12)(especially the n-hexyl derivative)
have found use in solid aluminum compos-
ite propellants as burning rate enhancers [136]
based on OH- or CO2 H-terminated polybutadi-
enes. Exceptionally high burning rates have
been achieved when part of the NH4 ClO4
oxidizer was replaced by carboranyl diferro-
cenylmethyl perchlorate or methyltricarboranyl-
methyl perchlorate [61919-09-3] [137]. A se-
ries of nido – closo dicage monoanions exhib-
ited high antifungal activity. The combination
of lipophilic closo-carboranyl groups with hy-
drophilic nido-dicarbollide anions may lead to
the antimicrobial activity [138]. A review covers
the physiology of various carbaborane deriva-
tives [139].
Several carbaborane derivatives may find
use in boron neutron-capture cancer therapy
(BNCT), based on the high cross section of 10 B
for thermal neutron capture. The products are
an α particle and a 7 Li ion with an average ki-
netic energy of 3.8 × 10−13 J. Use of boranes in
BNCT has been reviewed [139, pp. 610 – 631].
p-[1,2-Dicarba-closo-[1-3 H]-dodeca-bo-
rane(12)-2-yl]benzenediazonium chloride
[82187-51-7] was complexed with goat anti-
CEA IgC (carcinoembryonic antigen im-
munoglobin C), and the antibody lost little im-
munoreactivity up to five carbaborane cages per
molecule [140]. Thus carbaborane-substituted
tumor-specific antibodies may be a good method
of concentrating 10 B in tumors, a goal for many
years.
An approach to treatment of hormone-
sensitive tumors is to attach carbaborane cages to
estradiol or testosterone [141]. Growth of human
breast cancer cells was equally stimulated by 17-
α-carboranylestradiol [85197-15-5], Carbestrol
[142].
Carbaborane-substituted polyphosphonates
have shown a high affinity for calcified tissues.
14 Boron Compounds
They may be useful for BNCT of calcific tumors
[143].
6. Organoboranes
6.1. Alkyl- and Arylboranes
Physical Properties. Mono- and dialkylbo-
ranes usually associate as dimers through hy-
drogen bridges (see Fig. 1). However, if the
alkyl group is bulky, i.e., sterically hindered, the
mono- or dialkylborane can exist in monomeric
form, e.g., thexylborane [3688-24-2]. The bulk-
iness of the alkyl group considerably affects the
properties of the borane. Compounds containing
large hindered groups often are solid products,
and as the size of the group decreases, the normal
state of the compound goes from solid to liquid
to gas. Properties of selected organoboranes are
given in Table 6.
Chemical Properties. Generally the
organoboranes are very reactive with oxygen
and total exclusion is recommended on han-
dling. The low homologues (methyl to butyl)
are spontaneously combustible (pyrophoric) in
air. Although dilution of the alkylboranes to
about 15 wt % in an inert solvent reduces the py-
rophoricity, oxidation by air still occurs. The tri-
alkylboranes do not form strong donor-acceptor
complexes with ethers, but other stronger Lewis
bases form complexes, and stabilization toward
oxidation is dependent upon steric factors. The
trialkylboranes are insoluble in and unreactive
with water. They are not readily protonated by
water or alcohols, amines, or mineral acids; how-
ever, they are readily protonated by carboxylic
acids. They are soluble in and unreactive with
aliphatic and aromatic hydrocarbons.
Triarylboranes are generally solid, less sen-
sitive to oxygen, and also unreactive with water.
Table 6. Properties of selected organoboranes [144], [145]
Formula CAS registry no.
(CH3 )3 B [593-90-8]
(C2 H5 )3 B [97-94-9]
(C4 H9 )3 B [122-56-5]
[(CH3 )2 CHCH2 ]3 B [1116-39-8]
(C6 H5 )3 B [960-71-4]
(C2 H5 )2 BCl [5314-83-0]
(C4 H9 )2 BCl [1730-69-4]
Triorganoboranes can be stored indefinitely
at ambient temperature under an inert atmo-
sphere. Decomposition occurs at elevated tem-
perature: tetraethyldiborane [12081-54-8] is one
of the pyrolysis products from triethylborane,
and butene is observed from tri-n-butylborane at
100 ◦ C after an extended period of time. Isomer-
ization and cyclization occur at > 200 ◦ C, giving
complex mixtures. Alkylhaloboranes, like the
trihalides, react with water, alcohols, and alkox-
ides, and cleave ethers to yield the corresponding
derivatives of boron acids [146].
