Reaction of mercury(II) trifluoroacetate with deprotonated (η6-toluene)-, (η6-diphenylmethane)-, and (η6 -triphenylmethane)(η6-cyclopentadienyl) iron(II) complexes. Mercuration of some cationic (arene)(cyclopent

Article abstract of DOI:10.1023/B:RUGC.0000016024.46430.89

Treatment with mercury(II) trifluoroacetate of deprotonated (η⁶-toluene)- and (η⁶-diphenylmethane) (η⁵-cyclopentadienyl)iron(II) complexes gave mono-, di-, and trisubstituted [from (η⁶-toluene)-(η⁵- c

Full text of DOI:10.1023/B:RUGC.0000016024.46430.89

Russian Journal of General Chemistry, Vol. 73, No. 10, 2003, pp. 1567 1575. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 10, 2003,
pp. 1660 1668.
Original Russian Text Copyright
2003 by A. Boev, Moskalenko, V. Boev.
Reaction of Mercury(II) Trifluoroacetate
6
6
with Deprotonated ( -Toluene)-, ( -Diphenylmethane)-,
6
5
and ( -Triphenylmethane)( -cyclopentadienyl)iron(II)
Complexes. Mercuration of Some Cationic (Arene)(cyclopenta-
dienyl)iron(II) Complexes
A. M. Boev, A. I. Moskalenko, and V. I. Boev
Lipetsk State Pedagogical University, Lipetsk, Russia
Received January 25, 2002
Abstract Treatment with mercury(II) trifluoroacetate of deprotonated ( 6-toluene)- and ( 6-diphenyl-
methane)( 5-cyclopentadienyl)iron(II) complexes gave mono-, di-, and trisubstituted [from ( 6-toluene)-
(
5-cyclopentadienyl)iron(II) cation] mercury-containing salts. The reaction of mercury(II) trifluoroacetate
with deprotonated ( 6-triphenylmethane)( 5-cyclopentadienyl)iron(II) afforded only the corresponding sym-
metric mercury derivative. The same product was obtained by direct mercuration with mercury(II) trifluoro-
acetate of ( 6-triphenylmethane)( 5-cyclopentadienyl)iron(II) on heating the reactants in boiling unhydrous
ethanol. Reactions of the resulting mercury-containing compounds with acids, symmetrizing bases, and
acylating agents were studied.
In continuation of our studies on the synthesis of
new mercury-containing cationic ( 6-arene)( 5-cyclo-
pentadienyl)iron(II) complexes [1], in the present
work we examined reactions of a series of deprotonat-
ed species I III with mercury(II) trifluoroacetate.
Complexes I III were generated by the action of
a small excess of potassium tert-butoxide on the cor-
responding salts containing ( 6-toluene)- (IV, V),
+
CH3
CH2
t-BuOK
Fe
X
Fe
KX
IV, V
I
+
CH
CH2
t-BuOK
PF6
Fe
Fe
KPF6
VI
II
+
CH
C
t-BuOK
KPF6
Fe
Fe
PF6
VII
III
IV, X = BF4; V, X = PF6.
1070-3632/03/7310-1567$25.00 2003 MAIK Nauka/Interperiodica

1568
BOEV et al.
(
6-diphenylmethane)- (VI) and ( 6-triphenyl-
inorganic salt, and a required amount of electrophile,
methane)( 5-cyclopentadienyl)iron(II) cations (VII)
in a 1:1 mixture of anhydrous 1,2-dimethoxyethane
and acetonitrile at 0 C under argon. Judging by the
color change from yellow to deep red, deprotonation
of the above salts occurred almost instantaneously to
give the corresponding complexes I III.
mercury(II) trifluoroacetate, was added. In all cases,
the reaction readily occurred and was accompanied by
change of the color.
Depending on the ratio of potassium tert-butoxide
and mercury(II) trifluoroacetate, the reactions with
salts IV and V gave mono- (VIII, IX), di- (X, XI),
and trimercurated products (XII, XIII); from com-
pound VI, mono- and dimercurated complexes XIV
and XV were obtained.
