Ortho-mercurated [({N-methyl-N-arylamino}methyl)ferrocenes] and their transpalladation. Crystal structures of [(η5-C5H5)Fe{η5- C5H3(HgCl)CH2N(CH3)C6 H4OCH3-4}]2, [(η5-C5H5)Fe{η5- C5H ...

Article abstract of DOI:10.1016/j.poly.2006.06.012

Full title. Ortho-mercurated [({N-methyl-N-arylamino}methyl)ferrocenes] and their transpalladation. Crystal structures of [(η⁵-C₅H₅)Fe{η⁵- C₅H₃(HgCl)CH₂N(CH₃)C₆ H₄OCH₃-4}]₂, [(η⁵-C₅H₅)Fe{η⁵-C ₅H₃(HgCl)CH₂N(CH₃)C₆ H₄Cl-3}] and [(η⁵-C₅H₄HgCl)Fe{η⁵- C₅H₄CH₂N(CH₃)C₆ H₄Cl-4}]. Treatment of ferrocenylamines [(η⁵-C₅H₅)Fe{η⁵- C₅H₄CH₂N(CH₃)C₆H ₄R}] (4) (R = 4-MeO (a), 4-Me (b), H (c), 4-Cl (d), 3-Cl (e), 3-NO₂(f)) with mercury (II) acetate and lithium chloride yielded ortho-mercurated [(η⁵-C₅H₅)Fe{η⁵- C₅H₃(HgCl)CH₂N(CH₃)C₆ H₄R}] (6) (R = same as before) and a minor product [(η⁵-C₅H₄HgCl)Fe{η⁵- C₅H₄CH₂N(CH₃)C₆ H₄Cl-4}] (7) from 4d (R = 4-Cl). The character of the substituents on the phenyl rings might play an important role in governing the product distributions. The preference of intermolecular over intramolecular N-Hg interactions in 6 was observed and rationalized. Transpalladations of 6 via disodium tetrachloropalladate (II) gave the corresponding cyclopalladated complexes in low yields. The molecular structures of 6a, e, and 7 were determined by single crystal X-ray analysis.

Full text of DOI:10.1016/j.poly.2006.06.012

Polyhedron 25 (2006) 3305–3311
www.elsevier.com/locate/poly
Ortho-mercurated [({N-methyl-N-arylamino}methyl)ferrocenes]
and their transpalladation. Crystal structures of
[(g5-C5H5)Fe{g5-C5H3(HgCl)CH2N(CH3)C6H4OCH3-4}]2,
[(g5-C5H5)Fe{g5-C5H3(HgCl)CH2N(CH3)C6H4Cl-3}] and
[(g5-C5H4HgCl)Fe{g5-C5H4CH2N(CH3)C6H4Cl-4}]
a,
a
a
a
a
Hong-Xing Wang *, Ying-Jie Li , Hong-Fei Wu , Ren-Qing Gao , Feng-Ying Geng ,
a
a
b
c
c
Xiao-Li Yang , Li Wan , Rong Jin , Xiu-Ling Cui , Yang-Jie Wu
a
Department of Chemistry, College of Sciences, Tianjin University, No. 92, Weijin Road, Nankai District, Tianjin 300072, People’s Republic of China
b
Department of Ultrasound, the First Central Hospital of Tianjin, Tianjin 300192, People’s Republic of China
c
Department of Chemistry, Zhengzhou University, Zhengzhou 450052, People’s Republic of China
Received 11 April 2006; accepted 4 June 2006
Available online 30 June 2006
Abstract
Treatment of ferrocenylamines [(g5-C5H5)Fe{g5-C5H4CH2N(CH3)C6H4R}] (4) (R = 4-MeO (a), 4-Me (b), H (c), 4-Cl (d), 3-Cl (e),
3-NO2(f)) with mercury (II) acetate and lithium chloride yielded ortho-mercurated [(g5-C5H5)Fe{g5-C5H3(HgCl)CH2N(CH3)C6H4R}]
(6) (R = same as before) and a minor product [(g5-C5H4HgCl)Fe{g5-C5H4CH2N(CH3)C6H4Cl-4}] (7) from 4d (R = 4-Cl). The character
of the substituents on the phenyl rings might play an important role in governing the product distributions. The preference of intermo-
lecular over intramolecular N–Hg interactions in 6 was observed and rationalized. Transpalladations of 6 via disodium tetrachloropal-
ladate (II) gave the corresponding cyclopalladated complexes in low yields. The molecular structures of 6a, e, and 7 were determined by
single crystal X-ray analysis.
