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Mercury(II) Complexes of Imidazole and Histidine


Philip Brooks, and Norman Davidson
J. Am. Chem. Soc., 1960, 82 (9), 2118-2123 • DOI: 10.1021/ja01494a008
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211s PHILIPBROOKSAND NORMAN
DAVIDSON Vol. 82

The absorption band of medium intensity a t chelates. It was found that if the frequency of the
1308 cm.-' in the reagent, which is also probably band that appears between 1310 and 13% an.-' for
due to C-0 vibrations, is affected to a small the transition metal chelates of 4-hydroxybenzo-
extent in the case of Pb(I1) and Cd(I1) chelates thiazole was plotted against the stability constant
but is shifted to a marked degree in the chelates of (log &) of the chelate, a linear relationship was ob-
the transition metals. This implies that the tained. This type of relationship has been found
C-0 group vibrations in the metal chelates of in a number of metal c ~ m p l e x e s ' ~and
~ ' ~confirms
4-hydroxybenzothiazole are influenced to a slight the assignments made for the C-0 vibrations in
extent by the mass of the metal in the chelate ring. the 4-hydroxybenzothiazole chelates.
The interaction of the C-0 group with the Acknowledgment.-The authors are grateful for
n-bonds in the chelate ring as well as with the d- a grant from the U. S. Atomic Energy Commission
electrons of the metal atoms play a much more in support of this work.
important part in determining the extent of the (14) H. F. Holtzclaw, Jr., and J. P. Collman, THISJOURNAL,79,
shifts that are observed in C-0 group vibra- 3318 (1957).
tions as we go from the reagent to the metal PITTSBURGH
13, PENNWLVANIA

[COh"IR I U U r I O N S O . 2$YG F R O M THE GATESAXD CRELLIN LABORATORIES


O F CHEMISTRY, PASADENA, CALIFORSIA]

Mercury(I1) Complexes of Imidazole and Histidine


BY PHILIP DAVIDSON
BROOKSAND NORMAN
RECEIVED 31, 1959
AUGUST

The association constants of Hg*I with imidazole and L-histidine have been calculated From potential measurements of a
I-Ig, Hg" electrode in solutions containing the complexing agents. For imidazole, the main result is
H g + + 2C3114N: +
Hg(C3H&il)zf+ = 1016.7 A{-2

I\solid substance, H g ( C 3 1 i a S ~ ) C 1 0 ~ ~ Hprecipitates


:0, from solutions a t p H > 4. I t probably contains an infinite ch:iin:
(C3H3SzHg-)n+". For histidine, the main results are:
H g + + 2L- + HgL2 H g + + L - HL + +
HgL(HL)+ Hg++ + 2HL Hg(HL)z++
K = 1021.2 A I - 2 K = 1018.4 AJ-Z A' 1015.0 A[-2
where L- = (C3H3N2)CHzCH( SH?)CO2- and I-IL = (C3H3N2)CHCH(NHa+)CO:-. Because of the tendency of H g + + to
form two bonds in a linear configcration, chelate formation contributes only slightly to the ligand binding by Hg"+. There
is also evidence for the complex HgL+, with a formation constant of M-' (from L-).

