Synthesis and structural characterization of mercury(II) complexes with a novel ferrocenyliminophosphine

Article abstract of DOI:10.1016/j.ica.2006.01.007

Synthesis of the novel ligand ferrocenyliminophosphine [(η⁵-C₅H₅)Fe{(η⁵ -C₅H₄)CH{double bond, long}N(C₆H₄-2-PPh₂)}] (1, L) and studies on its complexation properties with mercury (II) are reported. Halogen-bridged binuclear mercury (II) complexes [HgX(μ-X)L]₂ (X = Cl (2a), Br (2b)) and a mononuclear mercury (II) complex HgCl₂L₂ (4a) have been obtained under different reaction conditions. In both cases, the ferrocenyliminophosphine acts as a P-monodentate ligand and the imino nitrogen does not participate in coordination to mercury (II). All the new compounds 1, 2a, 2b and 4a were characterized by elemental analysis, ¹H NMR, ³¹P NMR and IR spectra. In addition, structures of 2a and 4a have been determined by X-ray single-crystal analysis.

Full text of DOI:10.1016/j.ica.2006.01.007

Inorganica Chimica Acta 359 (2006) 2115–2120
www.elsevier.com/locate/ica
Synthesis and structural characterization of mercury(II) complexes
with a novel ferrocenyliminophosphine
*
*
Jun-Fang Gong , Da-Wei Wang, Yan-Hui Zhang, Yu Zhu, Yang-Jie Wu
Department of Chemistry, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan
Universities, Zhengzhou University, Daxue Road 75, Zhengzhou, Henan Province 450052, PR China
Received 17 October 2005; received in revised form 10 January 2006; accepted 14 January 2006
Available online 21 February 2006
Abstract
Synthesis of the novel ligand ferrocenyliminophosphine [(g5-C5H5)Fe{(g5-C5H4)CH@N(C6H4-2-PPh2)}] (1, L) and studies on its
complexation properties with mercury (II) are reported. Halogen-bridged binuclear mercury (II) complexes [HgX(l-X)L]2 (X = Cl
(2a), Br (2b)) and a mononuclear mercury (II) complex HgCl2L2 (4a) have been obtained under different reaction conditions. In both
cases, the ferrocenyliminophosphine acts as a P-monodentate ligand and the imino nitrogen does not participate in coordination to mer-
1
cury (II). All the new compounds 1, 2a, 2b and 4a were characterized by elemental analysis, H NMR, 31P NMR and IR spectra. In
addition, structures of 2a and 4a have been determined by X-ray single-crystal analysis.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Ferrocenyliminophosphine; Mercury (II) complexes; Crystal structures; Synthesis
1. Introduction
used in Heck reaction [7], Suzuki coupling [8] and the
dimerization of arylmercurials [9]. Considering the wide
applications of iminophosphines in catalysis and our inter-
est in the cyclometallation of ferrocenylimines, we prepared
Phosphorus–nitrogen mixed donor ligands are widely
used in catalysis due to the presence of both soft (phospho-
rus) and hard (nitrogen) donor atoms. As an important
class of P,N-ligands, iminophosphines have received
increasing attention recently owing to their excellent per-
formance in a number of catalytic reactions such as Heck
reaction [1], the Suzuki [2] and Stille coupling [3], the reg-
ioselective stannylative cycloaddition of conjugated enynes
[4], olefin polymerization and CO-olefin copolymeriation
[5]. During the past decades, we have systematically studied
the cyclometallation (also termed ortho-metallation,
including cyclomercuration, cyclopalladation and cyclopla-
tination) of Schiff base type of ferrocenylimines [6]. Some
of the cyclopalladated compounds have been successfully
a
novel ferrocenyliminophosphine [(g5-C5H5)Fe{(g5-
C5H4)CH@N(C6H4-2-PPh2)}] (1, L) and studied its
cyclomercuration with the aim of getting the ortho-mercu-
rated product of 1. However, the obtained product 2a from
direct cyclomercuration was proved to be a P-coordinated
binuclear mercury (II) complex. And another attempt led
to the formation of P-coordinated mononuclear mercury
(II) complex 4a. Herein, we report our results on the syn-
thesis and structural characterization of mercury (II) com-
plexes with 1.