ꢀ 2006 Elsevier Ltd. All rights reserved.
Keywords: Ferrocenylamines; Mercuration; Ortho-metallation; Crystal; Mechanism
1. Introduction
chemistry, selectivity, etc. Parish et al. [1b] reported that
when N,N-dimethylbenzylamines reacted with n-BuLi/
HgCl2 at ꢀ78ꢁ, the ortho-mercurated benzylamines 1 were
obtained in which an intramolecular N–Hg coordination
was probably involved. Jacob et al. [1f] found that treat-
ment of (N,N-dimethylamino)methylferrocene (FcN) with
n-BuLi/HgCl2 under the conditions mentioned above led
to an ortho-mercurated dimer 2 with a 10 membered ring
from which an intermolecular N–Hg coordination
Organic mercury compounds, especially those bearing
hetero atoms [1–3], are a class of important intermediates
in organic synthesis [4]. They are easily prepared by direct
mercuration of the corresponding substrates and then
undergo other transformations including halogenation [5],
transmetallation [6], as well as carbon–carbon bond forma-
tion [7], etc. In addition, most mercurated compounds are
very stable and easy to handle, which provides an excellent
opportunity to investigate the reaction mechanism, stereo-
˚
(2.780 A) was observed. Our previous results [8] demon-
strated that mercuration of ferrocenylimines under mild
conditions (Hg(OAc)2/LiCl/room temperature) resulted in
predominately theortho-mercurated 3. Furthermore, an
intramolecular N–Hg coordination is present in these
*
Corresponding author. Tel.: +86 22 27892355; fax: +86 22 27403475.
E-mail address: hongxing_wang@hotmail.com (H.-X. Wang).
0277-5387/$ - see front matter ꢀ 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2006.06.012

3306
H.-X. Wang et al. / Polyhedron 25 (2006) 3305–3311
molecules. Very recently, we described the synthesis of
tertiary aromatic ferrocenylamines 4 by methylation of
ferrocenylimines [9a] or secondary ferrocenylamines [9b].
In this paper, we wish to report the synthesis and charac-
terization of their ortho-mercurated complexes (R0 = H).
In addition, their transpalladation and the influence of
the structural factors of substrates on the product distribu-
tions and aggregations will also be discussed. As far as we
know it is the first reported example of ortho-mercurated
aromatic ferrocenylamines.
2.2. Spectra characterization of 6a–f, 7
Complexes 6 and 7 were characterized by elemental
1
analysis, IR and H NMR. Elemental analyses for 6 and
7 are in good agreement with the proposed formula. In
the IR spectra of 6, the presence of two medium absorption
bands, m 1100 and 1000 cmꢀ1, confirms that they all have
an unsubstituted cyclopentadienyl (Cp) ring [10]. On the
contrary, such absorptions in 7 are absent. In the 1H
NMR spectra of 6, a singlet appearing at d 4.20 ppm
N
R
R'
Cl Hg
N
C
N
Fe
N(CH3)2
Hg
Cl
N
Hg
R'
R1
R
Cl
Hg
R2
Cl
Fe
Fe
Fe
R1, R2 = MeO or NMe2
1
2
3
4
2. Results and discussion
2.1. Ortho-mercuration of ferrocenylamines 4
corresponds to the unsubstituted Cp ring, two doublets
approximately at d 4.10 ppm are assigned to H3 and H5,
respectively, and a multiplet appearing at d 4.40 ppm is
attributed to H4. In all cases the chemical shifts of H11
are overlapped with those of H4. In addition, the protons
in the phenyl rings also give their corresponding splitting
patterns.
The reactions of ferrocenylamines 4 (R0 = H) and an
equivalent amount of mercury (II) acetate were carried
out in methanol at room temperature (Scheme 1) and the
reactions progress were monitored by TLC. After the reac-
tions were completed, 1.5 equivalent of lithium chloride
was added and the mixtures were stirred for 30 min.
