Activation of the C{single bond}H bond in [(η5-C5H5)Fe(η5 -C5H4CH2N(CH3)CH2 C6H4R-4)] induced by platinum (II): Crystal structure of σ-Pt[(η5-C5H5)Fe(η 5-C5H3CH2N ...

Article abstract of DOI:10.1016/j.poly.2006.02.017

Full Title: Activation of the C{single bond}H bond in [(η⁵-C₅H₅)Fe(η⁵ -C₅H₄CH₂N(CH₃)CH₂C ₆H₄R-4)] induced by platinum (II): Crystal structure of σ-Pt[(η⁵-C₅H₅) Fe(η⁵-C₅H₃CH₂N(CH₃) CH₂C₆H₄OCH₃-4)]Cl(DMSO). Condensations of ferrocenylcarboxaldehyde (1) and p-methyl (2b) or p-chlorobenzylamines (2d) in methanol resulted in ferrocenylaldimines 3b, d which were reduced by lithium aluminum hydride to give 4b, d, respectively. Reductive methylations of 4b, d with aqueous formaldehyde, sodium cyanoborohydride and acetic acid afforded the tertiary ferrocenylamines 5b, d. Treatment of 5a-e [(η⁵-C₅H₅)Fe(η⁵ -C₅H₄CH₂N(CH₃)CH₂ C₆H₄R-4)] (R = CH₃O(a), CH₃(b), H(c), Cl(d), NO₂(e)) with cis-[Pt(DMSO)₂Cl₂] in methanol produced predominately cycloplatinated complexes 6a-e σ-Pt[(η⁵-C₅H₅)Fe(η ⁵-C₅H₃CH₂N(CH₃) CH₂C₆H₄-R-4)]Cl(DMSO) (R = same as before) in which the configurations consisted of R_NR_P and S_NS_P. In addition, the preferred activation of the C{single bond}H bond in the cyclopentadienyl ring rather than that in the phenyl ring was also observed. All compounds 3b-5b, 3d-5d, 6a-e were characterized by elemental analysis, IR and ¹H NMR. The structure of 6a was determined by X-ray single crystal diffraction. The possible mechanism for the formation of 6 was discussed.

Full text of DOI:10.1016/j.poly.2006.02.017

Polyhedron 25 (2006) 2530–2536
www.elsevier.com/locate/poly
Activation of the CAH bond in
[(g5-C5H5)Fe(g5-C5H4CH2N(CH3)CH2C6H4R-4)] induced by
platinum (II): Crystal structure of
r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)CH2C6H4OCH3-4)]Cl(DMSO)
a,
a
a
b
a
Hong-Xing Wang *, Hong-Fei Wu , Hui-Chao Zhou , Rong Jin , Ren-Qing Gao ,
a
a
a
a,
*
Feng-Ying Geng , Jian Xu , Ying-Jie Li , Wen-Qin Zhang
a
Department of Chemistry, College of Sciences, Tianjin University, No. 92, Weijin Road, Nankai District, Tianjin 300072, PR China
b
Department of Ultrasound, The First Central Hospital of Tianjin, Tianjin 300192, PR China
Received 5 December 2005; accepted 28 February 2006
Available online 18 March 2006
Abstract
Condensations of ferrocenylcarboxaldehyde (1) and p-methyl (2b) or p-chlorobenzylamines (2d) in methanol resulted in ferrocenyl-
aldimines 3b, d which were reduced by lithium aluminum hydride to give 4b, d, respectively. Reductive methylations of 4b, d with
aqueous formaldehyde, sodium cyanoborohydride and acetic acid afforded the tertiary ferrocenylamines 5b, d. Treatment of 5a–e
[(g5-C5H5)Fe(g5-C5H4CH2N(CH3)CH2C6H4R-4)] (R = CH3O(a), CH3(b), H(c), Cl(d), NO2(e)) with cis-[Pt(DMSO)2Cl2] in methanol
produced predominately cycloplatinated complexes 6a–e r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)CH2C6H4-R-4)]Cl(DMSO) (R = same
as before) in which the configurations consisted of RNRP and SNSP. In addition, the preferred activation of the CAH bond in the cyclo-
pentadienyl ring rather than that in the phenyl ring was also observed. All compounds 3b–5b, 3d–5d, 6a–e were characterized by elemen-
1
tal analysis, IR and H NMR. The structure of 6a was determined by X-ray single crystal diffraction. The possible mechanism for the
formation of 6 was discussed.