2. Results and discussion
2.1. Synthesis and characterization
*
Corresponding authors. Tel.: +86 371 67766667/3207; fax: +86 371
Ferrocenyliminophosphine (1) was easily synthesized by
condensation of formylferrocene with 2-(diphenylphosph-
ino)aniline in refluxing toluene in the presence of activated
67766667.
E-mail addresses: gongjf@zzu.edu.cn (J.-F. Gong), wyj@zzu.edu.cn
(Y.-J. Wu).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.01.007

2116
J.-F. Gong et al. / Inorganica Chimica Acta 359 (2006) 2115–2120
Al2O3 (Scheme 1). Since the cyclomercurated ferrocenyli-
mines were found to be useful precursors for organic syn-
thesis and the synthesis of other cyclometallated
ferrocenylimines [6], first we studied the reaction of 1 with
Hg(OAc)2/LiCl under our standard conditions for cyclom-
ercuration of ferrocenylimines. The reaction went well and
red solids of 2a were obtained after purification by prepara-
nuclear mercury (II) complex HgCl2L2 4a with P:Hg stoi-
chiometry being 2:1 by single crystal X-ray analysis. In
complex 4a, the ferrocenyliminophosphine also acted as a
P-monodentate ligand. Considering the cleavage of the
C–Hg bond was possibly due to the high reaction temper-
ature (refluxing toluene), the condensation was carried out
in CH2Cl2 at room temperature in the presence of a cata-
lytic amount of TsOH (Method 2). The reaction finished
in 1 h and surprisingly, we still only got complex 4a. It
seemed that the soft P atom coordinated so strongly to
Hg that made the usually stable C–Hg bond cleaved easily
even at room temperature. On the other hand, the conden-
sation of ortho-mercurated acetylferrocene 3b with 2-(diph-
enylphosphino)aniline could not be achieved either in
refluxing toluene in the presence of activated Al2O3 or in
CH2Cl2 at room temperature in the presence of TsOH.
Only acetylferrocene was isolated.
It was reported in the literature that [HgX(l-X)L]2 and
HgX2L2 (X = Cl, Br, I) type complexes could be produced
in yields exceeding 90% by direct reaction of mercury (II)
halides with stoichiometric amounts of the P-monodentate
ligand [10]. Since we only obtained the P-coordinated mer-
cury complexes in our experiments up to now, we were
interested to see whether we could get mercury complexes
with 1 by using this simple and efficient method. It was
found that the yield of 2a did increased dramatically
(81.7% versus 38.6% by Hg(OAc)2/LiCl method) from
the reaction of equimolar amounts of 1 with HgCl2
(P:Hg = 1:1) (Scheme 3). And the corresponding bro-
mine-bridged binuclear mercury (II) complexes 2b could
also be prepared by reacting equimolar amounts of 1 with
HgBr2 in 82.6% yield. In contrast, the mononuclear com-
plex 4a could not be obtained by reaction of 1 and HgCl2
in a 2:1 molar ratio (P:Hg = 2:1) and only 2a was isolated
from the reaction. The result was different from that
reported in the literature [10], where the authors got the
mononuclear mercury(II) complexes by reaction of their
ligand with HgX2 in a 2:1 molar ratio.
