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3.4. Sodium Tetrahydridoborate

Properties . (See table 2)Sodium tetrahydridoborate, sodium borohydride,

sodium boranate, NaBH4 , is a white, slightly hygroscopic salt that is stable
in dry air up to 300 C. It decomposes slowly in a vacuum at 400 C, quickly
above 550 C, with liberation of hydrogen; mp (under 1 MPa H2) 505 C. If
ignited with a naked flame it burns quietly. It can be stored in an airtight
container for many years without decomposition.
Sodium borohydride absorbs water from moist air to form the dihydrate,
NaBH4 2 H2O, which slowly decomposes to form sodium metaborate and
hydrogen. In acidic media rapid hydrolysis takes place:

BH4 + H+ + 3H2O __> H3BO3+ 4 H2;

D H = 372 kJ/mol

Sodium borohydride, in keeping with its ionic character, is readily soluble in

polar solvents, especially protic compounds such as water, lower alcohols,
and amines (see Table (4)).
With a few solvents it forms isolable though not very stable solvates (37). In
protic solvents, solvolysis occurs, and hydrogen is evolved:

NaBH4 + 4 ROH __> NaB(OR)4 + 4 H2

Thus, sodium borohydride is 80 % decomposed after 1 h in methanol at 0

C, 6 % decomposed after 1 h in ethanol at 60 C, but is stable in 2-propanol
and tert-butanol and at room temperature. The solubility and stability in
water, the most frequently used solvent, have been extensively investigated
(45) (see Fig. (4)). Protonolysis takes place in aqueous solution, the rate
increasing rapidly with increasing temperature and decreasing pH (1). These
solutions become more stable with increasing concentration of sodium
borohydride. At 24 C, a 102 M solution (pH = 9.56) decomposes to the
extent of 15 % in 1 h, whereas a 0.10 M solution (pH = 10.05) undergoes
only 5 % decomposition in the same time. On boiling or on acidification,

however, rapid hydrolysis occurs and all the combined hydrogen is released
(2.36 L/g at STP). A number of transition metal salts and finely divided
metals such as nickel, cobalt, iron, and copper (1) , (46) catalyze the
hydrolysis, but the addition of strong bases such as NaOH can stabilize
solutions of NaBH4 (Fig. (5)).

A solution of sodium borohydride in concentrated sodium hydroxide can be

stored virtually without decomposition, although concentrated solutions of
sodium borohydride in dimethylformamide must not be heated because of
the danger of explosion caused by autocatalytic decompositions; such
solutions should not even be stored for long periods at room temperature
(47). Contact with strong acid (e.g., concentrated sulfuric or phosphoric
acid, or methanesulfonic acid) or Lewis acids must be avoided as these
substances can liberate diborane, which is highly toxic and spontaneously
flammable.

Sodium borohydride is a powerful reducing agent with wide applications in

inorganic and particularly organic chemistry. The redox potential E0 of the
half reaction

BH4 + 8 OH __> B(OH)4 + 4 H2O + 8 e

at pH 14 is 1.24 V.

An aqueous solution of sodium borohydride will reduce a number of cations

and anions, the product obtained depending on the nature of the ion and
the reaction conditions. A metal ion of lower valency can be produced (e.g.,
iron(II) from iron(III)), a metal (e.g., all the platinum metals, cadmium,
mercury, lead, silver, and gold), a metallic boride (CrB2, Co2B, Ni2B), or a
hydride (GeH4, SnH4 , AsH3, BiH3). Many of these reductions are used for
the recovery of noble metals, the precipitation of toxic metals from water,
the preparation of f inely divided metals, and the electroless deposition of
metals and metallic borides onto metallic and nonmetallic substrates (48) ,
(49).

Another reaction of industrial importance is the reduction of sulfur dioxide or

sodium hydrogen sulf ite to sodium dithionite:

NaBH4 + 8 NaOH + 8 SO2 __> 4 Na2S2O4 + NaBO2 + 6 H2O

The reducing power of sodium borohydride towards some important

functional groups is shown in Table (3). This reveals that NaBH4 is a rather
milder but also more selective reducing agent than NaAlH4 , allowing the
reduction of aldehydes, ketones, acid chlorides, and imines in the presence
of esters, epoxides, amides, nitriles, or nitro groups. Much research has
been undertaken with the object of varying the reducing power over a wide
range (50) , e.g., by mixing sodium borohydride with metal salts (Pd(NO3)2 ,
AlCl3 , CoCl2 , NiCl2), thiols (e.g., ethanedithiol), or carboxylic acids (e.g.,
acetic acid, trifluoroacetic acid), by using different solvents (e.g., aprotic
solvents or solvent mixtures) (51) , or by using phase transfer catalysts (52).

