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Form 1cis-CNglyo-)2-H20
Copper(I1) acetate monohydrate 0.01 mole (2.0 g) is dissolved in
25 cm3of hot water. 25 cm3of hot ethanol is added and the solution
is kept hot Glycine 0.02 mole (1.5g) is dissolved in 25 cm30f hot water.
The two solutions are mixed while hot (-70C, on a steam bath).
The solution is cooled on ice. A needle-like precipitate of cis(Cu(g1yo-)z. Hz0 is obtained. This is filtered at the pump, and the
filtrate is preserved. The solid is washed once with ethanol and air
dried. Yields in the region of 60%to 70%are achieved easily.
Form 2 tran~-CNglyo-)~.H~O
(a) The crude product from above need not he dried to proceed.
A small quantity of the filtrate from 1(n10cm3)is placedinasmall
flask with approximately three quarters (-1.5 g) of the solid reaction
product from 1and 1g of glycine. This is heated under reflux for 1hr.
After this time the solid is filtered off from the hot solution and air
dried. (b) A small quantity of trans-Cu(g1yo-)n may be prepared by
heating cis-Cu(glyo-)%.Hz0in an oven at 180C. The reaction below
is essentially complete in 10 to 15 min (3).
trans-Cu(g1yo-I&)
~~~~~
Procedure
cis-Cu(g1yo-1%.HzO(s)
obscured by water of crystallization and broadened by hydrogen bonding. T h e greater complexity of the spectrum of
the cis isomer when compared to the centrosymmetric trans
isomer should be noted; this is particularly apparent in the
"fingerprint" region of the spectrum (800-1200 cm-1).
+ HlO(g)t
cis
cis
trans
trans
~ C T
cis C~(glyo-)~(aq)
====+
trans C~(glyo-)~(aq)
k~~
Figure 3. The M-N stretches for copper amino acid complexes occur in Me
rqion (6, 8) 450-500 cm-'. M-0 stretches occur at 250-350 cm-'.
uct. Since solution equilibria are rapid for copper(I1) com~ l e x e s(11). solutions will alwavs contain an eauilihrium
mixture of cis and trans isomer; On crystallizatibn the cis
form of the solid initially precipitates due to kinetic control
of crystallization rate. If this solid is allowed to stand in contact with a saturated solution of Cuklvo-)?, the solid is converted totally to the trans isomer (2,hj (thethermodynamic
product). This is redected by the solubility of the two forms
as measured by Ginherg and Gol'hraith (IO),who found the
trans isomer to he less soluble than the cis. Thus, the free
energy change associated with crystallization (in this case, AG
= RTlnK,,) is greater for trans than for cis. Hence, we may
accuratelv describe this as kinetic and thermodvnamic control
of reaction product. The equilibria involved are summarized
in Figure 4. The solid state thermal isomerization (4) is to the
author knowledge a unique reaction.
The experiment could make a worthwhile extension to the
recently described laboratory workshop (12). The experiment
1)
acid com~lexes
would be feasible with other c o ~ ~ e r ( Iamino
showing similar polymorphism.- he cis and trans isomers of
his L-alaninato copper (13) are known. Interestingly, here the
final (thermodynamic) solid product is the cis isomer. The
complexes of copper(I1)with the DL-phenyl alanine also show
similar isomerism (14).
Literature Cited
(1) Pssa, G., and Suteliffe, H., "Practical Inorganic Chemistry: Chapman HS.I
1968, p.
94.
(2) Msuthner, %and Suida, W.,Monotsh.,4,373 (1890).
(3) a. Ley, H.and Wiegner, G..Eloelrochem. 2,585 (1905).
b. Ksuffmsn, G.B., J. CHEM.EDUC.,60,693 (1973).
(4) Deli, B. W., Gillad, R D., and O'Brien,P., J. Chem. SOLDollon 1901 (1979).
(5) Nsksmoto, K., "Infrared and RamanSppctraof Coordination Compaunda: 3rdEd..
Wiley Intenieience. 1978, p. 305.
(61 Kinwid. J. R,and Nsksmoto, K., Sperfrnchim.Acto. 32A, 277 (19761.
(7) Ref. (51.p. 232.
(8) Herlinger, A. W., Wenha1d.S. L., and Long 11, T. Veach. J Amar. Chem. Sac. 32,6474
1,9701.
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