ꢀ 2006 Elsevier Ltd. All rights reserved.
Keywords: Ferrocenylamines; Reductive methylation; Cycloplatination; Stereoselectivity; Crystal
1. Introduction
produced the corresponding cycloplatinated FcN, while
Ryabov et al. [6a] observed that treatment of FcN with
enantiomeric cis-[PtCl2(S-SOMeC6H4Me-p)2] afforded the
cycloplatinated FcN with planar chirality. Lopez et al.
[7a] reported that the reactions of ferrocenylimines
[(g5-C5H5)Fe(g5-C5H4CH2N@CHC6H4R)] and Na2PdCl4
in the presence of NaAcO resulted in not only the cyclopal-
ladated complexes with a r Pd–C2sp;ferrocenyl bond, but also
the cyclopalladated complexes with a r Pd–C2sp;phenyl bond
due to the presence of the endo effect. In addition, the
preference of ferrocenyl over phenyl for cyclopalladation
was also documented in the literatures [7]. In a recent
paper, we described the synthesis of [(N-methyl-N-p-R-
benzyl)amino]methylferrocenes (R = CH3O(a), H(c), NO2(e))
Despite the extensive investigation of cyclopalladation
on N-donor ligands [1], there is an increasing interest in
cycloplatination reactions on these ligands due to their
applications in organic synthesis [2], material science [3],
macromolecular building blocks [4], antitumor activities
[5], etc. Up until now, a few classes of examples of cyclopla-
tinated complexes with N-donor ligands were reported [6].
Simpson et al. [5] reported that the reaction of N,N-dime-
thylaminomethylferrocene (FcN) and cis-[Pt(DMSO)2Cl2]
*
Corresponding authors. 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.2006.02.017

H.-X. Wang et al. / Polyhedron 25 (2006) 2530–2536
2531
starting from aminomethylferrocene and substituted ben-
2.2. Spectral characterization of 6a–e
zaldehydes [8a]. As a part of our current research related
to the cyclo-metallation of ferrocenylamines[8b], in this
communication, we wish to report the synthesis of ferroce-
nylamines [(g5-C5H5)Fe(g5-C5H4CH2N(CH3)CH2-C6H4R-4)]
(R = CH3(b), Cl(d)), starting from ferrocenylcarboxalde-
hyde and p-substituted benzylamines, and the cycloplatina-
tion reactions of these five ferrocenylamines as mentioned
above (Scheme 1) and to try to elucidate the relationship
between the structures of the substrates and their selec-
tivities.
Compounds 3b–5b, 3d–5d and 6a–e were characterized
by elemental analyses, IR and H NMR. Elemental analy-
1
ses for these compounds are in good agreement with the
1
proposed formula. The IR and H NMR spectra of com-
pounds 3b–5b, 3d–5d are very similar to their analogues,
e.g., 3a–5a [8]. The IR spectra of 6a–6e all display two med-
ium absorption bands around m 1100 and 1000 cmꢀ1, indi-
cating that the cycloplatination of 5a–e occurs at the
substituted cyclopentadienyl (Cp) rings [10]. In the 1H
NMR spectra, the d values of NACH3 range from 3.02
(6a) to 2.81 (6b), suggesting that NAPt coordination exists
2. Results and discussion
1
in these molecules. Also in the H NMR spectra of 6, a
2.1. Synthesis of 6a–e
doublet and multiplet around d4.10 ppm are assigned to
H5 and H4, respectively, and a singlet around d4.20 ppm
is attributed to H3. In addition, H11 exhibit a typical AB
spin–spin coupling system (d3.62 ppm) due to the forma-
tion of a five membered platinocycle (in 6a, the chemical
shifts of H11 are overlapped with those of H19 and
H20). It seems that H12 have a similar coupling system
(around d4.00 ppm) to that for H11. The protons in p-
substituted phenyl rings all give their corresponding
AA0XX0 splitting patterns.
