B. D.
James A Non-Hazardous, Bench Top Experiment
University of Queensland
st. Lucia, Q I ~4067,
, Australia
with an Electron-Deficient Compound
Perhaps the most spectacular property of simple elec-
tron-deficient compounds is their marked reactivity with
air and/or moisture. Those who have witnessed a diborane
explosion or a trimethylaluminum fire are usually imbued
with a healthy respect fbr such reagents. Experiments
with these compounds in undergraduate laboratory pro-
grams are generally used to teach the proper use of vacu-
um or inert-atmosphere techniques. There is a danger
that some interesting reaction chemistry may he obscured
in the preoccupation with technique. Also, manipulations
in air-free systems are generally time consuming and ne-
cessitate close instruction from a competent teacher. In
courses where laboratory time is limited or where the
staEstudent ratio is unfavorable, it is my personal view
that such experiments should he avoided. For a course at
this university, CH323: "Organometallic and Electron-
Deficient Compounds," in which only a limited time (14
hrl is available for practical work, an approach to an ex-
periment on an electron-deficient compound has been
made which stresses the properties of the compound rath-
er than the techniques generally employed in the area. A
particularly suitable compound is his(triphenylphosphinel
copper(1) tetrahydrohorate, [ ( C ~ H ~ I ~ P I ~ C Uwhich,
BH~,
while containing the covalent double hydrogen bridge be-
tween copper and boron (I), is unusually stable to air and
moisture and may be handled normally on the hench top
without the usual impediments.
The synthesis, following the procedure of Davidson 121,
is straightforward and reliable. The chemistry involved in
the synthesis is interesting in that the hydrohorate ion,
BH4-, first acts to reduce the copper(II1 species to cop-
per(1). This in turn is stabilized by interaction with the tri-
ohenvlohosohine lieands to eive a n intermediate such as
jrb3~i3ku+.' This copperili "intermediate finally reacts
with further B H a t o yield the hydroborate complex. This
reaction pathway compares with t h a t employed by Cariati
and Naldini (3) who first isolated (<baP)sCuCI,(from CuCl
and rhaP in chloroform) and then reacted it with NaBHa
in ethanol. While both preparations are perfectly reliable,
that of Davidson is recommended in a laboratory program
having restricted time since cuprous chloride does not
have to be prepared (or stored).
The infrared spectrum of the product shows the charac-
teristic vibrations of terminal (2386, 2353 cm-'1 and
bridging hydrogen (1984, 1924 cm-'1 attached to boron. In
common with other covalent metal tetrahydroborates, the
protons bound to horon appear equivalent in the nmr
spectrum, which suggests a rapid intramolecular exchange
pmcess in solution 14). On cooling, the signal sharpens to
a singlet at -160°C. indicating that even the coupling to
the horon nucleus has been lost ("thermal decoupling")
( 5 ) . A similar situation is fbund with the related com-
pound (m3P)ZC~B3H8 in which bridging hydrogens have
also been shown to occur (6). Here, however, on cooling
beyond the thermally decoupled stage, a n asymmetric
splitting of the singlet signal is observed, indicating that a
structure similar to that ihnnd in the crystal is heing oh-
served in solution (71.
Covalent metal tetrahydroborates typically display the
"bridge cleavage" reaction with Lewis bases, which ab-
stract BH3 groups, e.g. (81
260 / Journal ot Chemical Education
With his(triphenylphosphine1copper tetrahydrohorate,
this reaction does not occur (9).hut a ligand-borane ad-
duct (43PBH31 is formed during thermal decomposition of
the compound 12)
The separation of ,b3PBH3 and rh3P may he achieved by
careful extraction. T h e infrared spectrum of 63PBH3 no
longer shows vibrations due to bridging hydrogen (10).
Because of the relatively large number of phenyl protons,
their resonance only is clearly characterized in the proton
nmr spectrum. A weak 1:l:l:l quartet due to coupling
with the boron-11 nucleus (I = 3k) would be expected for
the BH3 group. T h e boron-I1 nmr spectrum, however,
shows an eight-line signal originating from overlapping
~98 H Z and h.i. = 57 Hz (Ti).
quartets due to J l l i , -=
With nmr spectra provided, this synthesis and decom-
position experiment occupies about six hours of student
time. The starting material may also be purchased' if the
instructor wishes toomit the synthesis.