The resulting solution containing complexes I III
was filtered from excess deprotonating agent and
+
CH2HgOOCF3
KX
Fe
X
I + Hg(OCOCF3)2
KOOCF3
VIII, IX
+
CH3 n(HgOOCF3)n
1) n t-BuOK;
2) nHg(OCOCF3)2
X
IV, V
Fe
nKOOCF3
X XIII
+
CH
HgOCOCF3
KPF6
Fe
PF6
II + Hg(OCOCF3)2
KOOCCF3
XIV
+
C
1) 2 t-BuOK;
2) 2Hg(OCOCF3)2
HgOCOCF3
HgOCOCF3
Fe
VI
PF6
2KOOCF3
XV
VIII, X, XII, X = BF4; IX, XI, XIII, X = PF6; X, XI, n = 2; XII, XIII, n = 3.
However, the reaction with salt VII (through
intermediate III), regardless of the ratio potassium
tert-butoxide mercury(II) trifluoroacetate
afforded only symmetric product XVI. Its formation
can be interpreted in terms of greater CH acidity
of salt VII due to effect of the two phenyl groups
at the -carbon atom of the coordinated arene
ligand.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

REACTION OF MERCURY(II) TRIFLUOROACETATE
1569
2+
C Hg C
Hg(OCOCF3)2;
KPF6
VII t-BuOK [III]
Fe
Fe
2PF6
KPF6
KOOCCF3
XVI
Hg(OCOCF3)2
C2H5OH, 78 C
C2H5OOCCF3
In fact, unlike salts IV VI, we succeeded in
effecting direct mercuration of VII with mercury(II)
trifluoroacetate by heating equimolar amounts of the
reactants for 3 h in boiling anhydrous ethanol. In this
case we also isolated in 87% yield only symmetric
mercuration product XVI. As in the above reaction,
the result of the reaction almost did not depend on
the reactant ratio, in particular when the amount of
Hg(OCOCF3)2 was increased.
complexes revealed that they are typical [4] organo-
mercury compounds with a localized covalent C Hg
bond. This bond is fairly labile, and it readily under-
goes dissociation by the action of acids, symmetrizing
reagents, and acylating agents. Treatment of VIII
XVIII with hydrochloric acid resulted in protode-
mercuration and formation of initial compounds IV
VII which were isolated in high yields as known [5]
tetraphenylborates and were identified by the melting
points and IR spectra (by comparison with authentic
samples).
It should be noted that the structure of the mercury-
containing products is essentially influenced by both
the reactant ratio and the experimental procedure. For
example, deprotonation of salts IV and V with the
use of 2.5 equiv of potassium tert-butoxide according
to the procedures proposed previously [2, 3], i.e.,
without preliminary separation of excess deprotonat-
ing agent, the subsequent addition of an equimolar
amount (with respect to IV or V) of mercury(II) tri-
fluoroacetate led to formation of new compounds
XVII and XVIII (Table 1) rather than mono- or di-
mercurated products VIII XI (see above).
Salts IX and XIV smoothly reacted with calcium
chloride in a mixture of ethanol, ethylene glycol
dimethyl ether, and acetonitrile at room temperature
to give complexes XIX and XX via replacement of
the OCOCF3 group by chlorine. Special emphasis
should be placed on the reaction of salts IX, XIV,
XVII, and XVIII with ammonia. For example, treat-
ment of compounds IX and XIV with ammonia in
a mixture of acetonitrile and ethylene glycol dimethyl
ether at room temperature led to symmetrization prod-
ucts XXI and XXII in high yields (Table 1) and with
no liberation of metallic mercury. By contrast, ana-
logous reactions of salts XVII and XVIII resulted in
decomposition with liberation of a considerable
amount of metallic mercury, and the yield of sym-
metric complex XXI was relatively low (40 42%).