1
tive TLC (see Section 3). H NMR spectrum of 2a exhib-
ited two singlet at d 4.65 and 5.10 for the substituted Cp
ring and one singlet at d 4.07 for the unsubstituted Cp ring
with the proton ratio being 4:5. The result showed clearly
that 2a was not ortho-mercurated product in which the
ratio should be 3:5. X-ray analysis of single crystals of
2a, which were obtained by slow evaporation of a chloro-
form–pentane solution of the complex, confirmed that 2a
was a chlorine-bridged binuclear mercury (II) complex
[HgCl(l-Cl)L]2 with P:Hg stoichiometry being 1:1. The
ferrocenyliminophosphine (1) acted as a P-monodentate
ligand in complex 2a (Scheme 2).
Next, we made another attempt by preparation of ortho-
mercurated acylferrocenes 3 first and then condensing 3
with 2-(diphenylphosphino)aniline (Scheme 2). The reac-
tion of 3a proceeded smoothly in refluxing toluene in the
presence of activated Al2O3 to afford red solids of the prod-
uct after preparative TLC (Method 1). The IR spectrum of
the product confirmed formation of the desired C@N
bond. However, 1H NMR spectrum indicated evidently
that the proton ratio between substituted and unsubsti-
tuted Cp ring was 4:5, suggesting the chloromercurio group
broke away from the substituted Cp ring. The molecular
structure of the product was finally proved to be a mono-
O
CH
N
H N
2
H
Al2O3
+
Fe
Fe
toluene, reflux
Ph2P
Ph2P
1
All the new compounds 1, 2a, 2b and 4a were character-
1
ized by elemental analysis, H NMR, 31P NMR and IR
Scheme 1.
Cl
Cl
Cl
Hg
Hg
CH
N
Ph2P
PPh2
Cl
1) Hg(OAc)2
2) LiCl
Fe
Fe
N
N
Fe
CH
Ph2P
CH
2a
Cl
1
Cl
O
Method 1
Al2O3, toluene
reflux
Hg
PPh2
Ph2P
H2N
Ph2P
Fe
R
Fe
N
+
N
Fe
HgCl
Method 2
TsOH(cat.)
CH2Cl2, r.t.
C
C
R
R
3 R = H(a), CH3(b)
4 R = H(a), CH3(b)
Scheme 2.

J.-F. Gong et al. / Inorganica Chimica Acta 359 (2006) 2115–2120
2117
X
X
X
Hg
Hg
CH
N
Ph2P
X
PPh2
HgX2, HOAc
Fe
Fe
N
N
Fe
CH
Ph2P
CH
1
2 X = Cl(a), Br(b)
Scheme 3.
spectra. The C@N absorption of the free ligand 1 was
appeared at 1618 cmÀ1, while those of mercury complexes
were shifted to lower energy ranging from 1604 to
1609 cmÀ1. This indicated that the electron density of
C@N bond decreased possibly due to the P–Hg coordina-
tion. All the compounds showed absorptions at approxi-
mately 1000 and 1100 cmÀ1
,
indicating of an
1
unsubstituted Cp ring [11]. The H NMR spectra of the
new compounds were consistent with the proposed struc-
ture. In comparison with 1, the corresponding chemical
shifts of mercury (II) complexes were shifted evidently to
downfield.
Fig. 2. Molecular structure of 4a.
