Oct.

5, 1960 Cobalt(III) Complexes; a New Intermediate 5031

[Contribution from the Department of Chemistry, University of California, Los Angeles, California]
A General Synthesis of Cobalt (III) Complexes; A New Intermediate,
Na3[Co(C03)3]-3H20
By H. F. Bauer and W. C. Drinkard
Received April 4, 1960

A general method of preparing symmetrical cobalt(III) complex compounds utilizing a new intermediate, sodium tris-
carbonatocobaltate (III) trihydrate, is discussed with respect to its advantages over present methods. A representative
number of symmetrical cobalt (III) complex compounds have been prepared. These include salts of cobalt amines, inner
charge complexes and a variety of cobaltates. The intermediate is easily prepared and stored. It is reactive under mild
conditions and gives good yields in most cases. Several new cobalt(III) complex compounds of easily oxidized ligands were
prepared and identified.

Introduction reaction to completion. When the ligand does not

Symmetrical cobalt(III) complex compounds carry a sufficient number of protons, additional
acid may be added in the form of HN03 or HCIO4.
generally have been prepared by the oxidation of Sodium tris-carbonatoeobaltate(III) trihydrate
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cobalt(II) ion in the presence of the ligand, direct is a stable compound which provides a reactive
coordination of the ligand with freshly prepared
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source of Co(III) in the presence of a proton donor.

hydrous cobalt(III) oxide or displacement of am- A representative group of cobalt(III) coordina-
monia from hexamminecobalt(III) ion.
tion compounds has been prepared to illustrate the
By far the largest number of complexes of cobalt-
(III) are prepared by oxidation of the cobalt (I I) general applicability of the method. The following
ion in the presence of the ligand. Such a procedure compounds, previously reported, were pre-
works well when applied to ligands which are inert pared using the intermediate Na3[Co(C03)3]·
toward oxidation and when the ligand shows a rela- 3H20: tris-ethylenediaminecobalt(III) chloride,2
tively strong coordinating ability. The preparation tris-acetylacetonatocobalt(III)3 and tris-benzoyl-
breaks down when applied to ligands which are sen- acetonatocobalt(III).4 5The following new com-
sitive to oxidation or when applied to ligands where pounds also were prepared: tris- (1,3-diamino-2-
solvent may be an effective competitor. propanol)-cobalt(III) nitrate (a cobalt (III) com-
Cobalt(III) oxide is difficult to filter and cannot pound containing two tridentate molecules of 1,3-
be utilized after storage. Its use has been restricted diamino-2-propanol has been reported6), tris (0-
to the preparation of amino acid complexes. aminophenol) -cobalt (111), sodium tris-mercapto-
The use of hexamminecobalt(III) ion as an inter- acetatocobaltate(III), tris-ethylenediamine-cobalt-
mediate is generally restricted to the preparation (III) tris-salicylatocobaltate(III) and sodium tris-
of amine chelates. Here, the increased stability ethylenedimercaptocobaltate (i 11).
which results from ring formation coupled with Experimental
the volatility of ammonia is sufficient to drive the Cobalt Analysis.—Cobalt was determined spectrophoto-
reaction to completion. metrically as the thiocyanate complex of Co(II).6
It should be noted also that in most cases synthe- Sodium Tris-carbonatocobaltatei.Ill) Trihydrate.—A 50
ses require the basic form of the ligand. Basic con- ml. solution of 29.1 g. of Co(N0s)í-6H20(0.10 mole) and 10
ditions will, in general, increase the sensitivity of ml. of 30% hydrogen peroxide (excess) was added dropwise
with stirring "to a cold slurry of 42.0 g. of sodium bicarbo-
the ligand to oxidation, allow C02 absorption by nate(0.50 mole) in 50 ml. of H2O. The mixture was allowed
the ligand and increase volatility problems. to stand at 0° for 1 hr. with continuous stirring. The olive
In an attempt to avoid the difficulties associated product was filtered, washed on the filter with three 10 cc.
with other general methods of synthesis, we have portions of cold water, then thoroughly washed with
absolute alcohol and dry ether; yield: 33.3 g., 92% of
investigated the utility of a new intermediate com- theoretical; 93° dec.
plex of cobalt(III). It is formed by the oxidation Anal. Caled, for Na3[Co(C03)3]-3H20: C, 9.95; H,
of cobalt(II) ion by hydrogen peroxide in the pres- 1.66; Co, 16.3. Found: C, 8.72, 9.03; , 1.39, 1.69;
ence of excess sodium bicarbonate. Duval1 has Co, 16.2.
reported that such an oxidation results in the forma- Tris-ethylenediaminecobalt(III) Chloride.—A slurry of
tion of the green, insoluble compound, Co2(C03)3. 3.6 g. of Na3[Co(C03)3]-3H20 (0.01 mole) was mixed with
4.0 g. of ethylenediamine dihydrochloride and warmed on
It is reported to be stable when dry. The compound a steam-bath for 30 minutes. Alcohol was added to precip-
isolated from a similar oxidation in the present in- itate an orange product which was recrystallized from an
vestigation may best be represented as sodium tris- ethanol-water solution; yield: 3.13 g., 91% of theoretical.
carbonatocobaltate(III) trihydrate, Na3 [Co(C03)3]· Anal. Caled, for [Co(en)3)Cl3: C, 20.8; H, 6.95. Found:
3H20. With our present data it is not possible to C, 20.9; H, 6.75.
exclude the structure Na3[Co(HC03)3(OH)3]. It is Tris-( 1,3-diamino-2-propanol)-cobalt(III) Nitrate.—A 25
ml. solution of 3.0g. of 1,3-diamino-2-propanol (0.033 mole)
important to notice, however, that the number of and 4.5 ml. of 70% nitric acid (0.71 mole) was added slowly
base equivalents per mole of intermediate is six in
both assignments. Thus, the number of coordina- (2) S. M. Jorgensen, J. prakt. Ckem., [21 39, 14 (1899).
tion positions per mole is equal to the number of (3) B. E. Bryant and W. C. Fernelius, "Inorganic Syntheses," Vol.
V, McGraw-Hill, New York, N. Y., 1957, p. 188.
base equivalents per mole. Ligands may be added (4) B. Emmert and O. Schneider, Ber., 69B, 1316 (1936).
in their acid form to liberate C02 and produce the (5) J. G. Breckenridge and J. W. R. Hodgins, Can. J. Res., 17B,
desired complex. Volatility of C02 will drive the 331 (1939).
(6) E. B. Sandell, "Determination of Traces of Metals,” 2nd Ed.,
(1) C. Duval, Compt. rend., 191, 615 (1930). Interscience Publishers, Inc., New York, N. Y., 1950, p. 281.
5032 H. F. Bauer and W. C. Drinkard Vol. 82