Mercury-containing compounds VIII XVIII are
as a rule yellow brown fine crystalline powders which
can be stored in the dark for a month without appreci-
able decomposition. On exposure to light, these prod-
ucts began to decompose fairly quickly with liberation
of metallic mercury. This process is especially charac-
teristic of compounds XVII and XVIII. Melting of
complexes VIII XVIII is also accompanied by their
decomposition. The solubility of VIII XVIII in
ethanol, acetone, acetonitrile, dimethylformamide, and
dimethyl sulfoxide sharply decreases as the percentage
of mercury increases. For that reason we failed to
record 1H NMR spectra for some di- and trimercurated
complexes. All the products are almost insoluble in
water, diethyl ether, and benzene.
These data unambiguously indicate the presence of
univalent mercury in XVII and XVIII, for just the
reaction with ammonia is used in analytical chemistry
[6 8] as a qualitative test for univalent mercury salts
(a fine black precipitate of metallic mercury is
formed). Finally, mercury salt IX as an example was
Study of the chemical properties of the prepared
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

1570
BOEV et al.
+
CH2HgCl
Fe
PF6
CaCl2
XIX
IX, XIV
CaCl(OCOCF3)
+
CH
HgCl
PF6
Fe
R
XX
R
2+
CH Hg CH
NH3
IX, XIV
Fe
Fe
(PF6 )2
H3N Hg(OCOCF3)2
XXI, XXII
NH3 (R = H)
Hg; H3N Hg(OCOCF3)2
XVII, XVIII
XXI, R = H; XXII, R = Ph.
brought into reaction with acetyl bromide in the
presence of a catalytic amount of anhydrous aluminum
bromide in methylene chloride. The reaction gave
known [9] complex XXIII via rupture of the C Hg
bond; the product was identified by the melting point
and spectral parameters (Table 2).
Table 1. Yields, melting points, and elemental analyses of mercury-containing salts VIII XXII
Found, % Calculated, %
Comp. Yield, Decomp.
Formula
no.
%
point,
C
C
H
Fe
Hg
C
H
Fe
Hg
VIII
IX
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII
XIX
XX
68
73
58
51
62
54
74
70
87
78
76
57
80
72
92
205 210 27.28
195 200 24.93
220 225 20.31
210 215 19.43
230 235 17.32
200 205 16.38
130 135 32.25
185 190 24.67
230 235 45.98
245 250 21.43
230 235 19.15
110 115 24.22
105 108 32.13
235 237 31.46
132 135 40.38
1.87
1.68
1.12
1.08
0.78
0.85
2.08
1.36
3.14
1.57
1.42
1.95
2.28
2.53
2.91
9.50 32.75 C14H12BF7FeHgO2
8.10 29.87 C14H12F9FeHgO2P
6.08 43.48 C16H11BF10FeHg2O4
5.18 40.76 C16H11F12FeHg2O4P
4.36 48.17 C18H10BF13FeHg3O6
4.50 45.65 C18H10F15FeHg3O6P
7.14 26.92 C20H16F9FeHgO2P
4.72 37.96 C22H15F12FeHg2O4P
8.85 16.59 C46H40F12Fe2HgP2
6.56 49.66 C14H12BF7FeHg2O2
6.38 45.97 C14H12F9FeHg2O2P
9.48 33.15 C12H12ClF6FeHgP
8.72 29.11 C18H16ClF6FeHgP
12.25 20.65 C24H24F12Fe2HgP2
10.88 18.08 C36H32F12Fe2HgP2
27.46
25.07
20.78
19.55
17.47
16.48
32.17
24.95
46.24
20.68
19.30
24.30
32.31
31.52
40.54
1.96
1.79
1.19
1.12
0.81
0.77
2.14
1.42
3.35
1.48
1.38
2.02
2.39
2.62
3.00
9.12 32.72
8.33 29.91
6.04 43.37
5.68 40.81
4.51 48.63
4.31 46.44
7.48 26.87
5.27 37.87
9.35 16.79
6.87 49.35
6.41 46.05
9.42 33.82
8.35 29.98
12.21 21.93
10.47 18.81
XXI
XXII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

REACTION OF MERCURY(II) TRIFLUOROACETATE
1571
+
CH2COCH3
AlBr3
IX + CH3COBr
Fe
PF6
HgBr(OCOCF3)
XXIII
Table 2. IR and 1H NMR spectra of mercury-containing salts VIII XXII and compound XXIII
Comp.
no.