2.2. Crystal structures of 2a and 4a
The crystal structures of 2a and 4a are shown in Figs. 1
and 2. All H atoms and the solvent molecules have been
omitted for clarity. Crystallographic and data collection
parameters for 2a Æ 4CHCl3 and 4a Æ 2CH2Cl2 are summa-
rized in Table 1. The selected bond lengths and angles
are given in Table 2. As depicted in Fig. 1, complex 2a is
a halogen-bridged centrosymmetric dimer in which each
mercury atom is four-coordinated by two bridging chloro
ligands, one terminal chloro ligand and a phosphorus atom
of the ferrocenyliminophosphine (1). The imino nitrogen of
the ligand does not participate in coordination to mercury
(II). The mercury center exhibits a significantly distorted
tetrahedral geometry with bond angles ranging from
84.78 (6)ꢁ to 132.66(7)ꢁ. The Hg–P distance, Hg–Clterminal
distance, P–Hg–Clterminal angle and Clbridge–Hg–Clbridge
angle (2.3913(16) A, 2.430(2) A, 132.66(7)ꢁ, 84.78 (6)ꢁ,
respectively) resemble the values found in [HgCl(l-
˚
˚
˚
˚
Cl)PPh3]2 (2.406(7) A, 2.370(10) A, 128.7(4)ꢁ and 85.4(4)ꢁ,
respectively) [12] and in [HgCl(l-Cl)Ph2Ppym 2
]
˚
(Ph2Ppym = 2-(diphenylphosphino)pyrimidine, 2.398(2) A,
2.375(3) A, 132.8(1)ꢁ and 85.2(1)ꢁ, respectively) [13]. How-
ever, these halogen-bridged dimers show an obvious differ-
˚
ence in the Hg–Clbridge distances. In complex 2a, the two
˚
Hg–Clbridge distances (2.8428(18) and 2.501(2) A) are quite
different, while in the latter two complexes, these bridging
˚
distances are almost equal (2.658(8) and 2.623(8) A,
˚
2.652(3) and 2.626(2) A, respectively). Fig. 2 shows com-
plex 4a to be a distorted tetrahedral monomer. The bond
angles around the mercury atom vary from 96.9(2)ꢁ (Cl–
Hg–Cl) to 140.03(18)ꢁ (P–Hg–P). The Hg–P and Hg–Cl
˚
bond lengths (2.522(4) and 2.601(4) A, respectively) are
comparable to those found for the related HgCl2(PPh3)2
˚
(2.47 and 2.552 A, respectively) [14], while the PHgP angle
in complex 2a (140.03(18)ꢁ) is larger than that in
HgCl2(PPh3)2 (134.1(1)ꢁ) possibly due to the steric effect
of the ferrocenyliminophosphine.
3. Experimental
3.1. General
Solvents were dried using the appropriate drying agents
(toluene/Na/benzophenone, MeOH/Mg, CH2Cl2/CaH2)
and distilled under nitrogen prior to use. Al2O3 was
Fig. 1. Molecular structure of 2a.

2118
J.-F. Gong et al. / Inorganica Chimica Acta 359 (2006) 2115–2120
Table 1
Crystallographic and data collection parameters for 2a Æ 4CHCl3 and 4a Æ 2CH2Cl2
2a Æ 4CHCl3
4a Æ 2CH2Cl2
Empirical formula
Formula weight
Temperature (K)
C58H48Cl4Fe2Hg2N2P2 Æ 4CHCl3
1967.08
291(2)
0.71073
triclinic
C58H48Cl2Fe2HgN2P2 Æ 2CH2Cl2
1387.97
291(2)
0.71073
monoclinic
C2/c
˚
Wavelength (A)
Crystal system
Space group
Unit cell dimensions
ꢀ
P1
˚
a (A)
10.729(2)
31.000(6)
˚
b (A)
12.429(3)
15.239(3)
9.3500(19)
22.134(4)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
105.47(3)
107.25(3)
92.35(3)
1854.3(6)
90
117.59(3)
90
5686(2)
3
˚
V (A )
Z
1
4
Dcalc (Mg/m3)
1.761
5.168
952
1.621
3.576
2760
Absorption coefficient (mmÀ1
F(000)
)
Crystal size (mm)
h Range for data collection (ꢁ)
Index ranges
Reflections collected/unique [Rint
Maximum and minimum transmission
Refinement method
0.20 · 0.18 · 0.18
1.46–25.00ꢁ
À12 6 h 6 12, 0 6 k 6 14, À18 6 l 6 17
5654/5654 [0.0000]
0.4564 and 0.4246
full-matrix least-squares on F2
5654/0/389
0.20 · 0.18c · 0.18
1.48–23.00ꢁ
À34 6 h6 9, À9 6 k 6 10, À20 6 l 6 24
6322/3562 [0.1283]
0.5654 and 0.5349
full-matrix least-squares on F2
3562/0/330
]
Data/restraints/parameters
Goodness-of-fit on F2
1.036
1.102
Final R indices [I > 2r(I)]
R indices (all data)
Largest difference peak and hole (e A
R1 = 0.0384, wR2 = 0.0927
R1 = 0.0479, wR2 = 0.0985
0.788 and À0.770
R1 = 0.0963, wR2 = 0.2308
R1 = 0.1127, wR2 = 0.2449
3.688 and À1.884
À3
˚
)
Table 2
Melting points were obtained using a WC-1 microscopic
apparatus and are uncorrected. Elemental analyses were
determined with a Carlo Erba 1160 Elemental Analyzer.