Removal of solvent yielded residues which were purified
by column chromatography (silica gel, ethyl acetate/
hexane = 1:1, v/v) to afford ortho-mercurated ferrocenyl-
amines 6 and the 1,10-disubstituted ferrocene derivative 7.
Complexes 6 and 7 are stable in air, and are soluble in most
of organic solvents, but poorly soluble in hexane.
Experimental results show that the character of the sub-
stituents on the phenyl ring will play an important role in
governing product distributions. For example, mercuration
of ferrocenylamines bearing electron-donating groups
(4a, b) normally give 6a (b) in higher yields (P62%),
whereas for mercuration of ferrocenylamines bearing
electron-withdrawing groups (4d, f), the yields of 6d (f)
are lower (6 58%). When ([N-methyl-N-4-nitrophenyl-
amino]methyl)ferrocene is treated with mercury (II) ace-
tate, the expected ortho-mercurated product is not isolated.
2.3. N–Hg intermolecular vs intramolecular coordination
The crystal structure of 6a (Fig. 1) demonstrates that the
crystal consists of two unsymmetric molecular units. The
˚
distance Hg1–N2 2.927(1) A is shorter than the sum of
˚
their van der Waals radii (3.00–3.23 A) [11a], indicating
that an intermolecular N–Hg coordination is present in this
molecule. However, such coordination between Hg2 and
N1 is absent. In the crystal structure of 6e (Fig. 2),
although the crystal consists of a monomer, the intermolec-
˚
ular N–Hg coordination (N1B–Hg1A 3.863(1) A) is still
present (Fig. 3). In addition, in these two crystals, a 10
membered ring, like in 2, is not formed. All these results
are partially consistence with Jacob’s observation [1f].
The intermolecular N–Hg distance in 6a is slightly longer
than that in 6e, but the intramolecular N–Hg distances in
˚
˚
6a, e (4.125(1) A, 4.100(1) A, respectively) are nearly same
and they all are significantly longer than the sum of their
12 13
12 13
11
2
11
2
14
N
N
N
Cl
14
N
5
1
5
1
HgCl 16
15
16 15
R
i
R
R
ii
4
4
HgOAc
Fe
Fe3
Fe3
Fe
6
10
6
10
7
HgCl
7
4
5
6
7
Scheme 1. (i) Hg(CH3CO2)2, methanol and (ii) LiCl, methanol. R = 4-MeO (a), 4-Me (b), H (c), 4-Cl (d), 3-Cl (e), and 3-NO2 (f).

H.-X. Wang et al. / Polyhedron 25 (2006) 3305–3311
3307
Fig. 1. Molecular structure of 6a with the numbering scheme (H atoms
are omitted for clarity).
Fig. 3. Intermolecular N(1B)ꢁ ꢁ ꢁHg(1A) interaction pattern for compound
6e (H atoms are omitted for clarity).
on the phenyl rings only increases or reduces the coordina-
tion ability of the N atom with Hg, but does not alter the
type of N–Hg coordination (intermolecular vs intramolec-
ular). Structurally, 4a–f are more like FcN than ferroce-
nylimines, therefore, the possible mechanism for the
formation of 6 is depicted as in Scheme 2.
According to the principle of ortho-metallation, initial
coordination of the metal with the hetero atom is neces-
sary, and then following is activation of its adjacent
C–H bonds. As shown in Scheme 2, the coordinated N–
Hg moiety can activate C–H bonds not only through path
i (N–Hg intramolecular coordination) but also through
path ii (N–Hg intermolecular coordination). However,
the preference of intermolecular over intramolecular
N–Hg coordination in our case is always observed. This
is probably because (1) the N–Hg coordination is a
non-covalent weak interaction, which is not sufficient to
keep the rigid five member ring (path i) more stable than
the corresponding palladocycles [12], and this weak coor-
dination is supported by the molecular structure of 7
(Fig. 4), which is formed by the attack of free mercury
(i.e., without coordination with an N atom) on the unsub-
stituted Cp ring; (2) unlike the ferrocenylimines, their
Fig. 2. Molecular structure of 6e with the numbering scheme.
van der Waals radii [11a], suggesting that an N–Hg intra-
molecular coordination pattern is absent in these crystals.