1
IR spectrum, , cm
1H NMR spectrum, , ppm (2JHgH, Hz)
VIII
IX
3120, 2965, 1695, 1508, 1465, 1428, 1288, 1204, 1160, 6.68 s (5H, C6H5Fe), 5.38 s (5H, C5H5), 2.83 s (2H, CH2,
1078, 1039, 852, 745, 710, 628, 550, 468 J 184)
3125, 2950, 1700, 1506, 1470, 1430, 1278, 1200, 1162, 6.67 s (5H, C6H5Fe), 5.40 s (5H, C5H5), 2.83 s (2H, CH2,
1081, 1042, 860, 741, 705, 622, 556, 460 J 185)
X
3120, 2920, 1705, 1512, 1472, 1428, 1270, 1206, 1160, 6.68 s (5H, C6H5Fe), 5.38 s (5H, C5H5), 3.24 s (1H, CH,
1075, 1030, 1001, 832, 752, 706, 628, 552, 472 J 125)
XI
3140, 2960, 1700, 1506, 1483, 1430, 1268, 1200, 1158, 6.65 s (5H, C6H5Fe), 5.38 s (5H, C5H5), 3.22 s (1H, CH,
1080, 1042, 852, 745, 700, 628, 552, 468
1720, 1442, 1304, 1218, 1145, 1042, 843, 812, 730,
625, 530, 450
2970, 1718, 1445, 1300, 1212, 1150, 1042, 850, 810,
732, 628, 542, 454
J 126)
XII
XIII
XIV
3140, 2950, 1695, 1505, 1460, 1430, 1290, 1208, 1155, 7.50 7.63 m (5H, C6H5), 6.71 d (5H, C6H5Fe), 5.43 s
1080, 1040, 848, 742, 715, 635, 560, 500, 464
(5H, C5H5), 4.46 s (1H, CH, J 110)
XV
3130, 1690, 1502, 1431, 1215, 1162
XVI
3140, 1505, 1460, 1428, 1330, 1090, 1040, 850, 726, 7.43 7.66 m (20H, 4C6H5), 6.78 s, 6.58 s, 6.15 s (10H,
632, 576, 480 2C6H5Fe), 5.31 s, 5.26 s (10H, 2C5H5)
XVII 3122, 2960, 1700, 1512, 1460, 1430, 1288, 1200, 1162, 6.68 s (5H, C6H5Fe), 5.37 s (5H, C5H5), 2.75 s (2H, CH2,
1040, 836, 755, 712, 620, 558, 462 J 75)
XVIII 3120, 2960, 1695, 1508, 1472, 1428, 1279, 1205, 1170, 6.68 s (5H, C6H5Fe), 5.36 s (5H, C5H5), 2.76 s (2H, CH2,
1043, 853, 812, 763, 710, 625, 552, 471 J 76)
3100, 2960, 1517, 1500, 1460, 1428, 1268, 1162, 1064, 6.68 s (5H, C6H5Fe), 5.36 s (5H, C5H5), 2.84 s (2H, CH2,
1026, 850, 748, 633, 552, 468 J 178)
3150, 2965, 1510, 1462, 1426, 1287, 1162, 1082, 1039, 7.52 7.63 m (5H, C6H5), 6.72 d (5H, C6H5Fe), 5.43 s (5H,
XIX
XX
852, 743, 712, 642, 560, 510, 460
3100, 1465, 1421, 1160, 1015, 860, 512, 455
C5H5), 4.48 s (1H, CH, J 98)
6.63 s (10H, 2C6H5Fe), 5.45 s (10H, 2C5H5), 2.79 s (4H,
2CH2, J 130)
XXI
XXII 3152, 1502, 1460, 1420, 1175, 1018, 858, 528, 460 7.48 7.60 m (10H, 2C6H5), 6.68 d (10H, 2C6H5Fe), 5.36 s
(10H, 2C5H5), 4.42 s (2H, 2CH, J 68)
XXIII 3120, 2920, 1705, 1508, 1470, 1420, 1325, 1285, 1167, 6.42 s (5H, C6H5), 5.22 s (5H, C5H5), 4.21 s (2H, CH2),
1069, 1033, 850, 786, 720, 634, 510, 465
2.26 s (3H, CH3)