I niidazole and histidine complexes with metal The principal experimental data were the potentials of a
ions are of intrinsic interest as a part of the chemis- mercury, mercury(I1) electrode as a function of ligand con-
centration and pH. The cell, in a water bath a t 27.0 &
try of complex ions, as well as being of possible 0.1', contained a J-type mercury electrode in which the mcr-
biological significance. Complex ion formation cury surface could be renewed by overflow, a 1.5 F S a S O a
with a nuniber of metal ions has been studied.' salt bridge connecting t o a saturated calomel electrode and
There is evidence that the imidazole ring is an provision for titrating in reagents and for maintaining a
nitrogen atmosphere. Potential differences were measured
important binding site for metal ions in serum with a Leeds and Northrup IC-2 potentiometer and a 0.01 p
: ~ l b u r n i n . ~In~ ~ general, mercury(I1) has the amp ./mm. galvanometer; p H measurements were made
greatest binding power for nitrogen ligands of any with a Beckman model GS p H meter. In every case ample
of the metal ions; the present investigation is con- time was allowed for the system t o attain equilibrium before
final measurements were made.
cerned with the mercury(I1) complexes of imidazole
and histidine. Results
Experimental Imidazole Complexes.-As anticipated, the bind-
Imidazole, from the Eastman Rodak Co. (m.p. 88-90', ing of mercury by imidazole is so great that, under
Eastman grade) and the Aldrich Chemical Co., and L-histi- practical conditions, the equilibrium
dine, cfp. grade (99.98y0 pure by nitrogen analysis) from the
California Corporation for Biochemical Research were dis- Hg++ + nIniH+ eHg(Im),++ + %€I+ (1)
solved in doubly distilled water. Concentrations calculated lies far to the right except for rather acid solutions
from PH titrations and from the weight of solute taken
agreed within 1yo. Imidazolium perchlorate solutions were with p H 5 2 . Under these circumstances, the pH
prepared by adding standard perchloric acid t o imidazole titration method for the study of complex ion for-
solutions. Mercuric perchlorate solutions were prepared mation is difficult. We have therefore used a po-
by dissolving reagent grade mercuric oxide in a known excess tentiometric method.
of 9 F perchloric acid and diluting. In all experiments so-
dium perchlorate was used to keep the ionic strength con- Insoluble mercury-imidazole compounds pre-
stant a t 0.15 M . cipitate a t pH's > 4, so measurements were made
(1) For a general review, see J. Bjerrum. G. Schwarzenbach, L.
in the pH 2-4 range. The predominant imidazole
S i l k , "Stability Constants, P a r t I." Special Publication No. 6, T h e species is the imidazolium ion, ImH+. Equation 1
Chemical Society, T.ondon, 1957, Tables 26 and 207; see also t h e then represents the over-all chemical rexction.
speciiic references in Table 111. Tlic Nernst law e m bc writteti
(2) F. R. N. Gurd and D. S. Goodman, THISJ O U R N A L , 74, 070
(1932).
( 3 ) C . ' I a i i f ~ ~ ridb,d . , 7 4 , '21 I ( I X d ) .
May 5, 1960 MERCURY OF IMIDAZOLE
(11) COMPLEXES AND HISTIDINE 2119

For Eo', the potential of the hypothetical Hg, TABLEI


1.00 M Hg++ electrode a t p = 0.15 M vs. the see. POTENTIAL OF Hg", I m H + SOLUTIOSS
MEASUREMENTS
(saturated calomal electrode), we take - 0.607 v. [Z
It is inconvenient to measure this quantity because -E,a [X Hgf*]b [H$++] ImH+] [ImH+] log
v. PH Fc F M 021
of the Hg, Hg++, Hgz++ equilibrium. Our choice 0.369 2 . 0 3 3 . 8 5 X 10-4 1.05 X 10- 0.0963 0.0055 2.53
is based on the values Eo (Hg++ vs. Hz) = -0.841 ,361 2.21 3.84 X 10-4 5.49 X 10-9 .0960 ,0952 2.46
in 1 F HC104,4 Eo (Hg++ DS. H2) = - 0.854 v. ,317 2.91 3.82 X 10-4 1.82 X 10-10 ,0954 .0946 2.54
,267 3.77 3.82 X 10-4 3.80 X 10-1' ,0954 ,0946 2.58
( p = O).6 It is t o be noted that the quantities .243 4.17 3.82 X 10-4 6.02 X 10-1' ,0954 ,0946 2.50
E that we quote are oxidation-reduction potentials
using the American convention; a Hg, Hg++ ,411 2.12 3.87 X 10-4 2.52 X 10-7 ,0160 .0153 2.55
electrode is electrically positive with respect to ,394 2.12 4.08 X 10-4 6.74 X 10' ,0317 .0309 2.54
,377 2.10 4.10 X 10-4 1.81 X 10-8 ,0642 ,0634 2.53
s.c.e. For the equilibria .366 2.10 3.88 X 10-4 7.71 X 10- .0972 ,0965 2.51
Hg++ + ImH+ HgIm++ +H+ ,395 2.58 5.11 X 10-4 7.76 X 10-8 ,0147 ,0138 2 . 3 8
[ H + ][HgIm++] .352 2.60 5.26 X 10-4 2.75 X 10-8 .0696 .0686 2 . 4 0
=
[Hg++][ImH+] ,361 2.59 1.01 X 10-8 5.49 X 10- .a692 .0674 2 . 4 2
Hg++ + 2ImH+ J_ HgImp++ + 2 H + ,388 2 . 6 0 6 . 4 4 X 10-8 4.46 X 10-
Av.
.Of384
log 81' =
,0567 2 . 4 6
2.50 f 0.06
[ H+]2[HgIrn2+'] a As already emphasized, these are conventional oxida-
P2' = tion-reduction potentials vs. s.c.e.; the electrode was elec-
[Hg++][ImH+]*
trically positive with respect to s.c.e. [ZHgII] is the
we have total (formal) concentration of Hg", corrected for Hg2++.
F and M arr formula weights per liter and moles per liter,
respectively.