Therefore, we believe that the character of the substituents
Fe
N
i
R
R
Hg(OAc)2
11
ii
LiCl
i
Intermolecular N-Hg
coordinated products
Intramolecular N-Hg
coordinated products
N
ii
1
LiCl
Hg(OAc)2
Fe
Scheme 2. Possible mechanism for the formation of 6, path i, intramolecular activation; path ii, intermolecular activation.

3308
H.-X. Wang et al. / Polyhedron 25 (2006) 3305–3311
Fig. 4. Molecular structure of 7 with the numbering scheme.
imino groups are coplanar with the substituted Cp rings
[8], the (N-methyl-N-phenyl)amino groups in 4 lie above
the substituted Cp rings [9], thus the N–Hg coordinated
intermediates adapting a similar conformation will disfa-
vor the activation of the intramolecular C–H bond (path
i). However, this conformation will enable the intermedi-
ates (Scheme 2) to activate the intermolecular C–H bonds
with a minimum energy and hence produce a flexible zig-
zag link (path ii). This hypothesis is supported by the fact
that both 6 and 4 keep a similar conformation (the tor-
sion angle C2–C21–N1–C23 (69.5(5)ꢁ) in 6a is the same
as that in 4a (70.0(3)ꢁ) [9b]. In addition, dimer complexes
with a 10 membered ring are also excluded because their
formation needs the N–Hg moiety in one intermediate to
rotate around the axis of the C1–C11 bond and subse-
quently activate the intermolecular ortho C–H bond in
another intermediate, and this rotation is probably
retarded due to steric hindrance between the phenyl and
the hydrogen in the Cp ring [12].
sented in Fig. 3. Crystal parameters and data collection
for 6a, e and 7 are summarized in Table 1. Their selected
bond lengths and angles are listed in Tables 2 and 3,
respectively.
Figs. 1 and 2 demonstrate that chloromercurio units
in 6a and e are connected directly to the ortho position
of the amino group, whereas in 7 it is connected to
the second Cp ring (Fig. 4). The Hg1–Cl bond lengths
˚
in 6a, e, and 7 (2.043(4), 2.044(2), and 2.045(4) A,
respectively) are nearly the same and are in the normal
˚
range. The distance Fe–Hg 3.607(1) A in 7 is nearly
equal to the sum of the constituent van der Waals radii
˚
(3.55 A) [11a], indicating that a weak Fe–Hg interaction
is present. However, such an interaction in 6a and e is
absent. The Cl1–Hg1–C1 bond angles in 6a, e, and 7
(176.2(2), 177.9(2), and 178.0(3)ꢁ, respectively) are closer
to the ideal value of 180ꢁ in organic derivatives of mer-
cury. The dihedral angle Cl1–Hg1–C1–C2 (ꢀ180(6)ꢁ) in
6e means that the chloromercurio unit is coplanar with
the substituted Cp ring. However, the Cl1 atom in 7 is
pocketed between two paralleled Cp rings. The angle
between the chloromercurio unit and the substituted Cp
ring is 75.9(1)ꢁ, implying that they are nearly perpendic-
ular to each other. In Fig. 1, the dihedral angle between
the substituted Cp ring and the intramolecular phenyl
2.4. Crystal structures of 6a, e, and 7
The molecular structures of 6a, e, and 7 were determined
by X-ray single crystal diffraction (Figs. 1, 2, and 4). The
intermolecular N–Hg coordination pattern in 6e is pre-