1
Apart from chemical transformations, the structure
of compounds VIII XXIII was confirmed by
elemental analysis (Table 1) and 1H NMR and
IR spectroscopy (Table 2). All the products showed in
the IR spectra absorption bands of various intensities
in the regions 1420 1460, 1112 1125, 1005 1015,
850 860, and 712 730 cm , which belong to vibra-
tions of bonds in the ( 6-arene)( 5-cyclopentadienyl)-
iron fragment [2, 10, 11]. In the IR spectra of com-
pounds VIII XV, XVII, and XVIII having a tri-
fluoroacetate group we also observed strong absorp-
1
tion bands at 1690 1720 and 1200 cm , which arise
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

1572
BOEV et al.
from stretching vibrations of the C O and C O
bonds, respectively [12]. The lack of such bands in
the spectra of XIX XXII indicates complete replace-
ment of the trifluoroacetate moiety by the correspond-
ing group. Stretching vibrations of the anions, PF6
and BF4 give rise to strong bands in the regions 830
+
CH2HgHgOCOCF3
Fe
X
1
840 and 1085 1095 cm , respectively [3]. In addi-
1
tion, the IR spectra contain bands at 540 560 cm ,
which can be assigned to vibrations of the Hg C
bond [13].
XVII, XVIII
1
XVII, X = BF4, XVIII, X = PF6.
The H NMR spectra of VIII XI, XIV, XVI, and
XVII are consistent with the proposed sandwich-like
cationic structures. In all cases, a peak corresponding
to resonance of five cyclopentadienyl protons was
present at 5.20 5.48 ppm [10]. Signals from protons
of the coordinated aromatic fragments ( 6.15
6.80 ppm) are displaced upfield relative to those
belonging to the noncoordinated benzene ring ( 7.43
7.65 ppm) in compounds XIV and XVI or to the
Thus, the results of our study demonstrate a wide
synthetic potential of mercury-containing salts derived
from cationic ( 6-arene)( 5-cyclopentadienyl)iron(II)
complexes. The relatively easy replacement of
mercury-containing substituents by a metal, halogen,
or alkyl, acyl, and other groups [4] opens further
prospects in using the prepared compounds in the
synthesis of new functionally substituted salts from
cationic ( 6-arene)( 5-cyclopentadienyl)iron(II) com-
plexes.
1
initial ligand. In the H NMR spectra of most com-
pounds, signals appear as fairly narrow peaks, so that
spin systems corresponding to coordinated and non-
coordinated rings are clearly seen.