Experimental Procedure
Synthesis of (@3P)2C~BH4
Finely ground CuSOn.5H2O (1 gl is mixed with triphenylphos-
phine (5 gl and ethanol (approximately 80 ml): then the mixture
is stirred and warmed on a hotplate until the blue solid has dis-
solved. (The yellowish solution formed may be decanted fmm any
small amount of blue residue.) Powdered sodium borohydride
(approximately 1 g) is added carefully, with stirring, until precip-
itation is complete and the vigorous effervescence has subsided.
The crude solid is filtered off and extracted into about 50 ml chlo-
roform. The small amount of undissolved, excess sodium borohy-
dride is filtered from the chloroform extract. The filtrate is
warmed an a hotplate until almost boiling and ethanol added
slowly with constant stirring (keeping the solution hot1 until the
faint cloudiness produced changes to h e , white crystals. The so-
lution is allowed to cool. The white cr,vstals ibrmed are filtered off
and air dried. Mp = 167'C (deel. Yields are generally ahout 1.5 g.
A further crop of the compound ma." be obtained by concentra-
tion of the mother liquor.
Thermal Decomposition
About 0.6 g of (</)3Pl~CuBHl in a test tuhe is decomposed gent^
ly over a yellow Bunsen flame with about 1 min of gentle, spas-
modic heating. The residue is allowed to cool and is then extraet-
ed with 3 X 2 rnl of benzene and filtered to remove any hlack
solid particles. The benzcne is evaporated from the filtrate and
the crude solid obtained is extracted with 3 X 2 rnl of ethanol.
Both theethanol filtrate and the residue are retained.
Filtrate: The filtrate is heated gently to hailing (hotplate) and
water is added dropwise, maintaining boiling, until the solution is
permanently cloudy. The mixt~ueis allowed to cool and crystal-
lire. The white crystals are filtered off and air dried. These may
be shown to be triphenylphosphine by their melting point (80'C)
and a mixed melting point with an authentic sample.
- --
'Strern Chemicals Inc.. 150 Andover Street, Danvers, Ma.,
01923.
 Residue: The residue is extracted into ahout 7 ml benzene and 13) Canafi. F..and Naldini. L., G u s chim ln.1.. 91.3.11965).
filtered. The filtrate is concentrated by evaporating some of the
solvent, the beaker removed from the hotplate, and ether added
!r:\w "~ i,p"p~s ~~ d~ .; ~a ~n~ d~ i~ ~~ ~~~K~~M..
S.I.
,"~,";e~~r~~~'f~~~m,Commun,7,,1,l1~7
e dr n.o r ~ .chrm..
R. 2755. I I ~ I .
until the solution becomes cloudy. The solution is set aside to 171 Beall. H.. Bushweller. C. H.. Ikwkett. W. d.. and Grace. M.. .I. ~ m r rc h ~ m
Soc.. 9'2.3484.1197Ul.
crystallize. The crystals are filtered off and air dried. The mp is ,81 B,rd,P.H,,andWallh M , C , H , , Chem ,,ym,,192:1,,196i ),
189°C (4,PBHd. 191 dames. 8. D., Nanda. R. K . , and Wdibridge. M. C.. H.. Innrr. ('hem.. 6. 1Y79.
(19~1.
Literature Cited (101 Frbrh. M . A , Heal. H. G., Mackle. H.. and Madden. I . 0.. J Chem Soc.. 899.
111 Lippard. S . 1 . and Melmed. K . .M..lnorg Chem.. 62223,119671. llY6Sl.
121 Davidson..J.M.. Chem ind 1Londonl. 2021, 119MI. I l l 1 Nainan. K C . . andRyrchkewirich.G. E..lnorz. Chlm.. R.2671.119691.

Volume 5 2 . Number 4 . April 1975 / 261