Table 1
Crystallographic data for 6a, e, and 7
Compound
Empirical formula
M
6a
C
1140.50
6e
C18H17Cl2FeHgN
574.67
7
38H40Cl2Fe2Hg2N2O2
C18H17Cl2FeHgN
574.67
Crystal dimensions (mm)
Crystal system, space group
0.26 · 0.20 · 0.12
triclinic, P1
0.14 · 0.12 · 0.10
triclinic, P1
0.22 · 0.20 · 0.18
triclinic, P1
ꢀ
ꢀ
ꢀ
˚
a (A)
12.546(5)
12.750(3)
14.135(3)
114.409(2)
100.633(3)
103.511(3)
1898.4(9)
2
7.9393(1)
10.4298(2)
12.268(2)
68.447(2)
72.426(2)
71.852(2)
877.4(3)
6.1781(1)
7.0755(2)
20.662(5)
91.197(6)
98.268(5)
103.698(5)
867.0(3)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
2
2
qcalcd (Mg mꢀ3
)
1.995
8.987
1088
2.175
9.866
544
2.201
9.985
544
l (mmꢀ1
F(000)
)
Reflections collected/unique [Rint
Data/restraints/parameters
Final R1, wR2
]
10428/6628 [0.0186]
6628/0/437
0.0255, 0.0555
0.677, ꢀ0.825
4945/3494 [0.0221]
3494/0/209
0.0307, 0.0733
1.575, ꢀ1.384
6076/3476 [0.0331]
3476/0/209
0.0674, 0.1675
5.181, ꢀ3.237
ꢀ3
˚
Largest difference in peak and hole (eA
)

H.-X. Wang et al. / Polyhedron 25 (2006) 3305–3311
3309
Table 2
Selected bond lengths (A) for 6a, e, and 7
˚
N
N
˚
˚
˚
6a
(A)
6e
(A)
7
(A)
R
R
HgCl
Pd Cl
PPh3
8
Hg(1)–N(2) 2.927(1) Hg(1)–C(1) 2.044(6) Hg(1)–C(1) 2.045(1)
Hg(1)–C(1) 2.043(4) Hg(1)–Cl(1) 2.324(2) Hg(1)–Cl(1) 2.324(4)
(i)
(ii)
Fe
Fe
Hg(1)–Cl(1) 2.318(1) Fe(1)–C(1)
2.055(5) Fe(1)–C(1)
2.057(6) Fe(1)–C(2)
1.445(8) Fe(1)–C(6)
1.477(8) C(6)–C(11)
2.033(1)
2.065(1)
2.043(1)
1.494(2)
Fe(1)–C(1)
Fe(1)–C(2)
C(1)–C(2)
C(2)–C(21)
2.047(5) Fe(1)–C(2)
2.028(4) C(1)–C(2)
1.435(6) C(2)–C(11)
6
Scheme 3. (i) Na2PdCl4, methanol, room temperature and (ii) PPh3,
methanol. R = 4-MeO (a), 4-Me (b), H (c), 4-Cl (d), 3-Cl (e), and 3-NO2
(f).
1.500(6) N(1)–C(11) 1.470(9) N(1)–C(11) 1.471(2)
N(1)–C(21) 1.487(6) N(1)–C(12) 1.375(9) N(1)–C(12) 1.440(2)
N(1)–C(23) 1.423(6) N(1)–C(18) 1.469(8) N(1)–C(13) 1.403(2)
N(1)–C(22) 1.458(6) C(12)–C(13) 1.413(9) C(13)–C(14) 1.410(2)
C(23)–C(24) 1.386(7) C(13)–C(14) 1.375(9) C(14)–C(15) 1.370(2)
C(24)–C(25) 1.387(7) C(14)–C(15) 1.357(1) C(15)–C(16) 1.390(2)
C(25)–C(26) 1.393(8) C(12)–C(17) 1.405(9) Cl(2)–C(16) 1.759(1)
prepared in our laboratory. Mercury (II) acetate, lithium
chloride and triphenylphosphine were obtained commer-
cially and used without further purification. All of the sol-
vents were purified with standard methods prior to use.
Melting points were obtained from Yanaco micro melting
point apparatus and were uncorrected. Elemental analyses
were measured on a Carlo Erba 1106 Elemental analyzer.
1H NMR spectra were obtained with a Bruker AV-400
spectrometer using CDCl3 as the solvent and TMS as inter-
nal standard. IR spectra were taken on a BIO-RAD 3000
spectrophotometer.
O(1)–C(26)
1.374(7) Cl(2)–C(14) 1.757(7)
ring is 56.8(1)ꢁ, the dihedral angle between the inter-
molecular two phenyl rings is 72.0(1)ꢁ. In addition, the
two pentagonal rings of the ferrocenyl moiety in 6a, e,
and 7 are planar and nearly parallel (interplanar angles
1.1, 2.2, and 0.9ꢁ, respectively). In addition, the Cp rings
are also nearly eclipsed.
