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Inorg. Phys. Theor. 2129
Convenient Synthesis of Trisdiaminechromium(Irl) Salts
By R. D. Gillard * and P. R. Mitchell, Inorganic Chemistry Laboratories, University of Kent at Canterbury, Canter-
bury
A new and convenient synthesis of the tris(ethy1enediamine)- and tris(propy1enediamine) -chrorniurn(lll) ions is
described, using metallic zinc as a catalyst.
TRISDIAMINE complexes of chromium(II1) have been
important from several viewpoints. First, the tris-
Published on 01 January 1968. Downloaded by Fudan University on 02/05/2015 17:11:23.
(ethylenediamine) complex is valuable as a synthetic
intermediate,l the action of heat on the chloride salt
giving the cis-dichlorobis(ethy1enediamine)complex, and
on the thiocyanate salt giving the trans-di-isothiocyanato-
complex. Secondly, the cations are resolvable, and
studies 2 of their optical activity have been fruitful in
establishing relations between signs of Cotton effects and
absolute stereochemistries. A large number of other
studies have used these complexes, including kinetic and
equilibrium work, which revealed the ready hydrolysis
to bis(ethy1enediamine)complexes.
The standard synthetic routes, although chemically
simple, are operationally tedious :
110' 3 days
(a) Cr2(SO,),,15H2O_____c) anhydrous Cr,(SO,),
zn vactm
I with 10% solution (50 ml.) of ethylenediamine in methanol
under reflux
overnight
T
E tOH-Hz0
-
[Cr en,]Cl, HC1 [Cr en,],(SO,),
Zn-HCl en
CrCl,,GH,O CrC1, -w [Cr en3]C1,
(b)
J Pt-Asbestos
[Cr en,]Cl,
We find that a good yield may rapidly be obtained by
allowing the commercially available green chromic
chloride, ' CrC13,6H,0 ', in methanol, to boil under
reflux with ethylenediamine in the presence of metallic
zinc. The product, hydrated tris(ethy1enediamine)-
chromium(II1) chloride, is obtained as a solid and is
readily purified. An exactly similar procedure was used
for the complex of IJ2-diaminopropane.
The zinc catalyst probably functions by generating
kinetically labile chromium(I1) species. The present
observation is reminiscent of several others, notably
(i) the ready dissolution of anhydrous chromium(II1)
chloride in water and other solvents only in the presence
C. L. Rollinson and J. C. Bailar, Inorg. Synth., 1946, 2,
196.
a (a) J. P. Mathieu, J . Chim. phys., 1936, 33, 7 8 ; (b) J. H.
Dunlop and R. D. Gillard, J . Inorg. Nuclear Chem., 1965, 27,
361; (c) A. J. McCaffery, S. F. Mason, and R. E. Ballard,
J . Chem. Soc., 1965, 2883.
of chromiurn(r1) ion or reducing agents, (ii) the synthesis
of complexes of chromium(II1) by the oxidation of a
preformed solution of chromium(I1) ion and the ap-
propriate ligand, e.g. [Cr(NH3)6]3+,4[Cr(CN)6]3-,5 and
[Cren3l3+,4and (iii) the catalytic effect of charcoal on
the formation of [CrenJ3+ by the action of ethylene-
diamine on aqueous chromium(II1) chloride.6 It is
noticeable that in aqueous solution the use of zinc as
catalyst gives only very low yields of Cr en,Cl,.
EXPERIMENTAL
A single piece (ca. 1 g.) of granulated zinc was added to a
solution of green chromium(rI1)chloride (CrC1,,6H20,26.6 g.,
0.11 mole) in methanol (50 ml.) and the mixture heated under
reflux on a steam bath. Anhydrous ethylenediamine
(40 ml., 36 g., 0.6 mole) was added and the heating continued
for 1 hr. After cooling, the solid product was collected and
the piece of zinc removed. The yellow product was washed
(till the washings were colourless), then with ether, and
air-dried.
The product, trisethylenediaminechromium(111)trichloride
trihydrate, (19.9 g., 0.051 mole, 51%) is pure; the analytical
sample was further purified by recrystallization from aqueous
ethanol containing a few drops of hydrochloric acid (Found :
C, 18.2; H, 7.6; C1, 27.0; Cr, 13-3; N, 21.4. Calc. for
C,H,,Cl,CrN,O,:
kx.
C, 18-3; H, 7.7; C1, 27.1; Cr, 13-3; N,
21.4%). The U.V. spectrum shows: lmx. 457 mp, E 75;
351 mp, E 61. (lit.2C,A,, 460 mp, E 74; k,, 353 mp,
E 65). The preparation does not succeed if aqueous solutions
are used, the yield then being very small. No trisethylene-
diaminechromium(II1) chloride is obtained in the absence of
a piece of granulated zinc. Magnesium ribbon or granulated
tin may be used instead, but the yields are lower (38% and
30% respectively), and with granulated tin the reaction is
much slower than with zinc or magnesium.
Tris-(1,2-diaminopropane)cbromium(m) chloride di-
hydrate was obtained in an exactly similar manner (Found:
C, 25.7; H, 8.1; C1, 25.8; Cr, 12.6; N, 20.2. Calc. for
CBH,4C13CrN,02:C, 25.9; H, 8.1; C1, 25.6; Cr, 12.5; N,
20.2%). The absorption spectrum showed: kK 459 mp,
E 76; kx 352 mp, E 63 (lit.2CAm= 460 mp, E 71;
353 mp, E 56).
[8/150 Received, February lst, 19681
H. L. Schlafer and 0. Kling, 2. anorg. Chem., 1956, 287,
296.
4 D. Berman, G. Bokerman, and R. W. Parry, Inorg. Synth.,
1967, 10, 35.
5 H. Moissan, A n n . Chim. Phys., 1882, 25, 401.
J. C. Bailar and J. B. Work, J . Amer. Chem. Soc., 1945,
67, 176.