EXPERIMENTAL
Signals from the methylene and methine protons
in the spectra of VIII XI, XIV, and XVII are located
The IR spectra were taken on UR-20 or IKS-29
spectrometer from samples pelleted with KBr or
dispersed in mineral oil. The H NMR spectra of
solutions in DMSO-d6 were recorded on a Bruker
WP-200SY spectrometer at 200.13 MHz using HMDS
as internal reference. Initial compounds IV VII were
synthesized by the procedures described in [2, 10,
18, 19]. All reactions with deprotonated complexes
IV VII were carried out under argon.
at
2.75 3.24 (cations VIII XI and XVII and
1
4.46 ppm (XIV). This means that mercury-containing
substituents deshield protons of the methylene and
methine groups: The downfield shift of the correspond-
ing signals relative to those of initial salts IV VI
[10, 14] ranges from 0.22 to 0.70 ppm. It is known
[15] that such displacement may be caused by both
the electron-acceptor effect of the mercury-containing
substituent and its magnetic anisotropy. Taking into
account the fairly similar electronegativities of the
hydrogen (2.1) and mercury atoms (1.9) [16], we
can conclude that the latter factor is more significant.
In the case of salt XVII, its effect is the weakest.
This also follows from comparison of the spin spin
(
5-Cyclopentadienyil)( 6-trifluoroacetoxy-
mercuriomethylbenzene)iron(II) hexafluorophos-
phate(V) (IX). To a solution of 0.36 g of ( 5-cyclo-
pentadienyl)( 6-toluene)iron(II)
hexafluorophos-
phate(V) (V) in 12 ml of a 1:1 mixture of anhydrous
acetonitrile and ethylene glycol dimethyl ether we
added with stirring at 0 C 0.13 g of potassium tert-
butoxide. After 20 min, the dark red solution contain-
ing compound I was filtered, and 0.43 g of mercury(II)
trifluoroacetate was added to the filtrate under stirring.
The mixture quickly changed from dark red to
yellow brown. It was stirred for 20 min at 20 C, the
solvent was removed under reduced pressure at room
temperature, and the residue was washed first with
hexane and then with water and dried in air until
constant weight. Yield 0.49 g.
2
coupling constants JHgH. Its value for compound
XVII is lower by a factor of 2.4 than those found for
salts VIII and IX. Evidently, the mercury-containing
substituents attached to the methylene carbon atom in
compounds XVII and in VIII and IX have different
natures. On the basis of our experimental results
(Tables 1, 2) and published data [6] we propose the
structure of XVII and XVIII shown below, where
the cation contains two univalent mercury atoms
linked through a Hg Hg bond.
1
The H NMR spectra of XIX XXII are charac-
terized by almost the same signal patterns as those ob-
Compound VIII was synthesized in a similar way.
2
served for VIII XI and XIV but different JHgH
values. The difference in JHgH conforms to published
[
6-Bis(trifluoroacetoxymercurio)methylben-
zene]( 5-cyclopentadienyl)iron(II) hexafluorophos-
2
data [6, 17].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

REACTION OF MERCURY(II) TRIFLUOROACETATE
1573
phate(V) (XI). To a solution of 0.36 g of complex V
in 12 ml of a 1:1 mixture of acetonitrile and ethylene
glycol dimethyl ether we added with stirring at 0 C
0.27 g of potassium tert-butoxide. After 20 min, the
dark red solution containing compound I was filtered,
and 0.85 g of mercury(II) trifluoroacetate was added
under stirring. The mixture quickly changed from dark
red to brown. It was stirred for 20 min at 20 C, the
solvent was removed under reduced pressure at room
temperature, and the precipitate was washed first with
hexane and then with water and dried in air until
constant weight. Yield 0.50 g.
II was filtered, and 0.85 g of mercury(II) trifluoro-
acetate was added under stirring. The mixture quickly
changed from dark red to red brown and then to blue
green. The mixture was stirred for 20 min at 20 C,
the solvent was removed under reduced pressure at
room temperature, and the residue was washed first
with hexane and then with water and dried in air until
constant weight. Yield 0.75 g.
Di( 5-cyclohexadienyl)[bis( 6-triphenylmethyl)-
mercury]diiron(II) bis[hexafluorophosphate(V)]
(XVI). a. To a solution of 0.51 g of ( 5-cyclopenta-
dienyl)( 6-triphenylmethane)iron(II) hexafluorophos-
phate(V) (VII) in 20 ml of a 3:1 mixture of anhy-
drous acetonitrile with ethylene glycol dimethyl ether
we added with stirring at 0 C 0.13 g of potassium
tert-butoxide. After 20 min, the crimson solution con-
taining compound III was filtered, and 0.43 g of
mercury(II) trifluoroacetate was added under stirring.