2.5. Transpalladation via 6 and disodium
tetrachloropalladate (II)
3.2. Preparation of [(g5-C5H5)Fe(g5-C5H3(HgCl)CH2N-
(CH3)C6H4-R)] (6) and [(g5-C5H4HgCl)Fe-
(g5-C5H4CH2N(CH3)-C6H4–Cl-4)] (7)
In order to assess the properties of 6a–f, their transpalla-
dation reactions via disodium tetrachloropalladate (II) were
carried out in methanol at room temperature. However,
most of the palladium (II) was reduced to palladium (0)
black by 6a–f, and the yields of the isolated cyclopalladated
complexes 8 were much lower (620%) than that of the cyclo-
palladated ({N-methyl-N-benzylamino}methyl)ferrocenes.
Direct cyclopalladation of 4a–f gave similar results [12]. It
is believe that intermolecular N–Hg coordination may
account for such low yields of the cyclopalladated com-
plexes see Scheme 3.
General procedure. To a stirred solution of the ferroce-
nylamines (4) (5 mmol) in methanol (20 ml) and dichloro-
methane (5 ml), was added dropwise a solution of
mercury (II) acetate (5 mmol) in sufficient methanol. The
reactions were monitored by TLC until they were com-
plete. A solution of lithium chloride (7.5 mmol) in metha-
nol was then added and the mixtures were stirred for
30 min. The solvent was removed and the residues were
extracted with dichloromethane (3 · 30 ml), the organic
layer was dried over anhydrous sodium sulfate and evapo-
rated under reduce pressure to give the crude products
which were purified by chromatography (silica gel, ethyl
acetate/hexane = 1:1, v/v), the second band eluted was col-
lected, the solvent was removed in vacuo to give 6 as yellow
powders.
3. Experimental
3.1. Materials and instruments
Ferrocenylamines were prepared according to the litera-
ture procedure [9b], disodium tetrachloropalladate (II) was
Table 3
Selected bond angles (ꢁ) for 6a, e, and 7
6a
(ꢁ)
6e
(ꢁ)
7
(ꢁ)
C(1)–Hg(1)–Cl(1)
C(11)–Hg(2)–Cl(2)
N(2)–Hg(1)–Cl(1)
N(2)–Hg(1)–C(1)
C(2)–C(1)–Hg(1)
C(15)–C(11)–Hg(2)
C(1)–C(2)–C(21)
C(11)–C(15)–C(30)
N(1)–C(21)–C(2)
N(2)–C(30)–C(15)
176.2(1)
174.3(1)
87.8(2)
C(1)–Hg(1)–Cl(1)
C(2)–C(1)–Hg(1)
C(5)–C(1)–Hg(1)
Hg(1)–C(1)–Fe(1)
C(1)–C(2)–C(11)
N(1)–C(11)–C(2)
C(12)–N(1)–C(11)
N(1)–C(12)–C(13)
C(13)–C(14)–Cl(2)
177.9(2)
127.4(4)
125.1(4)
125.0(3)
126.6(5)
112.7(5)
123.8(5)
122.3(6)
117.4(5)
C(1)–Hg(1)–Cl(1)
C(2)–C(1)–Hg(1)
Fe(1)–C(1)–Hg(1)
C(10)–C(6)–C(11)
C(11)–C(6)–Fe(1)
N(1)–C(11)–C(6)
C(13)–N(1)–C(11)
N(1)–C(13)–C(14)
C(15)–C(16)–Cl(2)
178.0(3)
125.8(1)
124.4(6)
127.6(2)
124.3(1)
112.3(1)
118.4(1)
122.5(1)
118.5(1)
94.5(2)
126.8(3)
124.8(4)
126.8(4)
126.2(4)
113.9(4)
114.0(4)

3310
H.-X. Wang et al. / Polyhedron 25 (2006) 3305–3311
3.2.1. [(g5-C5H4)Fe(g5-C5H3(HgCl)N(CH3)C6H4–
OCH3-4)] (6a)
1H, H5), 4.24 (s, 5H, g-C5H5), 4.41 (m, 3H, H4, 11),
6.97–7.57 (m, 4H, H12, H13, H14, H16) ppm.
Yellow solid. Yield 67%; m.p. 142 ꢁC (dec.). Anal.
Calc. for C19H20ClFeHgNO: C, 40.02; H, 3.54; N, 2.46.
Found: C, 39.87; H, 3.58; N, 2.50%. IR (KBr): 3085,
3.2.7. [(g5-C5H4HgCl)Fe(g5-C5H4CH2N(CH3)-
C6H4–Cl-4)] (7)
2934, 2832, 1511, 1455, 1244, 1037, 818, 480 cmꢀ1 1H
.