Equation 2 can then be written as tion and imidazole concentration shows that the
RT principal species is Hg(Im)2++.
E = Eo' - -In
2T
[ZHg"] + On changing concentrations of reagents, the
potentials usually were established to f 0.5 mv.
within a few minutes, although occasionally the
potentials drifted for 10-30 minutes before be-
Plots of the quantity (25/RT)E + In (I: Hg") coming constant.
os. In [ImH+]/[H+J were linear with a slope of In general a good way to investigate the possible
1.95-2.00. This shows that the dominant term influence of the first complex, HgIm++ and the
in the power series 1 +
Kl'[ImH+]/[H+] B?'. + term K,'[ImH+]/[Hf] is to start from the equa-
( [ImH+]/[H+])2 is the quadratic term and the tion
principal complex formed is Hg(Im)z++.
Representative data analyzed in terms of the
simple equation
E = Eo' - 0.0298log [Z Hg"] + Plots of the function on the left of equation 9 vs.
0.0596 log {B2'
[ImH+] (7) I
[ImH+]/ [H+]gave fairly good straight lines; how-
ever, it was not possible to obtain points close
are presented in Table I. In all cases from the enough to the origin to result in a reliable extrapo-
actual potential, we know that [ZHg"]/ [Hg++] 2 lation for K1'. The difficulty is essentially this.
400. The equilibrium constant for the reaction To emphasize the contribution to the binding by
Hg +
Hg++ Hgz++ (8) HgTm++, one should work a t low [ImH+]/[H+]
ratios. This decreases the ratio [I: Hg"]/[Hg++];
has been measured as 130.s We have assumed the amount of Hgsff according to equation 8 then
that the system was a t equilibrium with respect becomes large relative to [I: Hg"]. Under these
to this reaction, although we do not know that such circunlstances, the corrections involved in analyzing
is the case. With this assumption, [HgIm2++! = the data are too great to permit reliable interpreta-
[ 2 Hg"] = [Z Hq] - [Hg,++] where [I: Hg] is tion. There was no evidence for the formation
the total amount of mercury added as Hg(I1) in of Hg(Im)3++or Hg(Im)4++ even a t [TmH+] =
the solution and [I: Hg"] is the total amount of O.lOMandpH4.
Hg", !.e., after correction for the mercurous ion The pKa of imidazolium a t 27" and p = 0.15 14
formed. Then [ImH+] = TI: IrnH+] - 2[Hg- was measured by a pH titration to be 7.12. This
Imz++]. The corrections for the amount of Hgz++ can be compared with Edsall's value7 of 7.11 a t
present and for the amount of imidazole tied up as 23O, ,u = 0.16 M , and Tanford and Wagner's
HgTml++ are small in all cases and negligible for valuesof 7.12 a t 25", p = 0.15 M . Since
high ratios [ImH+]/[Z Hg], so errors in the cor-
rections are not very important. Hg++ +
2IrnH+ = HgImz++ + 2H+,
The constancy of the calculated values of p2' PZ' = 102." (10)
in Table I with varying PH, mercury(I1) concentra- H g + + + 2Im = HgImp++,
(4) E. H. Swift, "Introductory Quantitative Analysis," Prentice-
Hall, Inc., New York, N. Y.,1950, p. 509.
(5) W. bf. Latimer, "Oxidation Potentials," Prentice-Hall, Inc.,
Englewood Cliffs. N . J., 1956, p. 179. (7) J. T. Edsall, G. Felsenfeld, D. S. Goodman and F. R . N . Gurd,
(6) L. G. Sillen, A. Jonsson and I. Qvarfort, Acta Chem. Scand., 1, THISJOURNAL, 76, 3054 (1954).
461 (1947). (8) C. Tanford and M. L. Wagner, ibid., 76, 434 (1953).
2120 PHILIPBROOKSAND NORMAN
DAVIDSON 1701. 82