The mixture quickly changed from crimson to light
yellow and then greenish yellow. It was stirred for
20 min at 20 C, the solvent was removed under
reduced pressure at room temperature, and the residue
was washed first with hexane and then with water and
dried in air until constant weight. Yield 0.51 g.
Compound X was synthesized in a similar way.
(
5-Cyclopentadienyl)[ 6-tris(trifluoroacetoxy-
mercurio)methylbenzene]iron(II) hexafluorophos-
phate(V) (XIII). To a solution of 0.36 g of compound
V in 12 ml of a 1:1 mixture of acetonitrile and
ethylene glycol dimethyl ether we added with stirring
at 0 C 0.40 g of potassium tert-butoxide. After
20 min, the dark red solution containing compound I
was filtered, and 1.28 g of mercury(II) trifluoroacetate
was added under stirring. The mixture quickly
changed from dark red to brown. It was stirred for
20 min at 20 C, the solvent was removed under
reduced pressure at room temperature, and the precip-
itate was washed first with hexane and then with
water and dried in air until constant weight. Yield
0.70 g.
b. To a solution of 0.51 g of compound VII in
24 ml of anhydrous ethanol we added 0.43 g of
mercury(II) trifluoroacetate. The mixture was heated
for 3 h under reflux, the solvent was removed under
reduced pressure at room temperature, and the residue
was washed with water and dried in air until constant
weight. Yield 0.53 g.
Compound XII was synthesized in a similar way.
(
5-Cyclopentadienyl)[ 6-diphenyl(trifluoro-
(
5-Cyclopentadienyl)( 6-trifluoroacetoxydi-
acetoxymercurio)methane]iron(II) hexafluorophos-
phate(V) (XIV). To a solution of 0.43 g of ( 5-cyclo-
pentadienyl)( 5-diphenylmethane)iron(II) hexafluoro-
phosphate(V) (VI) in 12 ml of a 1:1 mixture of
anhydrous acetonitrile and ethylene glycol dimethyl
ether we added with stirring at 0 C 0.13 g of potas-
sium tert-butoxide. After 20 min, the dark red solution
containing compound II was filtered, and 0.43 g of
mercury(II) trifluoroacetate was added under stirring.
The dark red mixture quickly turned red brown and
then green. It was stirred for 20 min at 20 C, the
solvent was removed under reduced pressure at room
temperature, and the residue was washed first with
hexane and then with water and dried in air until
constant weight. Yield 0.55 g.
mercuriomethylbenzene)iron(II) tetrafluoroborate
(XVII). To a solution of 0.30 g of ( 5-cyclopentadi-
enyl)( 6-toluene)iron(II) tetrafluoroborate (IV) in
10 ml of anhydrous tetrahydrofuran we added with
stirring at 0 C 0.27 g of potassium tert-butoxide.
After 8 min, 0.43 g of mercury(II) trifluoroacetate was
added to the resulting red brown mixture which very
quickly turned black with a gray green tint. The
mixture was stirred for 15 min at 20 C and filtered,
the solvent was removed from the filtrate under
reduced pressure at room temperature, and the residue
was washed first with hexane and then with water and
dried in the dark until constant weight. Yield 0.63 g.
Compound XVIII was synthesized in a similar
way.