1H and 31P{1H}NMR spectra were recorded on a Bruker
DPX-400 spectrometer in CDCl3 with TMS as an internal
standard. IR spectra were collected on a Bruker VECTOR
22 spectrophotometer. Preparative TLC was performed on
dry silica gel plates developed with selected solvents as
eluents.
˚
Selected bond lengths (A) and angles (ꢁ) for 2a Æ 4CHCl3 and 4a Æ 2CH2Cl2
2a
Hg(1)–P(1)
Hg(1)–Cl(2)
N(1)–C(11)
P(1)–C(17)
P(1)–C(24)
2.3913(16) Hg(1)–Cl(1)
2.8428(18) Hg(1)–Cl(2A)
2.430(2)
2.501(2)
1.413(8)
1.791(7)
1.272(9)
1.799(6)
1.804(7)
N(1)–C(12)
P(1)–C(18)
P(1)–Hg(1)–Cl(1)
Cl(1)–Hg(1)–Cl(2)
Cl(1)–Hg(1)–Cl(2A)
Hg(1)–Cl(2)–Hg(1A)
C(17)–P(1)–C(24)
132.66(7)
99.89(7)
100.45(8)
95.22(6)
106.2(3)
P(1)–Hg(1)–Cl(2)
P(1)–Hg(1)–Cl(2A)
Cl(2)–Hg(1)–Cl(2A)
C(17)–P(1)–C(18)
C(18)–P(1)–C(24)
97.16(6)
124.93(7)
84.78(6)
109.1(3)
106.1(3)
3.2. Synthesis of ferrocenyliminophosphine (1)
A mixture of formylferrocene (0.860 g, 4.0 mmol) and 2-
(diphenylphosphino)aniline (1.322 g, 4.8 mmol) in toluene
was refluxed in the presence of activated alumina for 8 h
(monitored by IR). After cooling and filtration, the filtrate
was evaporated to dryness in vacuo and the residue was
recrystallized from dichloromethane–petroleum ether to
afford 1 (1.725 g, 90.1%) as a red solid. m.p. 170–171 ꢁC.
IR (KBr pellet): 3052, 1618, 1564, 1479, 1453, 1432,
4a
Hg(1)–P(1)
N(1)–C(11)
P(1)–C(17)
P(1)–C(24)
2.522(4)
Hg(1)–Cl(1)
N(1)–C(12)
P(1)–C(18)
2.601(4)
1.37(2)
1.836(17)
1.287(19)
1.838(16)
1.820(18)
P(1A)–Hg(1)–P(1)
P(1)–Hg(1)–Cl(1)
C(24)–P(1)–C(18)
C(18)–P(1)–C(17)
140.03(18)
101.43(14)
102.4(7)
P(1A)–Hg(1)–Cl(1)
Cl(1)–Hg(1)–Cl(1A)
C(24)–P(1)–C(17)
104.78(14)
96.9(2)
105.6(7)
1
1100, 1000, 823, 741, 696, 502 cmÀ1. H NMR (CDCl3):
103.4(7)
d 8.18 (s, 1H, CH@N), 7.32 (m, 11H, Ar–H), 7.09 (t,
J = 7.4 Hz, 1H, Ar–H), 6.99 (dd, J = 4.8, 7.6 Hz, 1H,
Ar–H ), 6.77 (dd, J = 4.0, 6.8 Hz, 1H, Ar–H ), 4.63 (s,
2H, C5H4), 4.38 (s, 2H, C5H4), 3.96 (s, 5H, C5H5).