Condensations of ferrocenylcarboxaldehyde and p-
methyl (2b) or p-chloroaniline (2d) in methanol at room
temperature produced the corresponding aldimines 3b, d,
which followed by reduction with lithium aluminum
hydride in THF afforded quantitatively 4b, d, respectively.
Methylation of 4b, d with sodium cyanoborohydride, aque-
ous formaldehyde and acetic acid [9] at room temperature
gave the aliphatic tertiary ferrocenylamines 5b, d [8] in
good yield. Like their analogues, compounds 5b, d are very
stable in air, and they are normally liquid or solid with low
melting points.
2.3. Chemoselectivity and stereoselectivity
The reactions of 5a–e and cis-[Pt(DMSO)2Cl2] were car-
ried out in methanol under nitrogen. The mixtures were
refluxed and stirred for 30 min and cooled down to room
temperature. The solvent was evaporated in vacuo and
water was then added. Extraction of the water phase with
dichloromethane three times (3 · 30 cm3) and removal of
solvent afforded residues which were further purified by
column chromatography (silica gel, ethyl acetate/hexane =
1:5 (v/v)) to give 6a–e as orange-yellow solids. The yields of
6a–e are relevant to the character of the substituents on the
phenyl ring. For instance, when the substituents are meth-
oxy (5a) or methyl (5b), the yields of 6a, b are moderate
(65%, 60%, respectively), whereas when the substituents
are chloro (5d) or nitro (5e), lower yields of 6d, e (55%,
40%, respectively) are normally obtained. Complexes 6a–
e are very stable in air and are easily soluble in most
organic solvents, but are poorly soluble in hexane.
In all cases, a preferred cycloplatination occurred at the
Cp ring over the phenyl ring in 5 (Scheme 2). According to
the rule of cyclometallation, the reactions of 5 and cis-
[Pt(DMSO)2Cl2] form initially the coordinated complexes
7 (Scheme 2) which then direct the platinum to activate
its adjacent CAH bonds and hence give the cycloplatinated
R
R
N
N
Pt
PtCl2
S
S
Cl
Fe
6a-e
Fe
O
O
7a-e
8a-e
Scheme 2. The preferred activation of CAH bond in Cp ring over that in
phenyl ring.
21
15
17
14 15
14
18
12 13
16
12 13
16
4
R
R
11
1
11
5
CHO
2
N
3
N
2
1
17
18
Cl
Pt
19
5
i
ii
iii
iv
Fe
Fe
Fe
4b, d
3b, d
O
6
S
6
7
7
10
19
10
20
1
5a-e
rac-6a-e
Scheme 1. (i) Amines 2: 4-RC6H4CH2NH2, R = CH3O(a); CH3(b); H(c) Cl(d), NO2(e), methanol, room temperature. (ii) LiAlH4, THF, reflux.
(iii) NaCNBH3, HCHO(aq), AcOH, room temperature. (iv) cis-[Pt(DMSO)2Cl2], methanol, reflux 30 min.

2532
H.-X. Wang et al. / Polyhedron 25 (2006) 2530–2536
compounds. It should be noted that two kinds of CAH
bonds are present in 5, i.e., the CferrocenylAH bond and
the CphenylAH bond, and activation of both CAH bonds
could afford the corresponding stable five membered plati-
nocycles 6a–e and 8a–e, respectively. In fact, only 6a–e
were isolated in our experiment. The compounds 8a–e
resulting from activation of CphenylAH bonds in 7a–e were
not observed. The preferred activation of the CferrocenylAH
bond over the CphenylAH bond is consistent with Lopez’s
observations [7], and this phenomenon is easily explained
by the fact that electrophilic substitution of platinum is
more facile on a ring with a high electron density (Cp ring)
than on one with a low electron density (phenyl ring) [11].
Surprisingly, of the cycloplatinated complexes 6a–e only
6a crystallizes in two forms, i.e., prismatic crystal and plate,
which are difficult to separate from each other in the mix-
ture. A prismatic crystal suitable for X-ray diffraction was
carefully picked out of the mixture and its configuration
was determined to be RNRP [12] (Fig. 1). The optical rota-
tions of 6a–e have been determined to be zero at a given
Fig. 1. Crystal structure of 6a with the numbering scheme (H atoms are
omitted for clarity).
the corresponding intermediates 7a,b with a similar confor-
mation to that of the coordinated PtAFcN complex [5].
