Synthesis, characterization and the crystal structure of 1-[(N-methyl-N-aryl)amino]ethylferrocenes

Article abstract of DOI:10.1016/S0022-328X(03)00552-7

The reactions of ferrocenylketimines [(η⁵-C₅ H₄CCH₃=NAr)Fe(η⁵-C₅ H₅)] (Ar=a variety of substituted phenyls) with methyl-iodide in refluxed dichloromethane followed by reduction with sodium borohydride in absolute ethanol led to [(η⁵-C₅H₄CH(CH₃) N(CH₃)Ar)Fe(η⁵-C₅H₅)]. Compound [(η⁵-C₅H₄ CH(CH₃)N(CH₃)-C₆H₄-Cl-p) Fe(η⁵-C₅H₅)] (3d) has been characterized structurally. Compound 3d is monoclinic, space group P2₁/n, with a=8.908(2) A?, b=13.63(1) A?, c=14.510(3) A? and β=107.03°.

Full text of DOI:10.1016/S0022-328X(03)00552-7

Journal of Organometallic Chemistry 679 (2003) 130Á134
/
www.elsevier.com/locate/jorganchem
Synthesis, characterization and the crystal structure of 1-[(N-methyl-
N-aryl)amino]ethylferrocenes
Hong Xing Wang a,*, Li Ding b, Yang Jie Wu b,*
a Department of Chemistry, The College of Natural Sciences, Tianjin University, Tianjin 300072, China
b Department of Chemistry, Zhengzhou University, Zhengzhou 450052, China
Received 22 January 2003; received in revised form 24 April 2003; accepted 30 April 2003
Abstract
The reactions of ferrocenylketimines [(h5-C5H4CCH3Ä
iodide in refluxed dichloromethane followed by reduction with sodium borohydride in absolute ethanol led to [(h5-
C5H4CH(CH3)N(CH3)Ar)Fe(h5-C5H5)]. Compound [(h5-C5H4CH(CH3)N(CH3)Ã Cl-p)Fe(h5-C5H5)] (3d) has been charac-
C6H4Ã
terized structurally. Compound 3d is monoclinic, space group P21/n, with aꢀ8.908(2) A, bꢀ
/
NAr)Fe(h5-C5H5)] (Arꢀ
/
a variety of substituted phenyls) with methyl-
/
/
˚
˚
˚
/
/
13.63(1) A, cꢀ
/
14.510(3) A and bꢀ
/
107.038.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Ferrocenylketimines; Methylation; Reduction; Ferrocenylamines; Crystal structures
1. Introduction
mercury reagents, etc. [1b,4]. These cyclometallated
ferrocenylketimines were found to be used in resolution
of racemic a-amino acids [5], Heck reaction [6], as well
as insertion of small molecules such as alkynes, alkenes,
CO, etc. [7]. In this paper, we will present the details of
our study on the synthesis, identification of 1-[(N-
methyl-N-aryl)amino]ethylferrocenes as well as the
crystal structure of 1-[(N-methyl-N-4-chlorophenyl)a-
mino]ethylferrocene.
N-Alkyl(or aryl)aminoferrocenes as a kind of impor-
tant organometallic compounds have attracted a great
deal of attention in the past two decades due to their
wide application in organic synthesis [1]. For an
example, 1-[(N,N-dimethyl)amino]ethylferrocene not
only served as a ligand to transition metals, which was
involved in cyclometallation, nucleophilic substitution,
and oxidation, etc., but also participated in asymmetric
organic synthesis for some optical materials because of
its chirality of a carbon atom [1]. To our best knowl-
edge, some of N-alkylaminoethylferrocenes have been
reported in the literatures [2]; in contrast, the synthesis
of N-arylaminoethylferrocenes and their properties are
still unknown. In the course of our investigation of
cyclometallation on ferrocenylketimines [3], we found
that these ferrocenylketimines could react with methyl-
iodide to form stable imine salts, which were further
reduced by sodium borohydride to yield the correspond-
ing N-arylaminoethylferrocenes. Ferrocenylketimines
could be cyclometallated by palladium, platinum, tin,
2. Synthesis and characterization of 1-[(N-methyl-N-
aryl)amino]ethylferrocenes
2.1. Synthesis of 1-[(N-methyl-N-
aryl)amino]ethylferrocenes 3aÁ
/
3f
The reactions of ferrocenylketimines 1aÁ
/1f with
excess methyl-iodide were carried out in dichloro-
methane (Scheme 1) and the reactions were monitored
by TLC. After the reactions completed, the mixtures
were cooled down to room temperature and excess
sodium borohydride was added. When the reactions
finished, water was added to decompose unreacted
sodium borohydride. Then the water phases were
extracted with dichloromethane and the solvent was
* Corresponding authors.
E-mail address: hongxing_wang@hotmail.com (H.X. Wang).
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00552-7

