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“Cobaloximes” 61
References
Submitted by G. N. SCHRAUZER*
Checked by G. W. PARSHALLt and E. R . WONCHOBAt
R = acid anion,
alkyl, or aryl
B = base, e.g.,
pyridine
A. CHLORO(PYRIDINE)COBALOXIME(III)~
CoC12.6HzO + 2DH2 + 2py + 402- +
CICO(DH)~PYpy.HCl+ 7Hz0
Procedure
Properties
B. DIAQUOCOBALOXIME(II)4*7
+
C O ( C ~ H ~ O ~ ) ~ .2DHz
~ H ~+ +
O Co(DH)z*2HzO 2C2H402 + 2HzO
A 1-1. round-bottomed flask, equipped with a magnetic
stirring bar, is filled with 400 ml. of dry methanol. While
flushing with dry nitrogen (complete exclusion of air is impera-
tive), 24.9 g. (0.100 mole) of cobalt(I1) acetate 4-hydrate and
23.2 g. (0.200 mole) of dimethylglyosime are added to the
methanol. The flask is closed, and the solution stirred for about
one hour. The orange crystalline product is collected on a
Buchner funnel under a stream of nitrogen. After washing
with 100 ml. of cold water, the Co(DH),.2H20is dried at 1 mm.
pressure at room temperature. Yield: 26.0 g. (8201,, based on
dimethylglyosime) . Anal. Calcd. for C8HI8N4O6Co : C, 29.56;
H, 5.54; N, 17.23. Found: C, 29.56; H, 5.59; N, 17.28.
Properties
C. METHYL(PYRIDINE)COBALOXIME3
CoClz.6Hz0 + 2DHz + py + 20H-
= &[CO(DH)~~ +
~ ] ~ 2C1-
8Hz0 +
+ +
+[Co(DH)zpylz [Hleg. OH- = Co’(DH)zpy- HzO +
+
Co(DH)zpp (CHa)zS04 = CH&o(DH)zpy CH3SO4-+
I n this procedure the complex CH,CO(DH)~PY is prepared
from the cobaloxime(1) obtained by reducing the dimeric
cobaloxime(II), [pyCo(DH)z]2, with sodium hydroborate,
NaBH,. The dimeric cobaloxime(I1) is prepared in situ and
not isolated. Instead of pyridine, other bases may be used in
the following procedure.
Procedure
Properties
D. METHY LAQUOCOBALOXIME3
Procedure
Properties
E. PHENYL(PYRID1NE)COBALOXIMEl
C6H& + R'Ig C6H531gBr
=
CsHsn!IgBr + C1Co(DH)2py = C6H&o(DH)zpy + RIgBrC1
The synthesis of organocobalosimes via Grignard reactions is
exemplified in the following preparation of phenyl(pyridine)-
cobalosime. Since the cobaloximes contain two acidic osime
protons, the Grignard reagent must be employed in threefold
excesses.
66
Cobaloximes” 69
Procedure
Properties
References
1. G. N. Schrauzer and J. Kohnle, Clieni. Ber., 97, 3056 (1964).
2. G. N.Schrauzer and R. J. Windgassen, ibid., 99, 602 (1966).
3. G. N. Schrauzer and R. J. Kindgassen, J . A m . Chem. SOC.,88, 3738 (1966)
4. G. N. Schrauzer and R. J. bvindgassen, ibid., 89, 1999 (1967).
5. L. Tschugaeff, Chem. Ber., 40, 3498 (190i).
70 Inorganic Syntheses
RU + IiClOs 1. KOH
K4[RuzClioO].HzO
Procedure
Potassium hydroside (9 g., 0.16 mole) is fused in a silver
crucible, using a Bunsen burner as a source of heat, until the
water is lost and a quiescent melt is obtained. Ruthenium
powder (1.5 g., 0.015 mole) is mised, without grinding, with 2.3 g.
(0.019 mole) of finely ground potassium chlorate. (m Caution.
* Chemistry Department, School of General Studies, Australian National
University, Canberra, A.C.T., Australia.
t Chemistry Department, University of New South Wales, Kensington, N.S.W.,
Australia.
1 Chemistry Department, University of Queensland, St. Lucia, Queensland,
Australia.
$ Department of Biochemistry, John Curtin School of Medical Research,
Canberra, A.C.T., Australia.
7 Department of Chemistry, University of North Carolina, Chapel Hill, N.C.
27514.
a