When platinum in 7a,b activates the C2(5)AH bonds, a
pair of racemers 6a,b will be generated. Alternatively, the
NAPt moiety in 7a,b could rotate freely around the axis
of the C1AC11 bond and subsequently activate the
C5(2)AH bonds to give another pair of racemers 6c,d.
Obviously, cycloplatination of 5 will produce two pairs of
enantiomers, and moreover, the pair 6a,b are the diastereo-
mers of the other pair 6c,d.
˚
wavenumber (k = 5893 A) and conditions (CH2Cl2,
T = 298 K), implying that complexes 6 are probably com-
posed of racemers. It is possible that each form of 6a cor-
responds to one isomer of the racemers. This result may be
echoed by the possible mechanism for the formations of 6
as shown in Scheme 3.
Theoretically, an orbital reversion at nitrogen is present
between the two isomers 5a and 5b (Scheme 3) and each
isomer will possess the same stable conformation as that
of [(N-methyl-N-4-methylbenzyl)amino]methyl-ferrocene
[13]. Thus, coordination of platinum and 5a,b will afford
On the other hand, the orientation of platinum in 7a,b
approaches the C2AH, C5AH bonds, respectively [5], the
2
N
1
11
2
Fe 5
1
N
11
Fe 5
R
5α
5β
R
cis-[Pt(DMSO)2Cl2]
cis-[Pt(DMSO)2Cl2]
O
2
Cl
S
Cl
1
Pt
11
N
Fe5
2
Rotate around C1-C11,
then attack at C5
1
Rotate around C1-C11,
then attack at C2
N
Cl
Pt
6γ (RNSp)
trace
6δ (SNRp)
trace
11
Fe 5
Cl
R
S
O
R
7α
7β
attack at C2
5
attack at C5
5
Cl
2
O
S
1
11
Pt
5
N
N
Fe
O
2
Pt
1
11
Fe 5
Cl
S
R
R
6α (RNRp)
6β (SNSp)
Scheme 3. The possible mechanism for the formation of 6.

H.-X. Wang et al. / Polyhedron 25 (2006) 2530–2536
2533
Table 1
Crystallographic data for 6a
listed in Table 2. X-ray diffraction studies for 6a (Fig. 1) dem-
onstrate that the structure of 6a consists of discrete molecules
r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)CH2C6H4OCH3-4)]-
Cl(DMSO) separated by van der Waals distances in which
platinum is in a slight distorted square-planar environment,
bonded to Cl1, S1, N1 and C1. The deviations of the atoms
from the mean plane defined by the former five atoms in 6a
are Pt1 0.0218, Cl1 ꢀ0.0317, S1 0.0225, N1 0.0272 and C1
Compound
6a
Empirical formula
M
C22H28ClFeNO2PtS
656.90
0.28 · 0.20 · 0.16
orthorhombic, P2(1)2(1)2(1)
9.4664(5)
12.5579(7)
18.9943(1)
90
90
90
2258.0(2)
4
Crystal dimensions (mm)
Crystal system, space group
˚
a (A)
˚
b (A)
˚
˚
ꢀ0.0398 A. In 6a, the DMSO moiety adopts a trans configu-
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
ration to the N1 atom with a bond angle N1–Pt1–S1
178.20(9)ꢁ and this array is very common in platinum com-
plexes [5,6a]. 6a contains two fused five-membered rings,
i.e., the substituted pentagonal ring of the ferrocenyl
fragment and a five-membered platinocycle with an enve-
lope-like conformation. The bond length of N1APt1
3
˚
V (A )
Z
qcalc. (g cmꢀ3
)
1.932
7.060
l (mmꢀ1
)
h Range for data collection
Limiting indices
2.14ꢁ 6 h 6 25.02ꢁ
ꢀ11 6 h 6 11,
ꢀ14 6 k 6 14,
ꢀ13 6 l 6 22
12027/3952 (0.0209)
3952/0/266
0.0155, 0.0359
0.458, ꢀ0.850
˚
˚
(2.128(3) A) is shorter than that in cycloplatinated FcN
(2.141(6) A) [5]. The metallated Cp and phenyl rings are
nearly perpendicular with an angle of 89.7ꢁ. The bond length
˚
of Pt1AC1 (1.985(3) A) is nearly the same as that in cyclopla-
Reflections collected/unique (Rint
Data/restraints/parameters
Final R1, wR2
)
˚
tinated FcN (1.988(7) A) [5]. The average CAC bond length
˚
in the pentagonal rings (1.410 A) is similar to the values
ꢀ3
˚
Largest difference peak and hole (e A
)
reported for other ferrocene derivatives [10]. The FeAC
˚
(Cp ring) bond lengths range from 1.381(6) to 1.424(5) A.