A solution of NaBH4 TiCl4 (ca. 3 : 1) in 1,2-dimethoxyethane reduces

carboxylic acids to alcohols and nitro compounds to amines. The NaBH4
CoCl2 system dissolved in lower alcohols or dioxane is also effective for
these reductions, as well as the reduction of sulfoxides to sulfides and the
hydrogenation of alkenes. Lithium chloride and sodium borohydride
dissolved in diethylene glycol dimethyl ether form the intermediate LiBH4
which, unlike NaBH4 , can reduce esters and epoxides. Sodium
triacetoxyborohydride, NaBH(OAc)3 , produced in situ from NaBH4 and three
equivalents of acetic acid, exhibits such a weakening of reducing power that
aldehydes are selectively reduced without ketones being affected (53).
Sodium borohydride and boron trifluoride in diglyme or THF yield diborane:

3 NaBH4 + 4 BF3 OEt2 __> 2 B2H6+ 3 NaBF4 + 4 Et2O

Diborane is used mainly for hydroboration, but also acts as a strong

electrophilic reducing agent, reducing carboxylic acids and nitriles but not
acyl chlorides or nitro groups (54).

Sodium borohydride is also an important starting material for the production

of tetrahydridoborates (borohydrides) of other metals, and of boranes and
organoboron compounds, their derivatives and adducts [1]. Some examples
of practical importance are:

Production. Since the discovery of sodium borohydride in 1942 by H. J.

SCHLESINGER, H. C. BROWN, H. R. HOECKSTRA, and L. R. RAPP (55) , over
100 methods of preparation have been described, but few of these have
achieved any practical significance. Industrial production in the United
States started in 1954 using the Schlesinger process (56) , in which

trimethyl borate reacts with an extremly fine dispersion of sodium hydride in

a high boiling hydrocarbon oil at 250 280 C and atmospheric pressure:

4 NaH + B(OCH3)3 __> NaBH4 + 3 NaOCH3

Water is then added, causing separation of the hydrocarbon oil, which is

recirculated. The aqueous phase contains the NaBH4 together with caustic
soda and methanol formed by hydrolysis of NaOCH3. The methanol is
recovered by distillation and used again for production of trimethyl borate.
The product solution contains 12 % NaBH4 and 42 % NaOH (r = 1.4 g/cm3 ;
h23 = 79 mPa s) and is sometimes marketed as Sodium Borohydride SWS
by Ventron or alkaline aqueous solution by Nokia. Solid sodium borohydride
is obtained from the alkaline aqueous solution by extraction with
isopropylamine; the yield is better than 90 %.

A process developed by Bayer (57) (see Fig. (6)) uses finely ground
borosilicate glass, sodium, and hydrogen:
Na2B4O7 7 SiO2 + 16 Na + 8 H2 __> 4 NaBH4+ 7 Na2SiO3
The borosilicate Na2B4O7 7 SiO2 is produced by fusion of borax and silica.
The borosilicate is cooled, ground, and then reacted with sodium in an
atmosphere of hydrogen at 300 kPa and 400 500 C in a partly
heterogeneous reaction. The sodium borohydride is extracted from the
borohydride silicate mixture with liquid ammonia under pressure. The yield
is in excess of 90 %. Other processes are described in Refs. (1) , (5), and
(57).

Commercial sodium borohydride is in powder lump form (bulk density 0.4

0.5 kg/L), the purity being typically 98 % (Bayer, Chemetall, Ventron).

Analysis. Two main methods are used for the analysis of sodium
borohydride: one gas volumetric and the other titrimetric. In the f irst of
these, the sodium borohydride is reacted with acid and the evolved
hydrogen measured. The second method is equally straightforward and
requires no special analytical equipment. The sodium borohydride is
converted to metaborate by reaction with excess oxidizing agent such as
sodium hypochlorite or potassium iodate:

NaBH4 + 4 NaOCl __> NaBO2+ 4 NaCl + 2 H2O

The excess oxidizing agent is determined by iodometric back-titration (48) ,

(49).
Uses. The present annual consumption of sodium borohydride is estimated
to be 2000 3000 t, mainly in the form of the 12 % solution. This means
that it is by far the most important commercially available complex hydride.
The largest amount is used in the paper and pulp industries, mainly in the
United States and Scandinavia. The 12 % solution (Ventron, Nokia) is used
for the in situ production of sodium dithionite, which is used to bleach wood
pulp. Both sodium dithionite (made from sodium borohydride and sulfur
dioxide) and sodium borohydride itself are used for reducing vat dyes to the
leuco bases (58). A recent patent claims that the reaction with sulfur dioxide
can be used for the purification of exhaust gases from power stations
burning fossil fuel (59).
Solid sodium borohydride is used as a reducing agent in the organic
chemical and pharmaceutical industries, and although the quantities used
for this purpose are considerably smaller than the demands of the paper
industry, the selective reduction of aldehydes and ketones has become of
major importance (24). One of the biggest uses is in the stereoselective
reduction of steroid ketones. Another is the synthesis of antibiotics such as
chloramphenicol, dihydrostreptomycin, and thiophenicol, and also vitamin A.
Other examples are reduction in the synthesis of prostaglandins, atropine,
scopolamine, and flavorings and aromas.