activated at 120 ꢁC for 2 h before use. Formylferrocene
[15], 2-(diphenylphosphino)aniline [16] and 2-(chloromer-
curi)-1-acylferrocene 3 [17] were prepared according to
published procedures. All other chemicals were used as
purchased.
31P{1H}NMR (CDCl3):
d
À15.46. Anal. Calc. for
C29H24FeNP: C, 73.59; H, 5.11; N, 2.96. Found: C,
73.38; H, 4.99; N, 2.87%.

J.-F. Gong et al. / Inorganica Chimica Acta 359 (2006) 2115–2120
2119
3.3. Synthesis of mercury (II) complexes with 1
(m, 22H, Ar–H), 7.21 (m, 4H, Ar–H), 6.96 (m, 2H, Ar–
H), 4.86 (s, 4H, C5H4), 4.50 (s, 4H, C5H4), 4.02 (s, 10H,
C5H5). 31P{1H}NMR (CDCl3): d 34.53. Anal. Calc. for
C58H48Cl2Fe2HgN2P2: C, 57.19; H, 3.97; N, 2.30. Found:
C, 56.97; H, 3.83; N, 2.19%.
Method 2: A solution of 2-(chloromercuri)-1-formylfer-
rocene (3a) (0.225 g, 0.5 mmol) and 2-(diphenylphosph-
ino)aniline (0.166 g, 0.6 mmol) in CH2Cl2 was stirred for
1 h at room temperature in the presence of catalytic
amount of TsOH (monitored by TLC). After evaporation
under reduced pressure, the crude was purified by prepara-
tive TLC using CH2Cl2–CH3OH (10:1) as eluent, giving
0.081 g (26.6%) of 4a as red solids.
3.3.1. Synthesis of 2
2a: Method 1: Mercuric acetate (0.160 g, 0.5 mmol) in
methanol was added dropwise to a stirred solution of 1
(0.237 g, 0.5 mmol) in 20 mL dichloromethane over a per-
iod of 30 min at room temperature and the reaction mix-
ture was stirred for 30 min. Then 0.5 mmol of lithium
chloride in 10 mL methanol was added dropwise, and stir-
red for another 30 min. The solution was washed with
water, dried over Na2SO4, filtered and evaporated under
reduced pressure. The crude was purified by preparative
TLC using CH2Cl2–CH3OH (10:1) as eluent, giving red
solids of 2a. Yield: 0.144 g (38.7%), m.p. >220 ꢁC (dec.).
IR (KBr pellet): 3052, 1609, 1564, 1478, 1435, 1102, 999,
3.4. X-ray crystallography
829, 750, 691, 500 cmÀ1 1H NMR (CDCl3): d 8.51 (d,
.
J = 2.2 Hz, 2H, CH@N), 7.69 (m, 2H, Ar–H), 7.58 (m,
20H, Ar–H), 7.33 (m, 4H, Ar–H), 7.07 (m, 2H, Ar–H),
5.10 (s, 4H, C5H4), 4.65 (s, 4H, C5H4), 4.07 (s, 10H,
Crystals of 2a were obtained by recrystallization from
chloroform–pentane solution and 4a from dichlorometh-
ane–petroleum ether at r.t. A single crystal of 2a or 4a suit-
able for X-ray analysis was mounted on a glass fiber. All
measurements were made on a Rigaku-IV imaging plate
area detector with graphite monochromated Mo Ka radia-
C5H5). 31P{1H}NMR (CDCl3):
d
18.42 (JHg–P =
3702 Hz). Anal. Calc. for C58H48Cl4Fe2Hg2N2P2: C,
46.76; H, 3.25; N, 1.88. Found: C, 46.71; H, 3.19; N, 1.81%.