In the reaction of 4d with mercury (II) acetate, the
third band eluted was also collected and 7 was isolated
as yellow powder. Yield 15%; m.p. 146 ꢁC (dec.). Anal.
Calc. for C18H17Cl2FeHgN: C, 37.62; H, 2.98; N, 2.44.
Found: C, 37.50; H, 2.84; N, 2.42%. IR (KBr): 3087,
NMR: d 2.78 (s, 3H, N-CH3), 3.76 (s, 3H, OCH3), 3.98
(d, 1H, H3), 4.08 (d, 1H, H5), 4.17 (s, 5H, g-C5H5),
4.33 (m, 3H, H4, H11), 6.78–6.85 (q, 4H, H12, H13,
H15, H16) ppm.
2937, 1595, 1496, 1245, 809, 730, 486 cmꢀ1 1H NMR:
.
3.2.2. [(g5-C5H5)Fe(g5-C5H3(HgCl)N(CH3)C6H4–
CH3-4)] (6b)
1H–NMR: d 2.70 (s, 3H, N-CH3), 3.92 (d, 2H, H7,
H10), 4.04 (m, 4H, H2, H5, H8, H9), 4.16 (d, 2H, H3,
H4), 4.23 (s, 2H, H11), 6.58–7.00 (q, 4H, H12, H13,
H15, H16) ppm.
Yellow solid. Yield 62%; m.p. 140 ꢁC (dec.). Anal. Calc.
for C19H20ClFeHgN: C, 41.17; H, 3.64; N, 2.53. Found: C,
41.00; H, 3.70; N, 2.48%. IR (KBr): 3087, 2957, 2860, 1520,
1457, 1104, 803, 483 cmꢀ1 1H NMR: d 2.16 (s, 3H,
.
3.3. Transpalladation of 6a–f via disodium
tetrachloropalladate (II)
Ar-CH3), 2.78 (s, 3H, N-CH3), 4.02 (d, 1H, H3), 4.15 (s,
5H, g-C5H5), 4.16 (d, 1H, H5), 4.28 (m, 3H, H4, H11),
6.76–6.83 (q, 4H, H12, H13, H15, H16) ppm.
To stirred solutions of 6 (2 mmol) in methanol (20 ml),
was added dropwise a methanol solution (30 ml) of diso-
dium tetrachloropalladate (II) (2 mmol) at room tempera-
ture over 1 h. The reactions progress were monitored by
TLC until they were complete, then triphenylphosphine
was added. The mixtures were filtered and the solvent
was removed in vacuo. The residues were purified by
column chromatography (silica gel, ethyl acetate/
hexane = 3:1, v/v) to give 8 as red–purple solids. The yields
of 8a–f were 20%, 20%, 17%, 14%, 18%, and 10%, respec-
tively. Their IR and NMR spectra were the same as the
authentic samples [12].
3.2.3. [(g5-C5H5)Fe(g5-C5H3(HgCl)N(CH3)C6H5)] (6c)
Yellow solid. Yield 65%; m.p. 180 ꢁC (dec.). Anal. Calc.
for C18H18ClFeHgN: C, 40.02; H, 3.36; N, 2.59. Found: C,
39.97; H, 3.40; N, 2.51%. IR (KBr): 3092, 2927, 2857, 2812,
1
1598, 1505, 1449, 1343, 1105, 819, 748, 691, 480 cmꢀ1. H
NMR: d 2.90 (s, 3H, N-CH3), 4.04 (d, 1H, H3), 4.11 (d,
1H, H5), 4.19 (s, 5H, g-C5H5), 4.34 (m, 3H, H4, H11),
6.75–6.80 (m, 5H, H12–H16) ppm.