This corresponds approximately to the formula


Hg(C104)(C3H3N2)*H20a
L-Histidine.-The ionization equilibria of histi-
dine are
HpL+ HL + H+ --f 1,- + 2H' (12)
K, fi,.-

~:
where
-100O I

t
-
>
w
-200

-400 ' I I ' ' I ' ' ' " ' I ' H

2.0 3.0 4.0 5.0


PH -
6.0

Fig. 1.-Potential it$. PH for fixed ZHg" and histidine


7.0 8.0 3.0
Our measurements give pKa = 6.08, PKa' = 8.12;
in good agreement with other results (AlbertJg
6.08, 9.20, 20°, I.L = 0.01 M ; Li and Manning.l0
6.05, 9.12,25',p = 0.15M).
concentrations. These concentrations, [2HgTr] = 3.80 X In a solution with constant ZHgl' concentration
F and [ZL] = 0.095 F, actually decreased slightly and a constant, rather large [ZL] (where [ZL] =
during the titration due to dilution; suitable corrections
were made. A similar straight line, displaced as expected
[HzL+] +[HL] +
[L-1) the potential was ob-
served to be a linear function of pH over the p H
by the Nernst law, was obtained for [ZHgII] = 3.4 X range 2.5 to 9, with a slope of 0.060 v. per p H unit,
F, [ZL] = 0.011 F. The solid line is calculated from equa- as displayed in Fig. I. The linear relation is rather
tion 15, and the values log pzl) = 2.98, log 8 2 1 = 9.18, log surprising since the transformation H2L+ F? H L +
/3zr = 14.99. H + has pKa = 6 0. I t is necessary to suppose
therefore that the complexes also can be protonated
Insoluble Hg (C3H3N2) (C104).H20.-Both the and we propose the following equilibria. It is
imidazole and histidine complexes with mercury convenient for the analysis to write all equilibria
become insoluble as the fiH is raised. The imida- terms of the species HL.
zole mercury complex precipitates copiously a t
pH's greater than 4.5, but the histidine complex is Hg++ + H L If HgL+ + 1% {9,0 (1';)
more soluble, solutions a t very alkaline pH's H g + + + HL HgHL-+ $ 1
(ca. 12-13) being just slightly cloudy.
To ca. 150 ml. of solution containing 10 mmoles H g + + + 2HL I_ HgLz + 2H+ 0.0

of Ha", 45 mmoles of Im, 35 mmoles of H f , was H g f C + 2HL I_ HgL(HL)+ + H + 1391

