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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
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 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
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
~:
where
-100O I
t
-
>
w
-200
-400 ' I I ' ' I ' ' ' " ' I ' H
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
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
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).