Production. Two general methods of pro-
ducing trialkylborane compounds are alkylation
and hydroboration. Alkylation of readily acces-
sible boron compounds, borate esters, or prefer-
ably boron halides is accomplished with organo-
metallic compounds of Mg (Grignard reagents),
Zn, Al, Sn, and alkali metals:
where R is alkyl. Aluminum alkyls are least
expensive and therefore the preferred alkylating
agents in commercial production of trialkylbor-
anes. The exothermic reaction can be controlled
at < 100 ◦ C and the product is easily distilled
[147]. Grignard reactions are especially useful
in producing trimethylborane as well as arylbo-
ranes. Triphenylborane has been prepared by
reacting finely divided sodium metal with a
haloaromatic and a secondary alkyl borate es-
ter [148]; it is made commercially by Du Pont
(USA). Hydroboration [66] can be conducted
in various ways, i.e., by direct addition of dibo-
rane to the olefin at 30 – 50 ◦ C, or by use of a
Lewis base as a reaction medium, with THF
mp, ◦ C bp, ◦ C (kPa) Density, g/cm3 (◦ C)
−160 −21.8 (101.3) 0.63 (−100)
− 93 95 (101.3) 0.685 (20)
− 34 170 (29.6) 0.756 (20)
− 88 88 (3.1) 0.731 (30)
142 203 (2.0) –
− 84.6 78.5 (101.3) –
– 173 (101.3) 0.879 (20)

and (CH3 )2 S being preferred. Various alkylbo-
ranes are commercially available by this method
(Callery Chemical Co., Aldrich Chemical Co.,
Ventron).
As the olefin becomes bulkier, fewer addi-
tions can be made. A tetrasubstituted olefin usu-
ally forms only the monoalkylborane. Lewis
base adducts of the mono- and dichloroboranes
yield the mono- and dichloroalkylboranes when
reacted with olefins. These can be converted to
their respective di- and monoalkylboranes by
hydride addition [149]. Mixed trialkylboranes
were obtained using this method [150].
Uses. Organoboranes are finding an ever in-
creasing role in organic synthesis. Mono- and
dialkylboranes have been used as stereoselec-
tive reducing agents, and asymmetric synthe-
sis, hydroborations, and reductions have been
accomplished using organoboranes [151]. Such
reactions are most significant for their biolog-
ical application in the pharmaceutical industry,
and may mean a small but cost effective use of
alkylboranes.
Significant volumes of trialkylboranes are
used in catalytic polymerization of ethylene,
vinyl derivatives (acetates and halides, acrylic
acid, acrylonitrile, and methyl methacrylate)
[152–154]. Free radicals are formed during au-
toxidation of the trialkylborane or during the
decomposition of the resulting peroxides [155],
[156]. Unique products have also been obtained
with copolymers and graft polymers. Water-
resistant dental and surgical adhesives having
high binding power and being nonirritating to
tissue have been developed using alkylborane as
a catalyst [157], [158]. The amine complexes of
triarylboranes can be used as catalysts for homo-
and copolymerization of acrylic monomers.
Several reactions of organoboranes have pos-
sible applications in the petroleum industry
[159]. Economics remain unfavorable because
of high costs of the organoborane and equip-
ment to implement recycle. Amine complexes
of the trialkylboranes have been used as addi-
tives to increase the cetane rating of diesel fuels.
The complexes also inhibit sludge formation in
fuel oils.
Triethylborane, because of its ease of oxida-
tion, provides rapid ignition of nonhypergolic
fuel in aircraft, and serves as an additive to pre-
vent flameout and increase flame speed.
Boron Compounds 15
Lithium and potassium hydride complexes of
trialkylboranes are highly reactive and selective
reducing agents, and have found small but grow-
ing commercial applications.
The tetraarylborates(1−) are used in chemi-
cal analysis because of their low solubilities with
specific cations (K, Cs, Rb, Ag, Tl). This prop-
erty can also be used to remove these materials
from various chemical waste streams.
The production of organoboron compounds
is relatively small compared to other organome-
tallic chemicals. Expensive raw materials and
low volume of production tend to keep manu-
facturing costs high.