added about 13 mmoles of NaOH. About half


the mercury precipitated as a white precipitate Hgf+ 4-2HL Hg(HL)s+ B.2

and t.he p H was 6.1. The precipitate was dried in The measurements used for qudntitative in-
a vacuum desiccator over Cas04 for several days terpretation were in the p H range 9-3, so that
and then analyzed. it is necessary to consider the three histidine species,
The analysis for mercury was carried out in 6 L-, H L and H2Lf (We can neglect HaL++,which
N HCW4 with NaSCN by a Volhard titration. has a PK, of 1 8).g lye write 21, for the total un-
About 60% of the NaSCN was added prior to the complexed histidine
titration to dissolve the complex. The analyses
for carbon, hydrogen, nitrogen and chlorine were
[ZL] = [L-1 + IHLl + [H*L+]
done commercially by Dr. A. Elek. understanding that any significant corrections for
the amount complexed have been made (if neces-
Element yo Present Relative molar amouut
sary, by a successive approximation procedure).
Hg 51.12 1.00 Then, from equation 12
c1 9.41 1.04
N 7.63 2.13
H 1.21 4.71
C 9.75 3.18 (9) A. hlbert, Bioclrem. J . , S O , GSO (19.52).
0 (by difference) 20.88 5.08 (IO) N. C . Li and R. A . l l a n n i n g . Tms J O U K X A L , 77, 5225 (1025).
May 5, 1960 MERCURY
(11) COMPLEXES
OF IMIDAZOLE
AND HISTIDIKE 2121

TABLE I1
SLOPE OF EQUATION
AND INTERCEPT 15b FOR EXPERIMENTS
AT FIXED
pH
PH 5.00 5.20 6.08 6.20 7.00
Intercept' 4.93(& 1)X lo9 1.30(* 1.3) X 1Olo 6.90(&2) X 10" 4.87(&3) X 1011 2.42(& 1 . 5 ) X 1013
Slope* 5.46(*0.1)X IO1* 1 . 8 4 ( f 0 . 1 ) X 1 0 1 * 1.42(1O.2)X1O16 2.46(&OO.2)X10'5 9.75(&0.1)X 10l6
Intercept = ' q ( p l o
IH 1
+ Pll[H+]). bSlope = + PzI[H+]4-P22[H+l2).
where the function f(H+) is defined by the second ments in the p H range 8-3; the data a t 9 and 2.5
equality. are also predicted fairly satisfactorily.)
The total mercury(I1) concentration is given
+
by the relation: [ZHgT1]= [Hg++]
[HgHL++] +[HgLzl +
[HgL(HL)+]
(HL)z++]. [HLl = [ZL]f(H+) from equation
[HgL+]
[Hg- + + 4.0 k
14. The equilibria 13 then permit us to ex-
c
press the quantities [HgL+], [Hg(HL)z++], etc.,
in terms of [Hg++], [H+] and [ZL]; for example,
[HgL(HL)+1 = Pzi [&?+I [~LIz(j"(H+))z/[H+l.
By substitution of these relations into the equation
o/o' 1
for [ZHg"] we obtain

