Cobaloximes as Vehicles for College Teaching

T. M. Brown and A. T. Dronsfield

Derbyshire College of Higher Education Derby, DE3 IGB,United Kingdom
C. J. Cooksey and D. Crich
University College London, London, WC1H OAJ. Unlted Kingdom

Cobaloximes belong to a recently discovered class of or-
ganometallic compounds that contain a covalent cobalt-
carbon bond. This species was thought to be elusive until it
was shown in 1962 to be present in coenzyme B n ( I ) . In this
molecule, the cobalt(II1) ion is stabilized by octahedral coor-
dination to five nitrogen atoms, with sixth site being the Co-
C covalent bond. Much simpler model compounds, with
similar chemical properties to coenzyme BIZ,may be synthe-
sized in which two molecules of the monoanion of dimethyl-
glyoxime provide four nitrogen atoms in a square plane and
the fifth nitrogen is provided by pyridiue. The cobalt-
carbon bond results from nucleophilic attack of a cobalt(1)
intermediate on R B I (R= alkyl) or Ar-CH2Br.
Cobalt(1) is an uncommon oxidation state for the metal
and immediatelv oxidizes in the Dresence of oxveen. There
are two widely ised methods for'the preparation of a suit-
able cobalt(1) comolex, both of which start from the corre-
sponding cobalt(1i) c&plex and require an inert atmo-
sphere. In his celebrated pioneering work Schrauzer (2)used
sodium borohydride as a reducing agent a t low temperature
t o achieve near-quantitative yields; however, for college use
we prefer the cheaper and wicker alkaline disproportion-
ation technique (3).Although the latter has the disadvan-
- -
amount, this does not complicate the workup procedure and
.
. . comnlex in eaual
taee of ~ r o d u c i n eunwanted cobalt(I1I) ~
A cohaloxime(I1) is prepared (eq 2) and then with excess
base disproportionates to a cobaloxime(1) and a cobaloxi-
me(II1) (eq 3). The cobaloxime(1) reacts with the halogen-
. .4).
oalkane to eive the alkvl cobaloxirne(II1). (ea .
orm mall; the class preparation of cobaloximes imposes
demands on sets of e a u i ~ m e nthat
t most colleee laboratories
would find excessive: pressure-equalized dripping funnels
and cylinders of nitrogen or argon to provide oxygen-free
atmospheres form the basis of most reported experimental
work (3).The modifications described here allow cobalox-
imes to be prepared without recourse to expensive glassware
or gas supplies other than natural gas (which is usually
sufficiently air-free to serve as the inert atmosphere). Re-
agents, too, are cheap with the only real expense being the
.. . bromoalkane for use in one of the
purchase of an aooro~riate
iater stages of the preparation.
Useful teachine- oointv
. which can arise from this exoeri-
ment are:
CobaLoximesare probably the most accessible
and
of ell organometalliccompounds;They have not been reported to
be associated with undue toxicological hazard.
2. The compounds are highly colored, which is a feature of sub-
stances based on transition metal ions: the color chanees from
oxidation state to oxidation state of the cobalt ion.
~~ ~ ~ ~~ ~ ~~~ ~ ~~~~ ~ ~ ~ ~~

3. The hlue/l,lack cohalttl, complex is an example of the rransrtim

adds little to the overall cost. Unlike Schrauzer's method. metal in a very unusual oxidation state. Iris very readily orrdined
the disproportionation synthesis of cobaloximes may be by atmospheric oxygen, hence the need to work under anaerobic
achieved in a matter of minutes, making it particularly suit- conditions (normallyonthe sidesof thereaction flasksomeslight
able for class use.
The compound represented in the figure can be summa-
rized as B ~ C o ( d m g H ) ~ and
P y arises from the sequence:

CH< PH CHq
C=N
I
,C=N
\
-NaOH
C=N
,C=N
1
\
CH3 OH CH3 OH
(dmgHd (dmgH) (1)
Dimethylglyoxime Mono anion of
dimethylglyoxime

2dmgHn + 2NaOH + CoC12 + Pyridine - (dmgH)&oPy (2)

+
(dmgH)~Co~Py(dmgH)&oe~y (3)
Cobalt(1) complex:
a potent nucleophile
(dmgH)2CoePy + C3H7-CHrBr
- C,Hr(dmgH)zCo""'Py
n-butylcobaloxime
(4)
Structure of b~lcobaloxlms.