Method 2: To a solution of 1 (0.119 g, 0.25 mmol) in hot
acetic acid (5 mL) was added a solution of HgCl2 (68 mg,
0.25 mmol) in acetone (2 mL). The mixture was stirred
for 30 min. Then cooled to 0 ꢁC and the resulting precipi-
tate was filtered off, washed with petroleum ether and puri-
fied by preparative TLC using CH2Cl2–CH3OH (10:1) as
eluent, to afford red solid of 2a. Yield: 0.152 g (81.7%).
When half of HgCl2 (34 mg, 0.125 mmol) was added, 2a
was isolated as the sole product. Yield (based on HgCl2):
0.079 g (84.9%).
˚
tion (k = 0.71073 A). The data were corrected for Lorentz
and polarization factors. The structure was solved by direct
methods [18] and expanded using Fourier techniques and
refined by full-matrix least-squares methods. The non-
hydrogen atoms were refined anisotropically, and the
hydrogen atoms were included but not refined. All calcula-
tions were performed using the TEXSAN [19] crystallographic
software package of Molecular Structure corporation.
Acknowledgements
2b was prepared by using method 2. Equimolar amounts
of HgBr2 was employed in place of HgCl2. The crude of 2b
was purified by preparative TLC using CH2Cl2–petroleum
ether (4:1) as eluent. 2b: red solids, Yield: 0.172 g (82.6%),
m.p. >210 ꢁC (dec.). IR (KBr pellet): 3052, 1604, 1566,
We thank the National Natural Science Foundation of
China (Project 20472074) and Education Ministry of China
for financial support of this work. We also thank Dr.
Zheng Duan for comments on this paper.
1
1478, 1435, 1101, 998, 826, 749, 691, 499 cmÀ1. H NMR
(CDCl3): d 8.46 (d, J = 2.4 Hz, 2H, CH@N), 7.68 (t,
J = 7.8 Hz, 2H, Ar–H), 7.56 (m, 20H, Ar–H), 7.33 (m,
4H, Ar–H), 7.06 (m, 2H, Ar–H), 5.07 (s, 4H, C5H4), 4.63
(s, 4H, C5H4), 4.10 (s, 10H, C5H5). 31P{1H}NMR (CDCl3):
Appendix A. Supplementary data
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic Data
Center, CCDC Nos. 278143 and 278142 for compounds 2a
and 4a, respectively. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: +44 1223
336 033, e-mail: deposit@ccdc.cam.ac.uk or on the web
www: http://www.ccdc.cam.ac.uk). Supplementary data
associated with this article can be found, in the online ver-
sion, at doi:10.1016/j.ica.2006.01.007.
d
16.66 (JHg–P = 3072 Hz). Anal. Calc. for C58H48-
Br4Fe2Hg2N2P2: C, 41.78; H, 2.90; N, 1.68. Found: C,
41.69; H, 2.79; N, 1.60%.
3.3.2. Synthesis of 4a
Method 1: A mixture of 2-(chloromercuri)-1-formylfer-
rocene (3a) (0.225 g, 0.5 mmol) and 2-(diphenylphosph-
ino)aniline (0.166 g, 0.6 mmol) in toluene was refluxed in
the presence of activated alumina for 6 h. After cooling
and filtration, the filtrate was concentrated in vacuo. The
residue was purified by preparative TLC using CH2Cl2–
CH3OH (10:1) as eluent, to produce 0.141 g (46.3%) of
4a as red solids. m.p. 151–152 ꢁC. IR (KBr pellet): 3052,
1604, 1562, 1479, 1454, 1434, 1101, 999, 824, 746, 692,
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