c I
v
1.0 d
o i
where and 6 2 are implicitly defined by comparison
of (15a) and (15b). The term on the left of (15)
was plotted os. [ZL] for experiments a t several
fixed values of the PH with varying [EL]. One of
the best plots is shown in Fig. 2. The values of the I
1
intercepts and slopes are collected in Table 11. 1 2 3 4 5 6 7
Examination of the plots, such as Fig. 2, strongly
suggssts that there is a significant contribution by [PL] x I03
the 81 term, but the intercept cannot be estimated
accurately, as we have tried to suggest by the Fig. 2.-Plot of eq. l5b for the determination of P1 and pz;
estimated uncertainties in the table. The two pH = 5.00 & 0.01, [ZHg"] = 1.4 X lo-* F.
best intercepts fo_rp H 7 and 5 give 81 = 2.6 X lo6 As already remarked, the fact that the variation
a t pH 7.00 and j31 = 6.5 X l o e a t pH 5.00. Ac- of potential with p H is quite linear with a slope of
cording to our formulation, 81 should increase RT/S in the p H 3-8 range (Fig. 1) was not to be
with decreasing pH. It is quite possible that there expected in general. Reference to equation 15a
is another complex such as HgL(OH), but we be- shows that this linearity requires that the function
lieve the data are not sufficiently good to warrant
such a conclusion. We provisionally conclude log {[fW+)I2(Pzo Pzi[H+I + +
Pzi[H+I')J should
be constant. For pH<8 where the Ka' term can
only that there is a complex with one histidine be neglected, this is equivalent to the constancy of
per mercury, HgL+, that probably Plo = lo6 and
that in the 5 to 7 p H range there is not much of a
contribution_by Hg(HL) ++.
A plot of 8 2 vs. pH is shown in Fig. 3, I n addi- which requires that (PzoIPzI) = K J 2 ; and ( P 2 1 , l P ~ z )
tion to the results in Table 11, we have used the = 2Ka. With the chosen values of the 0's we have
data of Fig. 1 where the fiH was varied a t a con-
stant high Z L concentration; a t this high concen-
tration, only the 8 2 term is important. The solid
lines in Figs. 1 and 3 are calculated from the Discussion
values The binding constants analogous to P2 of several
log p20 = 2.98 nitrogen bases for various metal ions are displayed
log Pzi(M-') 9.18 in Table 111.
log P Z Z ( M - ~ ) 14.99 Several significant trends are evident in Table
111. In the first place, as has been previously
The good agreement justifies the interpretation n 0 t e d ~ ~ 8 Jthe
~ ~ ' binding
~ Constants of imidazole
given. Incidentally, since different EHg" con- and ammonia for complexing metals are approxi-
centrations were used in different experiments, the mately equal but the pKa of imidazolium is less
fact that the complexes are monomeric as regards (12) N. C.Li, T.L.Chu, C. T.Fuji and J. bf. White, THISJOURNAL,
mercury has been demonstrated. (The constants 77. 859 (1955).
&, ~ ? Z Z were actually derived from the measure- (13) R. B. Martin and J. T. Edsall, ibid., 80, 5033 (1958).
2122 PHILIPBROOKS DAVIDSON
AND NORMAN Vol. 82

The increase in binding from imidazole to the


negative histidine anion (L-) is very marked for
the metals Zn++, Cd++, Ni++ and Cu++, whereas
it is rather small for Hg++. In fact the ratios
p&(L-)/pp2(Im) for these five metals are 2.8,
2.3, 2.7, 2.6 and 1.3, respectively. For the first
four metals, chelate formation with the probable
structuresQ

undoubtedly contributes very significantly to the


binding. Because of the tendency t o form only
two strong linear bonds, chelate formation contrib-
utes only slightly to the ligand binding for Hg++.
This point can be illustrated further by these
equilibria which can be calculated from data already
given.
H g + + -t 2L- HgL K = 1021.22 M - 2 (16a)
+ + HL
H g + + L-
0
9 8
-
7 6
PH
5 4 3

Fig. 3.-Log PZZJS. PH; the circles are calculated directly


from the experiments using l5b; the solid line curve is
2
HgL(HL)+
H g + + + 2HL J _ Hg(HL)*++
K = 10l8.m Al-'(16b)
K = 1014.9@
The binding constant of HL by Hg++, presum-
M-' ( 1 6 ~ )