The two pentagonal rings of the ferrocenyl moiety are planar
and nearly parallel (interplanar angle 2.2ꢁ). In addition, the
Cp rings are also nearly eclipsed and they are skewed from
the eclipsed conformation with an angle of 2.56ꢁ.
Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for compound 6a
˚
Bond lengths (A)
Pt(1)AN(1)
Pt(1)ACl(1)
Pt(1)AC(1)
Pt(1)AS(1)
S(1)AO(1)
2.128(3)
2.4148(1)
1.985(3)
2.1919(1)
1.465(3)
S(1)AC(22)
C(1)AC(2)
C(2)AC(11)
N(1)AC(11)
N(1)AC(13)
1.772(4)
1.424(5)
1.495(5)
1.505(5)
1.512(5)
3. Conclusion
Stereoselective cycloplatination of ferrocenylamines of
the formula FcCH2NMeCH2Ar produced the correspond-
ing two pairs of racemers in which the pair RNRP, SNSP
was the major product. No products resulting from the
activation of CphenylAH bonds were observed. It is antici-
pated that cyclometallation of ferrocenylamines such as
FcCHRN(CH3)CH2Ar or FcCH2N(CH3)CHRAr will
afford four diastereomers which can be easily separated
by column chromatography.
Angles (ꢁ)
C(1)APt(1)ACl(1)
N(1)APt(1)AS(1)
N(1)APt(1)ACl(1)
C(1)APt(1)AN(1)
173.15(1)
C(11)AN(1)APt(1)
C(13)AN(1)APt(1)
C(2)AC(11)AN(1)
C(14)AC(13)AN(1)
111.4(2)
178.20(9)
92.09(9)
81.79(1)
115.9(2)
108.2(3)
115.4(3)
activation of these two CAH bonds to produce 6a,b by
platinum will be favored. However, this orientation may
disfavor the activation of C5(2)AH bonds to generate
6c,d probably because the free rotation of the NAPt moiety
around the axis of the C1AC11 bond is retarded by the ste-
ric hindrance between the phenyl group and the H atom in
the Cp ring. Diastereomers are easily separated by column
chromatography, and we indeed obtained a trace product
(probably 6c,d) of insufficient quantity to identify. Based
upon the discussion as mentioned above and the configura-
tion of 6a (Fig. 1), it is suggested that 6 consists probably of
6a,b.
4. Experimental
4.1. Materials and instruments
Ferrocenylamines 5a, c, e [8] and cis-[Pt(DMSO)2Cl2]
[14] were prepared according to the literature procedure.
Ferrocenylcarboxaldehyde, p-methylbenzylamine, p-chloro-
benzylamine, lithium aluminum hydride, aqueous formal-
dehyde, sodium cyanoborohydride, acetic acid were
obtained commercially and used without further purifica-
tion. All of the solvents were purified by the standard meth-
ods prior to use. Melting points were obtained from a
Yanaco micro melting point apparatus and were uncor-
rected. Elemental analyses were obtained from a Carlo
Erba 1106 Elemental analyzer. IR spectra were taken on
2.4. Crystal structure of 6a
The structure of 6a was also confirmed by X-ray single
crystal diffraction (Fig. 1). Crystallographic data for 6a are
presented in Table 1, selected bond lengths and angles are
1
BIO-RAD 3000 and Digilab FTIR spectrometers. H NMR
spectra were measured with a Bruker AV-400 spectrometer

2534
H.-X. Wang et al. / Polyhedron 25 (2006) 2530–2536
by using CDCl3 as a solvent and TMS as the internal
standard.