6.2. Borinic and Boronic Acids
Borinic and boronic acids are the mixed
hydroxyorganoboranes R2 BOH and RB(OH)2 ,
respectively. Two commercially available acids
are: phenylboronic acid [98-80-6], phenyl-
boric acid, C6 H5 B(OH)2 , M r 121.93, mp
217 – 220 ◦ C; and diphenylborinic acid – eth-
anolamine complex [524-95-8], 2-aminoethyl
diphenylborinate, (C6 H5 )2 BOCH2 CH2 NH2 ,
M r 225.10, mp 192 – 194 ◦ C. Replacement of
the organo group by hydroxyl changes the prop-
erties of the boranes dramatically. Most of them
are stable, water soluble, less susceptible than
triorganoboranes to autoxidation, and do not
initiate olefin polymerization. Their acidity is
dependent on the organo moiety, with the aryl
derivatives being the more acidic. The anhy-
drides of borinic acids are the boroxines, trimeric
cyclic (RBO)3 compounds, whereas the anhy-
drides of the boronic acids are R2 B−O−BR2 .
Production. These acids have been pre-
pared by Grignard synthesis. Borate esters
give methyl-substituted acids [160]. Alkyl
acids can readily be prepared from hydrobo-
ration of olefins using complexes of halobo-
ranes followed by hydrolysis. Rearrangement
of triorganoboranes with triorganoborates yields
esters, which are susceptible to hydrolysis to the
acids.
Uses. The acids are of great interest because
they are utilized in the production and reactivity
of biologically active compounds. Boronic acids
have been prepared in high optical purity for
16 Boron Compounds
application in organic synthesis [161]. Specific
boronic acids have been found to inhibit the cat-
alyzed hydrolysis of enzymes [162]. Stabilizers
are also formed from phenols and arylboronic
acids. Benzeneboronic acid derivatives, such as
cyclic condensation products with o-aminophe-
nol and pyrocatechol, have a sterilizing effect on
insects (flies) [163]. Also, compounds of ben-
zeneboronic acid are stimulants for plant root
growth. The acids are used in chromatographic
columns to enhance separation. They also serve
as inhibitors for the autoxidation of fuels and
mineral oils.
6.3. Borazines
Borazine [6569-51-3], s-triazaborane, B3 N3 H6 ,
M r 80.53, sometimes called inorganic benzene,
is a low-boiling liquid (bp 55 ◦ C, mp −58 ◦ C),
consisting of a six-membered ring containing al-
ternating boron and nitrogen atoms, each bonded
to a hydrogen atom.
Production. Borazine can be prepared by
copyrolysis of NaBH4 and NH4 Cl in a high-
boiling glyme [164], by reduction of trichloro-
borazine [933-18-6] [165], or by pyrolysis of
ammonia borane in diglyme [166].
A large body of literature exists on the prepa-
ration and chemistry of symmetrically and un-
symmetrically substituted borazines [167]. B-
Substituted trihaloborazines, readily prepared
from BX3 and NH4 Cl, react with Grignard
reagents to give symmetrical trialkyl- or tri-
arylborazines. Symmetrically substituted N-
trialkyl- or N-triarylborazines are readily pre-
pared from LiBH4 and RNH3 Cl, or by pyrolysis
of RNH2 BH3 .
Borazine is thermally stable at 0 ◦ C, but de-
composes slowly at ambient temperature. Bo-
razine hydrolyzes slowly, but trihaloborazines
hydrolyze quite rapidly. Hydrogen halides form
1 : 3 adducts with borazine, which decompose
to trihaloborazines on warming.
Uses. Films that were deposited thermally
from borazine vapor were found to be too re-
active to be suitable for fabricating masks for
X-ray lithography [168]. However, films con-
taining predominately cubic boron nitride, CBN
[10043-11-5], were deposited using ions ex-
tracted from a borazine plasma via an ion beam.
Very hard, adherent films were deposited on ce-
ramic, glass, stainless steel, etc. [169]. An obvi-
ous practical application is the hardening of tool
surfaces to markedly extend their life.
A thermally deposited film of hexagonal BN
[10043-11-5], from B3 N3 Cl6 [19087-72-0] at
900 ◦ C, protected SiO2 tubes from halide cor-
rosion [170].
A copolymer between 2,4,6-tributylborazine
[7325-06-6] and an unsaturated N,N  -
hexamethylenebiscarboxamide was useful for
hardening epoxy resins [171]. Trichloroborazine
was used as part of a catalyst mix for the poly-
merization of propene [172].
Flexible BN coatings on copper or copper-
base alloys were formed from gaseous 2,4,6-tri-
chloroborazine. The films were stable to 700 ◦ C
in air [173].