Volume 67 Number 11 November 1990 873

 oxidation takes place, converting the cohalt(1) intermediate to
orange-brown cohalt(I1) compounds).
4. Mast demonstrations of nucleophilic attack in organic chemistry
are apt t o he usually unexciting. Here we have the vivid color
change (blueblack t o orange brown) when the cohalt(1) interme-
diate displaces Br from the hromoalkane.
5. Cohaloximes, being highly colored, lend themselves to chromato-
graphic investigation without the need to visualize with UV light.
Commercially available silica gel plates are perhaps the best t o
use, hut they are expensive. "Homemade"TLC plates using silica
gel with ethyl ethanoate as eluant have yielded acceptable results
and show the principle. We have not had success with paper
chromatography separations.
Teachers w h o would like to use the cobaloximes prepared
in class f o r f u r t h e r investigative work are referred to o u r
earlier paper on the photolysis of these compounds (4).
Because naturalgas isused wprovide the inert atmosphere neces-
sary for the preparaticm, it is essential that this experiment (up to
and including the addition of the bromo alkane) he carried out in a
fume hood. If necessary, the addition of waterlice can he carried out
in the open laboratory, hut care should he taken that there are no
naked flames in the vicinity.
. .. -
A 250-mL flask is eouiooed with a water or air condenser of leneth
at least 25 em. (Shorter condensers sometimes permit back-percola-
tion of air inm the reaction mixture.) Methanol is added (100 ml.')
and deoaygensted by bubbling m natural gaa through a glass tube
' Ethanol a even industrial methylated spirit (denatured alcohol)
are suilaole alternative solvents. The suspension produced alter the
addlion of the cobalt chloride is initially brown but assumes a dull
green color after a minute or so. The other color changes are identical
to those seen with methanol as solvent.
Most primary halogeno4kanes or benzyl bromides (or iodides)
are suitable:
~~~~
thav era
~ ~ ~
--~
lachrvmatarv, linulds. Halooenobenzenes
- ~~~ ~~ are t w unreactlve
~~ ~ ~ ~
-
~.however.. benzvlic halides oossess the disadvantaoe that
to be attacked by the Co(l) Intermediate. Lower molecular mass
halogeno-alkanes yield cobaloximes that are sparingly water soluble
s o the volume of (ice cold) water used in the precipitation stage
should not exceed 300 mL. A good halogeno-alkane to practice with
Is l-bromobutane, which is widely available and not too expensive.
974 Journal of Chemical Education
led down the condenser. T o the alcohol is added pyridine (0.80 mL,
0.80 g, 11mmol) and, having momentarily detached the condenser,
dimethylglyoxime (2.32 g, 20 mmol). Still maintaining the flow of
gas, the flask is swirled until most of the solid is dissolved. Excessive
shaking may risk introducing traces of air into the mixture. Finely
mound cohalt(I1) chloride hexahvdrate (2.37 a. 10mmol) isadded in
a similar manner. The mixture should t u r n a rich brown color. It
seems important t o complete the formation of cohaloxime(I1) before
the addition of excess base. Next a solution of sodium hydroxide (1.6
g, 40 mmol) in water (5 mL) is added over 30 s to the mixture in the
flask uia the top of the condenser and rinsed in with a little alcohol.
If air is adequately excluded and if there is only a trace amount of
oxygen in thegas supply that still blankets thereaction mixture, the
suspension should turn an inky black color within 30 s. If the gas is
too impure or if the flow is too slow that air enters down the con-
denser, then the eobalt(1) intermediate will he oxidized in a second
or two to form a medium brown product. If this happens, the prepa-
ration should he repeated. T o the blueblack cohalt(1) suspension is
added (again via the top of the condenser) the appropriate hala-
geno-alkane (5 mmal) dissolved in alcohol (5 mL) and rinsed in with
a little more alcoh01.~Only a few seconds should elapse between the
formation of the eobalt(1) complex and the addition of the halogeno-
alkane solution: i t is advisable to have this solution to hand before
the addition of the sodium hydroxide.
The oranee-brown color of the cohaloxime should become aooar- ..
ent wlthln a few secondr. The gas flow can then he turned uff, the
apparatus drsrnantled, and the cobalox~meprecrpmted hy pouring
the mrxture intocold water (about 400 ml.~,or,better atill, a ~ l u a h01
icelwater. Vigorous stirring oxygenates and solubilizes impurities
and side products and encourages crystallization. The cohaloxime is
filtered off, advantageously with suction but this is not essential,
and washed with water until the washings are colorless. Finally i t is
allowed t o air-dry in the dark without the application of heat. Yields
depend largely upon the effectiveness of the natural gas supply in
~ ~~~~~ air from the Later stares of the exoeriment. In oracticed
axelodinen~~~
~~~~~
~
hands ahout :W: yields seem to he typrcal. (:rystallization is possi-
ble (from methanol,, although the product ir pure enough for most
purposes without this retincment. The product ir stable in air but
slowly discolors in daylight.
Literature Clted
1. Prsft. J. M.Inormnic Chrmisfw 01 Vitom~nB1,: Academic: New Yark, 1972