ably via the imidazole group, is less than the bind-


calculated from 15a and the values log ,920 = 2.98, log 1921 = ing constant of imidazole for Hg++ by about lo2,
9.18, log /j22 = 14.99. which is just about what would be predicted from
than that of ammonia. Thus, relative to ammonia the differences in proton binding.
imidazole shows a preference for binding transition The small increase in binding constants in the
metal ions rather than protons. series of reactions 16c, 16b and 16a may be partly
due t o chelate formation; it is also partly due to
TABLE
I11 charge effects.
FORMATION
CONSTANTS IONS"
OF COMPLEX It is instructive t o write out the acid ionization
Imidazole Histidine equilibria
li.letal/ligand (CaHdN:) "11 (L-)
HL/H++L- K = 10-8.12
H+ 14.28 18.48 18.24
Zn++ 4.17' 4.43 11.78l Hg(HL)zC+ Hg(HL)L+ + H+ K = 10-b.81
Cd++
Hg++
4.901
16.74
4.47
17.5
11.101
21.22
Hg(HL)L+ HgLz H++ I( = 10-6.20
Xi++ 5.951 4.79 15.8411
In each case, the protonated amino group is
cu++ 7.15* 7.33 18.601'
ionizing; coordination of Hg++ to the imidazole
0 The values listed are Be's; ;.e., equilibrium constants for
the reaction Cu++ 21m + Culmz++. To compare with group increases the ionization constant by a factor
of only lo3; a much larger factor would be expected
the 82 values, we list twice the pK, of the ligand, for example,
the equilibrium constant of the reaction if chelation by L- were very significant.
2Hf +
2NH1 e2XH4+, etc. In addition to its basic properties, iniidazole is
;&o a weak acid.
As is well known, Hg++ ion typically binds two
ligands very strongly in a linear configuration and
shows only a small tendency to form a third and a
fourth coordinate bond. The other metals in
Table 111 generally have coordination numbers of
4 or 6, with, typically, only a small gradual de-
crease in the intrinsic binding constants
MLn-I +L MLn K -
-
WLnl
[MLn-II [LI The pK for this reaction has been estimated as
14.2.14 We presume that the insoluble mercury
(where L here is any monodentate ligand and not
histidine) as n increases from 1 t o 4 or 6. cornpound, Hg(CsI13N~)C104~H~0, contains the
linear polymer
(11) N. C. Li, Br. E. Doody and J. M. White, T H I S JOORNAL, 79,
5859 (1957). (14) H. Walba and R. W, Isensee, ;bid. 77, 5488 (1955).
May 5, lOGO MERCURY(I AND 11) COhIPLEXES 2123

H H H
H
H
\’ H’\H
with one positive charge per polymer unit. A
similar subrkance Hg(C3H3N2)C1 has been re- Acknowledgments*-Mr* Tetsuo de-
ported. 15 The structure proposed above is similar signed and developed the cell and potentiometric
to that which occurs in H ~ ( N H ~ ) B and~ ~Hg-
B techniques which we have used. We have profited
(NHp)Cl.l7 also from his advice and criticism regarding other
features of this research. We are grateful to the
AEC for support of this work via t h i contract AT-
(15) K . Birttcher. Chcm. Zcnrralblolf, 102, 11, 2757 (1931).
(18) L. Nijsseri and W. N . Lipscomb, Acla Cryst., 6, 604 (1952). (11-1)-188*
(17) W.N. Lipscomb, ibid., 4, 266 (1951). PASADENA, CAI.IFORNIA

No. 2522 FROM


[COSTRIBUTION THE GATESA N D CRELLINLABORATORIESOF CHEMISTRY, INSTITUTE
CALIFORNIA OF
TECHNOLOGY, PASADENA, CALIFORNIA]

Complexes of Mercury(1) with Polyphosphate and Dicarboxylate Anions and Mercury


(11) Pyrophosphate Complexes1
BY TETSUO
YAMANE
AND NORMAN
DAVIDSON
RECEIVED
OCTOBER
30, 1959