to 3.6 g. of Nag[Co(C03)3]·3 20 (0.01 mole) warmed

on a steam-bath for 30 minutes. The dark
was
position temperature of 93° precludes further at-
roseproduct
10 ml., filtered and washed
was precipitated by evaporation to tempts to elucidate the structure by dehydration.
with acetone; yield: 4.1 g., 79% of theoretical; 122-124° There has been some controversy as to whether
dec. carbonate can form a stable four-membered ring in
Anal. Caled, for [Co(C3H10N2O)a](NOg)3: C, 21.0; H, carbonato complexes or whether a molecule of
5.82. Found: C, 20.4; H, 5.55. water is needed for a bicarbonato-hydroxo structure.
Tris-acetylacetonatocobalt(III).—A mixture of 3.6 g. The fact that carbonate can indeed fill two coordi-
of Na3 [Co(C03)3] ·3 20 (0.01 mole), 3.0 g. of acetylacetone-
(0.03 mole) and 2.0 ml. of 70% nitric acid was refluxed for
nation sites has been shown unequivocably by
30 minutes in a 60% acetone-water mixture. The solution McCutcheon and Schuele7 in their isolation of
was evaporated until a green precipitate appeared. The
mixture was cooled and filtered. The product was recrystal-
[Co(NH3)e] [Co(C03)3]. Moreover, Lamb and
lized from acetone and water; yield: 3.4 g., 95% of theo- Mysels found8 that one may remove water from
retical ; 220° dec. [Co(NH3)6C03]N03-H20 without destruction of
Anal. Caled, for [0 (03 - 2)3]: C, 50.5; , 5.90. Found: the complex. A chelate structure, similar to that
C, 50.2; , 6.08. proposed for Na3[Co(C03)3]-3H20, has been postu-
Tris-benzoylacetonatocobalt(III).—The procedure for lated for the analogous potassium compound9 on
tris-acetyl.acetonatocobalt(III) was employed; yield: 4.4 the basis of analytical data and absorption spectra.
g., 81% of theoretical; 213° dec. A striking solubility difference is responsible for
Anal. Caled, for [Co(C,0H9O2)3]: C, 66.4; H, 4.98.
Found: C, 65.9, H, 5.28. the increased utility of sodium tris-carbonatoco-
Tris-o-aminophenolocobalt(III).—A slurry of 3.6 g. of baltate(III) trihydrate over the potassium analog.
Na3 [Co(COs)3]'3H20 (0.01 mole) in 30 ml. ethanol was added Sodium tris-carbonatocobaltate is water insoluble.
to 4.4 g. of o-aminophenol hydrochloride (0.03 mole) and the It may be easily separated from the reaction mix-
mixture was refluxed for an hour. The NaCl was removed ture, and when completely dry it can be stored on
by filtration and the filtrate was concentrated to precipitate the shelf for future use. In contrast, potassium
a brown product which was washed with cold water. The
product was recrystallized from an alcohol-water solution; tris-carbonatocobaltate(III) trihydrate is water
yield: 3.4 g., 88% of theoretical; 208-211° dec. soluble and difficult to isolate from the potassium
Anal. Caled, for [Co(C6H6NO)3]-1.5H20: C, 52.7; bicarbonate impurity. Its aqueous solution is some-
, 5.14. Found: C, 52.9; , 5.18. what unstable in the absence of excess bicarbonate,
Sodium Tris-mercaptoacetatocobaltate(III).—A 50 ml.
aqueous solution of 2.8 g. of mercaptoacetic acid (0.03 mole)
forming hydrous cobalt(III) oxide. Yet once iso-
was added to 3.6 g. of Na3[Co(C03)3I-3H20 (0.01 mole) lated, it too can be used for the synthesis of cobalt
with stirring. The mixture was warmed on a steam-bath (III) compounds.10