4.2.5. [(g5-C5H5)Fe(g5-C5H4CH2N(CH3)-
CH2C6H4CH3-4)] (5b)
5b was prepared according to the literature method
[9]. Yellow solid. Yield 80%. M.p. 32–34 ꢁC. Anal. Calc.
for C20H23FeN: C, 72.08; H, 6.96; N, 4.20. Found, C,
71.99; H, 6.94; N, 4.21%. FT-IR (KBr): m 3091(w),
2928(w), 1513(s), 1453(s), 1361(w), 1105(s), 1020(vs),
4.2. Synthesis of [(g5-C5H5)Fe(g5-C5H4CH2N-
(CH3)CH2C6H4R-4)] (5b, d)
4.2.1. [(g5-C5H5)Fe(g5-C5H4CH@NCH2C6H4CH3-4)]
(3b)
805(vs) cmꢀ1
.
1H NMR (CDCl3):
d
2.12(s, 3H,
ArACH3), 2.34(s, 3H, NACH3), 3.40(s, 2H, H11),
3.43(s, 2H, H12), 4.09(s, 5H, g5-C5H5), 4.12(m, 2H,
H2, H5), 4.18(d, 2H, H3, H4), 7.20–7.28 (AA0XX0, 4H,
H15, H17, H14, H18) ppm.
3b was prepared by condensation of ferrocenyl-carbox-
aldehyde and 4-methylaniline in methanol at room temper-
ature under nitrogen. Red brown solid. Yield 54%. M.p.
70–72 ꢁC. Anal. Calc. for C19H19FeN: C, 71.94; H, 6.04;
N, 4.42. Found: C, 71.84; H, 6.01; N, 4.42%. FT-IR(KBr):
m 3092(w), 2935(w), 2888(w), 1636(vs), 1516(s), 1340(m),
4.2.6. [(g5-C5H5)Fe(g5-C5H4CH2N(CH3)-
CH2C6H4Cl-4)] (5d)
1246(w), 1167(s), 1106(m), 1000(m), 809(s) cmꢀ1
.
1H
NMR (CDCl3): d 2.10(s, 3H, ArACH3), 3.84(d, 2H, H2,
H5), 4.14(m, 2H, H3, H4), 4.17(s, 5H, g5-C5H5), 4.50(s,
2H, H12), 7.70–7.89 (AA0XX0, 4H, H15, H17, H14,
H18), 8.10(s, 1H, H11) ppm.
5d was prepared with the same procedure as that for
5b. Yellow solid. Yield 72%. M.p. 38–40 ꢁC. Anal. Calc.
for C19H20ClFeN: C, 64.52; H, 5.70; N, 3.96: Found, C,
64.33; H, 5.68; N, 3.95%. FT-IR (KBr): m 3085(m),
2929(s), 2834(s), 1492(s), 1452(s), 1361(w), 1105(s),
4.2.2. [(g5-C5H5)Fe(g5-C5H4CH@NCH2C6H4Cl-4)]
(3d)
1022(vs), 1000(vs), 818(vs) cmꢀ1 1H NMR (CDCl3): d
.
2.12(s, 3H, NACH3), 3.42(s, 4H, H11, H12), 4.06(s,
5H, g5-C5H5), 4.10(m, 2H, H2, H5), 4.16(d, 2H, H3,
H4), 7.12–7.19 (AA0XX0, 4H, H14, H18, H15, H17)
ppm.
3d was prepared with the same procedure as that for 3b.
Red brown solid. Yield 88%. M.p. 57–59 ꢁC. Anal. Calc.
for C18H16ClFeN: C, 64.03; H, 4.78; N, 4.15. Found: C,
63.98; H, 4.76; N, 4.13%. FT-IR(KBr): m 3085(w),
2917(w), 2823(w), 1638(vs), 1449(s), 1240(w), 1105(m),
4.3. Synthesis of r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)-
CH2C6H4-R-4)]Cl(DMSO) (6a–e)
1
1001(m), 817(s) cmꢀ1. H NMR (CDCl3): d 3.86(d, 2H,
H2, H5), 4.15(m, 2H, H3, H4), 4.18(s, 5H, g5-C5H5),
4.51(s, 2H, H12), 7.81–7.93 (AA0XX0, 4H, H14, H18,
H15, H17), 8.15(s, 1H, H11) ppm.