(
5-Cyclopentadienyl)[ 6-diphenylbis(trifluoro-
acetoxymercurio)methane]iron(II) hexafluorophos-
phate(V) (XV). To a solution of 0.43 g of compound
VI in 12 ml of a 1:1 mixture of acetonitrile and
ethylene glycol dimethyl ether we added with stirring
at 0 C 0.27 g of potassium tert-butoxide. After
20 min, the dark red solution containing compound
(
6-Chloromercuriomethylbenzene)( 5-cyclo-
pentadienyl)iron(II) hexafluorophosphate(V)
(XIX). To a solution of monomercurated complex IX
prepared as described above (without isolation) we
added 0.22 g of calcium chloride in 5 ml of a 1:1
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1574
BOEV et al.
mixture of ethanol with acetonitrile. A light brown
solid immediately precipitated, and the color of the
solution became much less intense. After 20 min, the
solvent was removed under reduced pressure at room
temperature, and the residue was washed first with
hexane and then with 5 ml of cold water and dried
in air until constant weight. Yield 0.34 g.
hexane and then with 5 ml of cold water and dried in
air until constant weight. Yield 0.49 g.
(
5-Cyclopentadienyl)( 6-1-phenyl-2-propa-
none)iron(II) hexafluorophosphate(V) (XXIII). To
a mixture of 1 mmol of salt IX and 1.2 mmol of acetyl
bromide in 10 ml of dry methylene chloride, protected
from atmospheric moisture, we added 0.1 g of anhy-
drous AlBr3. The mixture was stirred for 3 h at 20 C,
5 ml of 5% hydrochloric acid and 3 ml of a saturated
solution of NH4PF6 were added, and the mixture was
stirred for 0.5 h. The organic layer was separated,
and the aqueous layer was extracted with CH2Cl2
(3 10 ml). The extracts were combined with the
organic phase and dried over anhydrous Na2SO4, the
solvent was removed under reduced pressure at room
temperature, and the residue was recrystallized from
acetone diethyl ether (1:1). Yield 0.18 g, mp 87
88 C [9].
[
6-Chloromercurio(diphenyl)methane]( 5-cy-
clopentadienyl)iron(II) hexafluorophosphate(V)
(XX). To a solution of monomercurate complex XIV
prepared as described above (without isolation) we
added 0.22 g of calcium chloride in 5 ml of a 1:1
mixture of ethanol with acetonitrile. A yellow green
solid immediately precipitated, and the color of the
solution sharply decreased in intensity. After 20 min,
the solvent was removed under reduced pressure at
room temperature, and the residue was washed first
with hexane and then with 5 ml of cold water and
dried in air until constant weight. Yield 0.52 g.
REFERENCES
(Di- 6-benzylmercury)di( 5-cyclopentadienyl)di-
iron(II) bis[hexafluorophosphate(V)] (XXII). a. To
a solution of monomercurated complex IX prepared
as described above (without isolation) we added 4 ml
of a saturated solution of ammonia in acetonitrile.
A small amount of a light yellow solid immediately
precipitated, and the color of the solution became
less intense. After 20 min, the solvent was removed
under reduced pressure at room temperature, and the
residue was washed first with hexane and then with
5 ml of cold water and dried in air until constant
weight. Yield 0.33 g.
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b. To a solution of 1 mmol of compound XVII or
XVIII in 15 ml of acetonitrile we added 4 ml of a
saturated solution of dry ammonia in acetonitrile.
The originally yellow brown solution immediately
turned black, and (after 20 min) finely dispersed
metallic mercury separated from the solution as
a light gray precipitate. A saturated aqueous solution
of NH4PF6, 3 ml, was added, the mixture was filtered,
the solvent was removed from the filtrate under
reduced pressure at room temperature, and the residue
was washed first with hexane and then with 5 ml of
cold water, and dried in air until constant weight.
[Bis( 6-diphenylmethyl)mercury]di( 5-cyclo-
pentadienyl)diiron(II) bis[hexafluorophosphate(V)]
(XXII). To a solution of monomercurated derivative
XIV prepared as described above (without isolation)
we added 4 ml of a saturated solution of dry ammonia
in acetonitrile. A small amount of a yellow green
solid immediately precipitated, and the mixture
became less intensely colored. After 20 min, the
solvent was removed under reduced pressure at room
temperature, and the residue was washed first with
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