It has been discovered that mercurous mercury forms complexes with pyrophosphate, tripolyphosphate, oxalate, a-
dimethylmalonate and succinate. These complexes are stable toward disproportionation to mercury( 11) complexes and
mercury, If L-9 is the anion, the principal complexes are Hg,L2-2q+2 and Hg?L(OH)-q+‘. The formation constants de-
termined from the potential of a mercury-mercurous electrode in ligand solutions are: Hg2(P~O~)r-’,(2.4 f 0.6)101*M - * ;
Hg,(OH)P201-3, (4.4 f 0.6)1015 M-2; Hgz(PsOiO)z-*, (1.7 f 0.3)1011. Hg,(OH)P3010-‘, (1.0 f 0.2)1015; H ~ J ( C ~ O ~ ) Z - : ,
(9.5 f 0.2)106; Hg2(OH)CzOa-l, (1.1 f 0.2)1013. H ~ [ ( C H ~ ) Z C ( C O L ) ~ (3.3 ~ , 0.6)10’; Hgz(OH)[(CH!)zC(COz)21 - ,
] Z -f
~ - 2 ,i 0.5)107; Hgz(0H) [(CH2)2(C02)2]-l, (2.8 f 0.6)1013. (The ionic strength
(3.8 f 0.5)lOl3; H g ~ [ ( C H 2 ) 2 ( C 0 ~ ) ~ ](1.9
was 0.75 M (NaNO?), except for oxalate and succinate, where I t was 2.5 M ( Nal’;Oa).) The mercurous compounds have a
characteristic ultravlolet spectrum. Theory and experiment agree that mercurous complexes of ligands (such as NH3 and
CN-) which form strong covalent bonds to mercury are unstable toward disproportionation to give mercuric complexes
but “ionic” chelating ligands can form stable mercurous complexes. The mercury( 11) pyrophosphate complex was studied
from the potential of a Pt electrode in Hg2, Hg”, pyrophosphate solutions a t PH 7-10. The principal species is Hg(0H)-
(P201)-3,with a formation constant of (2.8 f 0.6)1017M - 2 .

The equilibrium constant €or the formation of Sillen and co-workers have suggested, on the basis
mercurous ion from elementary mercury and mer- of potentiometric evidence, that there are weak
curic ion is 130 in 0.5 M NaC104.2 complexes of Hgz++ formed by nitrate, sulfate
and perchlorate anions, with formation constants
of: 2.5 M-’ (Hg,N03+), 0.5 (Hgz(N03)2), 20
M-’ (HgzS04), 250 (Hgz(S0&-2) and 0.9
The equilibrium is readily reversible. When a M-’ (HgzC104+)..2~5This presumably is mainly
complexing ligand is added to a mercurous solution, ion-pair association. It is also possible that the
the usual reaction that occurs is disproportionation assumption of constant activity coefficients a t
of the mercurous ion to give elementary mercury constant ionic strength is not sufficiently reliable
and a complexed mercuric ion. This occurs, for to enable one to identify such weak complexes
example, with the complexing ligands, CN- with certainty by potentiometric experiments.
and ”3. I t is due to the relatively greater sta- However some time ago, Stromeyers and then
bility of the mercuric complexes. The same situa- Brand7 reported that when sodium pyrophosphate
tion occurs for many insoluble compounds. Thus, solution is added to a mercurous solution, a white
mercurous ion is unstable in basic solutions and
in the presence of sulfide ion. Compounds such the precipitate forms and then redissolves in excess of
as “mercurous sulfide” or “mercurous oxide” strong, reagent, which suggests the formation of a
reported in the past have been shown to be a mix- stable complex.
ture of mercury and the corresponding mercuric We have confirmed and extended these observa-
comp~und.~,~ tions and have now found that mercurous ion forms
The general impression conveyed by textbooks stable complexes with pyrophosphate (Py-”,
and by the chemical literature is that there are tripolyphosphate (TP-~), oxalate OX-^), a-di-
no known stable complexes of mercurous ion. (5) G.Infeldt and L. G. SillCn. Suensk kern. Tidskr., 6 8 , 104 (1946).
(1) Presented at the 136th National Meeting of the American (6) F. Stromeyer, Schwciggcr’s Journal, 68, 130 (1830); as reported
Chemical Society, Atlantic City, N . J., September, 1959. in J. W. Mellor “A Comprehensive Treatise on Inorganic and Theo-
(2) S. Hietanen and L. G . Sill&, Arkiu Kcmi. 10, 103 (1956). retical Chemistry,” Vol. IV, Longman, Greens & Co., Londoii, 1923,
(3) R. Fricke and P. Ackermann, 2. anorg. Chcm., a l l , 233 (1933). p. 1003.
(4) W.N . Lipscomb, THISJOURNAL, 1 3 , 1015 (1951). (7) Brand, 2. enol. Chcm., 28, 592 (1889).