General procedure: To a stirred solution of amine
(0.5 mmol) in methanol (20 cm3) was added cis-[Pt
(DMSO)2Cl2] (105 mg, 0.25 mmol). The mixture was stir-
red and refluxed for 30 min under nitrogen and cooled
down to room temperature. The solvent was removed in
vacuo and water was then added. The mixture was
extracted with dichloromethane (3 · 30 cm3) and sepa-
rated. The organic layer was dried over anhydrous sodium
sulfate and filtered. Removal of solvent gave the crude
product which was further purified by column chromatog-
raphy (silica gel, ethyl acetate/hexane = 1:5 (v/v)) to afford
6.
4.2.3. [(g5-C5H5)Fe(g5-C5H4CH2NHCH2C6H4CH3-4)]
(4b)
4b was prepared by reduction of imine 3b with lithium
aluminum hydride in THF under nitrogen. Yellow solid,
Yield 80%. M.p. 28–30 ꢁC. Anal. Calc. for C19H21FeN:
C, 71.49; H, 6.63; N, 4.39. Found: C, 71.45; H, 6.60;
N, 4.38%. FT-IR (KBr): m 3329(s), 3093(s), 2920(s),
2814(m), 1514(vs), 1449(s), 1354(w), 1105(vs), 1001(s),
809(vs) cmꢀ1 1H NMR(CDCl3): d 1.88(s, 1H, NH),
.
2.11(s, 3H, ArACH3), 3.47(s, 2H, H11), 3.71(s, 2H,
H12), 3.80(d, 2H, H2, H5), 4.09(s, 5H, g5-C5H5),
4.13(t, 2H, H3, H4), 6.85–7.23 (AA0XX0, 4H, H15,
H17, H14, H18) ppm.
4.3.1. r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)-
CH2C6H4OCH3-4)]Cl(DMSO) (6a)
Yellow powder. Yield 65%. M.p. 218–220 ꢁC. Anal.
Calc. for C22H28ClFeNO2PtS: C, 40.22; H, 4.30; N, 2.13.
Found: C, 40.18; H, 4.29; N, 2.13%. FT-IR (KBr): m
3091(w), 1610(s), 1511(vs), 1455(m), 1253(s), 1132(s,
S@O), 1101(m), 1000(m), 819(s) cmꢀ1. Far IR (Nujol): m
4.2.4. [(g5-C5H5)Fe(g5-C5H4CH2NHCH2C6H4Cl-4)](4d)
4d was prepared with the same procedure as that for 4b.
Yellow liquid. Yield 80%. Anal. Calc. for C18H18ClFeN: C,
63.65; H, 5.34; N, 4.12. Found: C, 63.41; H, 5.24; N, 4.11%.
FT-IR (KBr): m 3298(w), 3086(s), 2911(s), 2828(m),
272(PtACl), 352(PtAS) cmꢀ1
.
1H NMR (CDCl3): d
1487(m), 1452(s), 1104(vs), 1000(vs), 818(vs) cmꢀ1
.
1H
3.02(s, 3H, H21), 3.18(s, 3H, OCH3), 3.55(m, 8H, H19,
H20, H11), 3.72(AB, 2H, J = 14.8 Hz, H12), 3.82(d, 1H,
JPtAH = 33.2 Hz, H5), 4.00(s, 5H, g5-C5H5), 4.11(m, 1H,
H4), 4.22(s, 1H, H3), 6.86–6.94 (AA0XX0, 4H, H15, H17,
H14, H18) ppm.
NMR(CDCl3): d 1.90(s, 1H, NH), 3.49(s, 2H, H11),
3.72(s, 2H, H12), 3.81(d, 2H, H2, H5), 4.11(s, 5H, g5-
C5H5), 4.15(t, 2H, H3, H4), 6.93–7.45 (AA0XX0, 4H,
H14, H18, H15, H17) ppm.