Sodium borohydride is also used for cleaning and stabilization of process

streams of many organic products. It chemically reduces harmful impurities
such as aldehydes, ketones and peroxides, thereby improving color, odor,
and the stability of the products towards heat, light, and oxidation. The
technique is used in the production and subsequent treatment of epoxides,
alcohols, amines, ethers, esters, carboxylic acids, alkenes, polymers (58) ,
and paper (60).

The reduction of metal cations already mentioned is used on a large scale

for the electroless deposition of metals and metal borides onto metals and
other materials such as glass, ceramics, and plastics ("Nibodur 1098"
Bayer (61) , for the recovery of mercury from wastewater from the chloralkali electrolytic process (Ventron process, Koertrol) of lead from lead
tetraalkyl production, and of silver and cadmium from spent photographic
developing solutions (62) , (63). Finely divided metals of the iron group for
high quality magnetic tapes are produced by sodium borohydride reduction
(58) , (64). Nickel boride and cobalt boride obtained by the reduction of the
appropriate salt solutions are used as catalysts in gas- and liquid-phase
reduction (58). One final application for sodium borohydride depends on its

ability to generate hydrogen gas: it is used as a foaming agent for organic

polymers and inorganic construction materials (58) , (65).

(37) B. D. James, M. G. H. Wallbridge: "Metal Tetrahydroborates," Prog.

Inorg. Chem. 11 (1970) 99 231.
(45) E. H. Jensen: A Study on Sodium Borohydride, Nyt Nordisk Forlag,
Arnold Busck, Copenhagen 1954.
(1) Gmelin
(46) A. Levy, J. B. Brown, C. J. Lyons, Ind. Eng. Chem. 52 (1960) 211.
(47) D. A. Yeowell, R. L. Seaman, J. Mentha, Chem. Eng. News 57 (Sept. 24,
1979) 4.
(48) Bayer AG, Firmenschrift, Natriumboranat, 1975.
(49) Ventron Corp., Firmenschrift Sodium Borohydride, 1979.
(50) R. C. Wade, J. Mol. Catal. 18 (1983) 273 297.
(51) R. S. Varma, G. W. Kabalka, Synth. Commun. 15 (1985) 985 990.
(52) F. Rolla, J. Org. Chem. 46 (1981) 3909 3911.
(53) G. W. Gribble, C. F. Nutaitis, Org. Prep. Proced. Int. 17 (1985) 317 384.
(54) M. Follet, Chem. Ind. (London) 1986, 123 128.
(55) H. C. Brown: Boranes in Organic Chemistry, Cornell Univ. Press, Ithaka
1972.
(56) H. J. Schlesinger, H. C. Brown, J. Am. Chem. Soc. 75 (1953) 186 205;
H. J. Schlesinger, H. C. Brown, US 2 534 533, 1945.
(57) W. Bchner, H. Niederprm, Pure Appl. Chem. 49 (1977) 733 743.
(5) A. Hajos: Complex Hydrides, Elsevier, Amsterdam 1979.
(58) R. C. Wade, Spec. Publ. R. Soc. Chem. 40 (1981) 25 58.
(59) Gea Wiegand GmbH, DE-OS 3 525 377, 1985 (U. Hochberg, G. Klinke, P.
Sauglet).
(24) A. Kleemann, J. Engel: Pharmazeutische Wirkstoffe, Thieme Verlag,
Stuttgart 1982; Ergnzungsband, Thieme Verlag, Stuttgart 1987.
(60) L. C. Tang, Adv. Chem. Ser. 212 (1986) 427 441.
(61) R. N. Duncan, T. L. Arney, Plat. Surf. Finish. 71 (1984) 49 54.

(62) J. A. Ulman, Spec. Publ. R. Soc. Chem. 61 (1986) 173 196.

(63) M. J. Lindsay, M. E. Hackmann, R. I. Tremblay, Proc. Ind. Waste Conf. 40
(1985) 477 482.
(64)Mitsubishi Denki KK, DE-OS 3 704 075, 1986 (H. Ogama, Y. Fukotomi, M.
Okutani).
(65)Mosc. Eng. Cons. Inst., SU 126 167, 1984 (A. P. Merkin, B. M.
Runyantsev, L. E. Vitels).

Taken from Ullman's encyclopedia of industrial chemistry

I will post the tables tommorow, they need a lot of editing to fit this forum