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 With his(triphenylphosphine1copper tetrahydrohorate,
explosion or a trimethylaluminum fire are usually imbued this reaction does not occur (9).hut a ligand-borane ad-
with a healthy respect fbr such reagents. Experiments duct (43PBH31 is formed during thermal decomposition of
with these compounds in undergraduate laboratory pro- the compound 12)
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 The separation of ,b3PBH3 and rh3P may he achieved by
in air-free systems are generally time consuming and ne- careful extraction. T h e infrared spectrum of 63PBH3 no
cessitate close instruction from a competent teacher. In longer shows vibrations due to bridging hydrogen (10).
courses where laboratory time is limited or where the Because of the relatively large number of phenyl protons,
staEstudent ratio is unfavorable, it is my personal view their resonance only is clearly characterized in the proton
that such experiments should he avoided. For a course at nmr spectrum. A weak 1:l:l:l quartet due to coupling
this university, CH323: "Organometallic and Electron- with the boron-11 nucleus (I = 3k) would be expected for
Deficient Compounds," in which only a limited time (14 the BH3 group. T h e boron-I1 nmr spectrum, however,
hrl is available for practical work, an approach to an ex- shows an eight-line signal originating from overlapping
periment on an electron-deficient compound has been ~98 H Z and h.i. = 57 Hz (Ti).
quartets due to J l l i , -=
made which stresses the properties of the compound rath- With nmr spectra provided, this synthesis and decom-
er than the techniques generally employed in the area. A position experiment occupies about six hours of student
particularly suitable compound is his(triphenylphosphinel time. The starting material may also be purchased' if the
copper(1) tetrahydrohorate, [ ( C ~ H ~ I ~ P I ~ C Uwhich,
BH~, instructor wishes toomit the synthesis.
while containing the covalent double hydrogen bridge be-
tween copper and boron (I), is unusually stable to air and Experimental Procedure
moisture and may be handled normally on the hench top Synthesis of (@3P)2C~BH4
without the usual impediments.
The synthesis, following the procedure of Davidson 121, Finely ground CuSOn.5H2O (1 gl is mixed with triphenylphos-
is straightforward and reliable. The chemistry involved in phine (5 gl and ethanol (approximately 80 ml): then the mixture
is stirred and warmed on a hotplate until the blue solid has dis-
the synthesis is interesting in that the hydrohorate ion, solved. (The yellowish solution formed may be decanted fmm any
BH4-, first acts to reduce the copper(II1 species to cop- small amount of blue residue.) Powdered sodium borohydride
per(1). This in turn is stabilized by interaction with the tri- (approximately 1 g) is added carefully, with stirring, until precip-
ohenvlohosohine lieands to eive a n intermediate such as itation is complete and the vigorous effervescence has subsided.
jrb3~i3ku+.' This copperili "intermediate finally reacts The crude solid is filtered off and extracted into about 50 ml chlo-
with further B H a t o yield the hydroborate complex. This roform. The small amount of undissolved, excess sodium borohy-
reaction pathway compares with t h a t employed by Cariati dride is filtered from the chloroform extract. The filtrate is
and Naldini (3) who first isolated (<baP)sCuCI,(from CuCl warmed an a hotplate until almost boiling and ethanol added
and rhaP in chloroform) and then reacted it with NaBHa slowly with constant stirring (keeping the solution hot1 until the
faint cloudiness produced changes to h e , white crystals. The so-
in ethanol. While both preparations are perfectly reliable, lution is allowed to cool. The white cr,vstals ibrmed are filtered off
that of Davidson is recommended in a laboratory program and air dried. Mp = 167'C (deel. Yields are generally ahout 1.5 g.
having restricted time since cuprous chloride does not A further crop of the compound ma." be obtained by concentra-
have to be prepared (or stored). tion of the mother liquor.
The infrared spectrum of the product shows the charac-
Thermal Decomposition
teristic vibrations of terminal (2386, 2353 cm-'1 and
bridging hydrogen (1984, 1924 cm-'1 attached to boron. In About 0.6 g of (</)3Pl~CuBHl in a test tuhe is decomposed gent^
common with other covalent metal tetrahydroborates, the ly over a yellow Bunsen flame with about 1 min of gentle, spas-
protons bound to horon appear equivalent in the nmr modic heating. The residue is allowed to cool and is then extraet-
spectrum, which suggests a rapid intramolecular exchange ed with 3 X 2 rnl of benzene and filtered to remove any hlack
pmcess in solution 14). On cooling, the signal sharpens to solid particles. The benzcne is evaporated from the filtrate and
the crude solid obtained is extracted with 3 X 2 rnl of ethanol.
a singlet at -160°C. indicating that even the coupling to Both theethanol filtrate and the residue are retained.
the horon nucleus has been lost ("thermal decoupling") Filtrate: The filtrate is heated gently to hailing (hotplate) and
( 5 ) . A similar situation is fbund with the related com- water is added dropwise, maintaining boiling, until the solution is
pound (m3P)ZC~B3H8 in which bridging hydrogens have permanently cloudy. The mixt~ueis allowed to cool and crystal-
also been shown to occur (6). Here, however, on cooling lire. The white crystals are filtered off and air dried. These may
beyond the thermally decoupled stage, a n asymmetric be shown to be triphenylphosphine by their melting point (80'C)
splitting of the singlet signal is observed, indicating that a and a mixed melting point with an authentic sample.
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- 'Strern Chemicals Inc.. 150 Andover Street, Danvers, Ma.,
stract BH3 groups, e.g. (81 01923.
260 / Journal ot Chemical Education
 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