H.-X. Wang et al. / Polyhedron 25 (2006) 2530–2536
2535
4.3.2. r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)-
CH2C6H4CH3-4)]Cl(DMSO) (6b)
4.4. X-ray determination of 6a
Yellow powder. Yield 60%. M.p. 184–186 ꢁC. Anal.
Calc. for C22H28ClFeNOPtS: C, 41.23; H, 4.40; N, 2.19.
Found: C, 41.18; H, 4.38; N, 2.18%. FT-IR (KBr): m
3094(w), 2917(w), 1457(m), 1411(s), 1132(vs, S@O),
1103(m), 1000(m), 807(s) cmꢀ1. Far IR (Nujol): m
The prismatic single crystal of 6a suitable for X-ray
analysis was obtained by slow evaporation of a mixture
of ethyl acetate and hexane at room temperature over a
period of one week. This single crystal was mounted on a
Bruker SMART CCD diffractometer equipped with graph-
273(PtACl), 353(PtAS) cmꢀ1
.
1H NMR (CDCl3): d
ite monochromated Mo Ka (k = 0.71073 A) radiation at
˚
2.32(s, 3H, ArACH3), 2.81(s, 3H, H21), 3.53(s, 3H, H19),
3.57(s, 3H, H20), 3.62(AB, 2H, J = 12.8 Hz, H11),
4.04(AB, 2H, J = 14.8 Hz, H12), 4.12(s, 5H, g5-C5H5),
4.16(d, 1H, JPtAH = 33.2 Hz, H5), 4.25(m, 1H, H4),
4.31(s, 1H, H3), 6.89–7.77 (AA0XX0, 4H, H15, H17, H14,
H18) ppm.
ambient temperature (T = 293 K) using the x-2h multi-
scans technique for data collection. Semi-empirical absorp-
tion corrections were applied using the SABABS program
[15]. The structure was solved by direct methods and
refined by full-matrix least-squares procedure on F2 using
the SHELX suite of programs [16].
4.3.3. r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)-
CH2-C6H5)]Cl(DMSO) (6c)
5. Supplementary materials
Yellow powder. Yield 56%. M.p. 210–212 ꢁC. Anal.
Calc. for C21H26ClFeNOPtS: C, 40.24; H, 4.18; N, 2.23.
Found: C, 40.19; H, 4.16; N, 2.20%. FT-IR (KBr): m
3092(w), 1559(w), 1457(m), 1130(vs, S@O), 1102(m),
1000(m) cmꢀ1. Far IR (Nujol): m 274(PtACl), 353(PtAS)
Crystallographic data (excluding structure factors) for
the structure of 6a in this paper has been deposited with
the Cambridge Crystallographic Data Centre as supple-
mentary publication no. CCDC 286580. Copies of the data
can be obtained, free of charge, on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: +144
1223 336033 or e-mail: deposit@ccdc.cam.ac.uk).
1
cmꢀ1. H NMR (CDCl3): d 1.55(s, 3H, H21), 2.83(s, 3H,
H21), 3.54(s, 3H, H19), 3.57(s, 3H, H20), 3.62(AB, 2H,
J = 12.8 Hz, H11), 4.10(AB, 2H, J = 14.8 Hz, H12),
4.13(s, 5H, g5-C5H5), 4.21(d, 1H, JPtAH = 33.2 Hz, H5),
4.29(m, 1H, H4), 4.34(s, 1H, H3), 7.04–7.94 (m, 5H, H14,
H15, H16, H17, H18) ppm.
Acknowledgement
We are grateful to the Natural Scientific Foundation of
Tianjin City, People’s Republic of China, for financial sup-
port for this project (Project No. 033609011).
4.3.4. r-Pt[(g5-C5H5)Fe(g5-C5H3CH2N(CH3)-
CH2C6H4Cl-4)]Cl(DMSO) (6d)
Yellow powder. Yield 55%. M.p. 181–183 ꢁC. Anal.
Calc. for C21H25Cl2FeNOPtS: C, 38.14; H, 3.81; N, 2.12.
Found: C, 38.00; H, 3.78; N, 2.11%. FT-IR (KBr): m
3081(w), 2915(w), 1455(m), 1407(w), 1130(vs, S@O),
1103(m), 1002(m), 806(m) cmꢀ1. Far IR (Nujol): m
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