6.4. Boric Acid Esters
The first boric acid esters were prepared in
1846 by reactions of aliphatic alcohols with
boron trichloride [174] and represent the ear-
liest known examples of organoboron com-
pounds. Simple boric acid esters have the for-
mula B(OR)3 , where R can be alkyl or aryl; re-
lated compounds, such as boroxines, (ROBO)3 ,
as well as boric acid esters of di- and poly-
functional hydroxy compounds can be prepared
readily and are included in the general category
of boric acid esters. The IUPAC committee on
boron chemistry suggested naming simple boric
acid esters as trialkoxy- and triaryloxyboranes,
and this nomenclature has been adopted by the
American Chemical Society [175] and by Chem-
ical Abstracts. However, this system is not nor-
mally used in industry or in the scientific lit-
erature, where these compounds continue to be
referred to as boric acid esters, alkyl (or aryl)
borates or orthoborates, trialkyl (or aryl) borates
or orthoborates, and (rarely) boron trialkoxides
or aryloxides. For example, the most common
derivatives are usually referred to as methyl bo-
rate, ethyl borate, phenyl borate, etc. Extensive
discussions of the chemistry of boric acid esters
can be found in [176], [177].

Table 7.Properties of some boric acid esters
Physical Properties. Boric acid esters range
from colorless, low-boiling liquids to high-
melting solids. Physical properties of some of
the more common materials are given in Table 7.
For a more extensive compilation see [176],
[178]. Boric acid esters are monomeric com-
pounds generally soluble in organic solvents.
They dissolve in water with hydrolysis to boric
acid and the corresponding alcohol or phenol.
Chemical Properties. Alkyl boric acid es-
ters from straight-chain alcohols and aryl boric
acid esters are stable to relatively high temper-
atures. Branching in the alcohol chain leads to
reduced stability.
Most boric acid esters react readily with wa-
ter to yield boric acid and the respective alcohol
or phenol, and this tendency to react with atmo-
spheric moisture has seriously restricted their
general utility. Reactivity toward water can be
modified by either steric or electronic effects
as shown by the improved hydrolytic stabil-
ity of compounds, such as tri-tert-amyl borate
[22238-22-8] and triethanolamine borate. Com-
parative hydrolysis rates have been reported for
a number of boric acid esters [179].
Boron Compounds 17
Other reactions of boric acid esters include
the formation of amine complexes, transesterifi-
cation, usually by displacement of lower boiling
alcohols by higher boiling alcohols or phenols,
reactions with organometallic reagents to form
alkylboranes, and reactions with metal hydrides
to produce boron hydrogen compounds.
Preparation. Boric acid esters have been
prepared in the laboratory by a variety of meth-
ods, but the standard approach involves the re-
action of boric acid with alcohols or phenols:
B(OH)3 + 3 ROH
B(OR)3 + 3 H2 O
This equilibrium reaction, which favors the hy-
drolysis products boric acid and ROH, is dis-
placed to the right by using excess alcohol and
removing water by azeotropic distillation with
hydrocarbon solvents. This procedure is com-
plicated in the case of methyl and ethyl borates
by the formation of azeotropes between the alco-
hols and the boric acid esters. A closely related
method in which boric oxide is substituted for
boric acid has also been used.
The relatively easy transesterification of
boric acid esters results in ready displacement
of lower boiling alcohols and the preparation of
higher molecular mass alkyl and aryl derivatives.
18 Boron Compounds
A number of less practical laboratory procedures
for boric acid esters have been reported, starting
with boron halides, trisaminoboranes, and other
boron-containing compounds.
Production, Economic Aspects. No pub-
lished data are available on manufacturing pro-
cesses for boric acid esters or on their annual
production rates. Commercial usage is very lim-
ited except for the internal production of methyl
borate by the Ventron Division of Morton-
Thiokol. This ester is a key intermediate in
the Ventron process for sodium borohydride.
Some additional quantities of methyl borate
and its methanol azeotrope are used in welding
and brazing applications. Other commercially
available boric acid esters include ethyl borate,
n-propyl borate, isopropyl borate, n-butyl bo-
rate, and cresyl borate. A number of boric acid
esters prepared from butylene and hexylene gly-
cols are also available commercially, as well as
methyl and isopropyl boroxines. Probably, all
of these compounds are prepared by the stan-
dard reactions of boric acid with the appropriate
alcohols or phenols.
Prices for the commercially available boric
acid esters are relatively high because of their
limited usage. At higher production volumes
these prices would be reduced significantly.
Methyl borate was available in 1985 at ca. $ 3/kg,
and the other esters are generally in the range of
$ 3 to $ 10/kg.
Uses. Methyl borate is the boric acid ester of
greatest commercial interest because it is used
internally for the production of sodium borohy-
dride (and diborane). Methyl borate azeotrope is
used as a gaseous flux for brazing and welding,
particularly in Europe.