for 30 minutes. The dark green solid that separated upon The use of tris-carbonatocobaltate(III) trihy-
cooling was washed with acetone; yield: 3.4 g., 85% of drate offers several desirable features. An oxidant
theoretical; 262° dec.
Anal. Caled, for Nas[Co(C2H,0S)3]-6H20: C, 14.25; need not be present, for a source of cobalt(III) ion
H, 3.55. Found: C, 14.3; H, 3.45. is available. The acid form of ligands may now be
Tris-ethylenediaminecobalt(III) Tris-salicylatocobaltate" used. The intermediate is easily prepared, storable
(III).—A solution of 4.3 g. of salicylic acid (0.03 mole) and for later use and reactive under mild conditions.
4.2 g. of tris-ethylenediaminecobalt(III) nitrate (0.01 mole) Because the source of cobalt(III) ion obviates
in 500 ml. of H20 ivas prepared. With stirring, 3.6 g. of the need for an oxidant, the reaction of compounds
Na3 [Co(C03)3]-3H20 (0.01 mole) was added in small por-
tions and the mixture heated to boiling. The insoluble such as o-aminophenol, mercaptoacetic acid and
residue was discarded and the filtrate was evaporated at ethylenedimereaptan is possible without the usual
room temperature to 20 ml. A rose-beige product was col- accompanying oxidative decomposition.
lected and washed with ethanol; yield: 0.9 g., 15% of Basic forms of ligands such as amines are suscep-
theoretical; 223-229° dec.
Anal. Caled, for [Co(C2HSN2)3][Co(C,H403]: C, 45.9; tible to contamination with carbonate from the air
, 5.10; N, 11.88. Found. C, 46.9; , 5.41; N, 10.83. as well as oxidation. The presence of six basic
The analysis indicated contamination with a small amount equivalents per mole of intermediate which are
of salicylic acid.
replaceable and volatile in acid allows the use of
Sodium Tris-ethylenedimercaptocobaltate(III).—To a acid forms of ligands such as amine hydrochlorides,
warm solution of 3.1 g. of ethylenedimereaptan (0.033
mole), 3.6 g. of Na3 [Co(C03)3]-3H20 (0.01 mole) was added carboxylic acids, phenols and mercaptans.
with stirri íg. A black precipitate appeared immediately. Conditions for the preparation of the intermedi-
The mixture was warmed for 30 minutes and filtered. The ate are not critical or time consuming. The starting
product was washed repeatedly with hot water, washed materials are readily available and purification is
with acetme and dried at 110° for 8 hr.; yield: 4.2 g.,
95% of theoretical. simple. The intermediate is stable on storage if
Anal. Caled, for Na3 [Co(C2H4S2)3]-2H20: C, 16.4; kept dry and may be prepared in quantity. If
H, 3.64. Found: C, 15.9; H.3.06. sufficient acid is present during the reaction the
Discussion evolution of C02 gas drives the reaction to comple-
tion even under relatively mild conditions.
The structural formula Na3[Co(CC>3)3]-3H20 is
the simplest formula to fit available analytical (7) T. P. McCutcheon and W. J. Schuele, This Journal, 76, 1845
data. Since no weight was lost after drying at 80° (1953).
(8) A. B. Lamb and K. J. Mysels, ibid., 67, 468 (1945).
over 2 in vacuo for 10 hr., an alternate structure (9) M. Mori, el al., Bull. Chem. Soc. Japan, 29, 883 (1956).
Na3[Co(HC03)3(011)3] is possible. The decom- (10) M. Mori, el al., ibid., 31, 291 (1958).