3.2.4. [(g5-C5H5)Fe(g5-C5H3(HgCl)CH2N(CH3)-
C6H4–Cl-4)] (6d)
Yellow solid. Yield 60%; m.p. 138 ꢁC (dec.). Anal. Calc.
for C18H17Cl2FeHgN: C, 37.62; H, 2.98; N, 2.44. Found:
C, 37.36; H, 3.06; N, 2.36%. IR (KBr): 3088, 2937, 1593,
3.4. Crystal structure determination for 6a, e, and 7
1
1497, 1244, 1101, 999, 809, 731, 486 cmꢀ1. H NMR: d
Prismatic single crystals of 6a, e, and 7 suitable for X-
ray analysis were obtained by slow evaporation of a mix-
ture of ethyl acetate and hexane at room temperature over
a period of one week. The single crystals of 6a, e, and 7
were mounted on a Bruker SMART CCD diffractometer
equipped with graphite monochromated Mo Ka (k =
2.90 (s, 3H, N-CH3), 4.03 (d, 1H, H3), 4.10 (d, 1H, H5),
4.22 (s, 5H, g-C5H5), 4.38 (m, 3H, H4, H11), 6.70
(d, 2H, H12, H16), 7.20 (d, 2H, H13, H15) ppm.
3.2.5. [(g5-C5H5)Fe(g5-C5H3(HgCl)N(CH3)C6H4–
Cl-3)] (6e)
˚
0.71073 A) radiation at ambient temperature (T =
294 K) using the x-2h multi-scans technique with the
ranges 1.76ꢁ 6 h 6 26.03ꢁ (6a), 1.83ꢁ 6 h 6 26.32ꢁ (6e),
and 1.00ꢁ 6 h 6 26.59ꢁ (7) for data collection. Semi-
empirical absorption corrections were applied using the
SABABS program [13]. The structures were solved by direct
methods and refined by full-matrix least-squares proce-
dures on F2 using the SHELX suite of programs [14]. The
values of R1 were given based on Fo with a typical thresh-
old of F2 P 2r(F2). The weighted R-factors wR were
Yellow solid. Yield 64%; m.p. 188 ꢁC (dec.). Anal. Calc.
for C18H17Cl2FeHgN: C, 37.62; H, 2.98; N, 2.44. Found:
C, 37.40; H, 3.00; N, 2.30%. IR (KBr): 3091, 2933, 2890,
1
1594, 1495, 1251, 1188, 1102, 987, 820, 795, 483 cmꢀ1. H
NMR: d 2.90 (s, 3H, N-CH3), 4.07 (d, 1H, H3), 4.11 (d,
1H, H5), 4.25 (s, 5H, g-C5H5), 4.40 (m, 3H, H4, H11),
6.78 (m, 3H, H12, H13, H14), 7.18 (t, 1H, H16) ppm.
3.2.6. [(g5-C5H5)Fe(g5-C5H3(HgCl)CH2N(CH3)C6H4–
NO2-3)] (6f)
2
based on F2 with w ¼ 1=½r2ðF 2oÞ þ ð0:0265PÞ þ 0:0000Pꢂ
where P ¼ ðF 2o þ 2F c2Þ=3 for 6a, w ¼ 1=½r2ðF 2oÞ þ
Yellow solid. Yield 58%; m.p. 176 ꢁC (dec.). Anal. Calc.
for C18H17ClFeHgN2O2: C, 36.94; H, 2.93; N, 4.79.
Found: C, 36.70, H, 3.02, N, 4.70%. IR (KBr): 3087,
2
ð0:0265PÞ þ 0:0000Pꢂ where P ¼ ðF 2o þ 2F c2Þ=3 for 7.
Crystallographic data for 6a, e, and 7 are summarized
in Table 1. Selected bond lengths and angles for 6e, 7
are presented in Tables 2 and 3, respectively.
2922, 1524, 1454, 1343, 1252, 1103, 734, 483 cmꢀ1 1H
.
NMR: d 2.92 (s, 3H, N-CH3), 4.10 (d, 1H, H3), 4.12 (d,

H.-X. Wang et al. / Polyhedron 25 (2006) 3305–3311
3311
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4. Supplementary materials
Crystallographic data (excluding structure factors) for
the structures of 6a, e, and 7 in this paper have been depos-
ited with the Cambridge Crystallographic Data Centre as
supplementary publication numbers CCDC 290135,
275037, and 275036. Copies of the data can be obtained,
free of charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44 1223 336033 or e-mail:
deposit@ccdc.cam.ac.uk).
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We are grateful to the Natural Scientific Foundation of
Tianjin Metropolitan, People’s Republic of China for their
generous support for this project (Project No. 033609011),
the Opening Fund from The State Key Laboratory of
Elemento-organic Chemistry, Nankai University, People’s
Republic of China is also acknowledged.
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