Although numerous patents have been issued
on the use of boric acid esters as polymer addi-
tives, this application apparently has remained
small unless there are proprietary uses that have
not been disclosed. Application of small quan-
tities of several derivatives as epoxy resin cur-
ing agents has continued with little measurable
growth. Despite wide patent coverage, boric acid
esters have not been used in any quantity for
polymer stabilization. In the 1950s and 1960s
boric acid esters derived from glycols were used
extensively as gasoline additives. A mixture of
these glycol derivatives is being manufactured
by U.S. Borax & Chemical Corp. under the trade
name Biobor JF for the control of microorgan-
isms in fuel systems containing water. This prod-
uct can be used successfully in jet fuels, diesel
fuels, and fuel oil systems that have water con-
tamination.
Borate esters have also been patented for use
as flame retardants for cotton batting, modi-
fiers for the oxidation of hydrocarbons, start-
ing materials for the preparation of trialkylbor-
anes, such as triethylborane and triphenylbo-
rane, wood preservatives, hydraulic fluids (par-
ticularly alkylated glycol borates), and lubri-
cants.
Transportation, Handling. Shipping regu-
lations for boric acid esters vary depending on
the nature of the alcohol or phenol that is bound
to boron. Lower molecular mass derivatives have
very low flash points, and those derived from
alcohols containing one to four carbon atoms
must be labeled as flammable, and shipped and
stored accordingly. Higher molecular mass com-
pounds present no particular difficulty except in
specific cases, such as the easily hydrolyzed bo-
rates derived from phenols. Boric acid esters in
general hydrolyze rapidly and their exposure to
the atmosphere should be minimized. Particu-
larly reactive compounds should be transferred
and stored in a moisture-free atmosphere of ni-
trogen or other inert gas.
Shipping in metal cans or drums is normally
acceptable except in cases where hydrolysis can
lead to a corrosive product, such as a halogenated
alcohol.
Toxicology. The published toxicities of the
most common boric acid esters vary from acute
oral LD50 s of ca. 400 mg/kg in rats for aro-
matic borates to 1200 – 2100 mg/kg for simple
aliphatic esters. These toxicities are directly re-
lated to the toxicity of the alcohol or phenol pro-
duced on hydrolysis.
7. Toxicology and
Occupational Health
The toxicology of boron compounds has been re-
viewed in 1980 [180]. Experimental animal tox-
icity data, cases of human exposures, industrial
 Boron Compounds 19
Table 8. Maximum concentrations in the work environment [184], [185]

CAS TWA STEL MAK

3 3
registry no. ppm mg/m ppm mg/m ppm mg/m3

Diborane(6) [19287-45-7] 0.1 0.1 – – 0.1 0.1

Pentaborane(9) [19624-22-7] 0.005 0.01 0.015 0.03 0.005 0.01
Decaborane(14) [17702-41-9] 0.05 0.3 0.15 0.9 0.05 0.3

hygiene, and medical treatments are discussed.
There are also other readily accessible sources of
information [181], [182]. Diborane(6) is primar-
ily a pulmonary irritant [183]; TLVs and MAKs
are given in Table 8 [184]. Overexposure causes
respiratory tract injury, and secondary infections
may follow [186]. Prolonged exposure to low
concentrations causes headaches and other cen-
tral nervous system (CNS) effects [187]. Dibo-
rane is a flammable gas and must be handled
in a closed system. Pentaborane(9) and decabo-
rane(14) affect the CNS and can have effects that
may be delayed for up to 48 h [187]. TLVs have
been set (see Table 8) [184]. Pentaborane(9) is
a liquid which should be treated as pyrophoric
and must be handled in a closed system. Decabo-
rane(14) is a solid but has sufficient vapor pres-
sure at room temperature to make it a hazard
by inhalation, as well as by the dermal and oral
routes [188].
Animal toxicity testing of amine boranes has
shown that they also affect the CNS [189]; how-
ever, no TLVs or MAKs have been set for them.
Toxicity is affected by the number and kind of
substituents and varies from compounds that are
highly toxic to those with low toxicity [189],
[190].
The few toxicity studies on borohydrides
show that they are corrosive to the skin and eyes
[191]. When ingested, sodium borohydride pro-
duced death from gas embolism in animals.
The lower trialkylboranes have some toxic-
ity to small rodents at nonpyrophoric concentra-
tions in air [180], [192].
Toxicity of carbaboranes depends mainly on
the nature of the substituents [180], [193].
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