H.X. Wang et al. / Journal of Organometallic Chemistry 679 (2003) 130Á
/134
131
Scheme 1.
removed to yield residue. Recrystallization of the crude
products afforded yellowish needles 3aÁ3f. The struc-
tures of 3aÁ3f were identified by elemental analysis,
NMR, IR (see Section 3). In addition, the crystal
structure of 3d was also determined.
atom. In addition, the average FeÃ
/
C bond length in 3d
˚
˚
was 2.039 A (for substituted Cp ring) and 2.043 A (for
/
/
unsubstituted Cp ring), respectively, which were shorter
˚
˚
than those (2.041 A for substituted Cp ring and 2.044 A
for unsubstituted Cp ring) in 1c [3a]. All these indicated
that the structure of 3d was tightly packed than that of
1c.
2.2. Spectral characterizations of
3f
arylaminoethylferrocenes 3aÁ
/
3. Experimental
All the compounds of 3aÁ
/
3f displayed two absorption
bands around at n 1100 and 1000 cmꢁ1 and this feature
is in accordance with the structures of mono-substituted
ferrocene derivatives [8]. The fact that the absorption
3.1. Materials and instruments
band at the region of 3600Á
indicated that no NÃH group existed in these molecules.
The absence of CÄ
N absorption band (at 1620 cmꢁ1
together with the presence of absorption band at 1300
cmꢁ1 confirmed that the reduction of CÄ
N double
bond by sodium borohydride was achieved.
/
3200 cmꢁ1 was not observed
Melting points were obtained on a WC-1 microscopic
apparatus and were uncorrected. Elemental analyses
were performed with Carlo Erba 1106 Elemental
/
/
)
Analyzer. IR spectra were recorded on a PerkinÁElmer
/
1
/
FT-IR 1730 spectrophotometer. H-NMR spectra were
measured with DPX 400 spectrometer using CDCl3 as a
solvent and TMS as an internal standard. All solvents
were treated according to the standard methods. Ferro-
cenylketimines 1aÁ
literature procedures [9].
In their NMR spectra, a singlet appeared at d 2.45
ppm corresponded to the CH3 group which attached
directly to nitrogen atom; similarly, a doublet appeared
at d 1.46 ppm was assigned to the methyl group which
attached directly to tertiary carbon. These hydrogen
nuclei in methyl group split the tertiary hydrogen nuclei
(appeared at 5.00 ppm) into quartet, and the coupling
constants all were 6.8 Hz, which further confirmed that
/
1f were prepared according to the
3.2. Preparations of compounds 3aÁ
/
3f
General procedure. Ferrocenylketimines
1
(0.3
3
they were J coupling pattern.
mmols) were dissolved in 10 ml of dry dichloromethane
with the protection of nitrogen gas. Then two equiva-
lents of methyl-iodide was added. The mixtures were
refluxed and stirred for 24 h. TLC monitored the
reactions until ferrocenylketimines were consumed com-
pletely. Later, the mixtures were cooled down to room
2.3. The crystal structure of 3d
The crystal structure of 3d was presented in Fig. 1.
The related atomic coordinates, selected bond lengths
and angles were listed in Tables 1 and 2, respectively.
From the structure of 3d, it was found that N-phenyl
ring was not coplanar with substituted Cp ring, the sp3-
hybridized C(11) caused N atom and substituted Cp ring
temperature and petroleum ether (30Á60 8C) was added.
/
The corresponding imine salts precipitated and were
filtered. The imine salts were dissolved in 20 ml of
absolute ethanol and 1.5 equivalents of sodium borohy-
dride was added in portions. The mixtures were stirred
vigorously at room temperature until the bubble ceased.
The unreacted sodium borohydride was hydrolyzed by
water and yellowish solids precipitated and were filtered.
If no solids precipitated, the water phase was extracted
with chloroform until the color of water phase was near
colorless. The organic portions were combined, and the
were not in the same plane. The Ú
(110.48) was smaller than ÚC(1)ÃC(11)Ã
and ÚN(1)ÃC(11)ÃC(12) (1128). The bond lengths of
C(11)ÃN(1) and C(13)Ã
/
C(1)Ã
/
C(11)Ã
/
N(1)
/
/
/
C(12) (113.38)
/
/
/
˚
/
/N(1) were 1.473 and 1.465 A,
respectively. However, the bond length of N(1)Ã
/
C(14)
˚
(1.385 A) was shorter. The plausible explanation comes
from the conjugation of p bond and p electrons at N

132
H.X. Wang et al. / Journal of Organometallic Chemistry 679 (2003) 130Á134
/
Fig. 1. Molecular structure of 3d.
Jꢀ
4.01Á
/
6.8 Hz), 2.40 (s, 3H, NÃ
/
CH3), 3.75 (s, 3H, p-OCH3),
4.15 (m, 4H, substituted Cp ring), 4.10 (m, 5H,
Table 1
Atomic coordinates and equivalent isotropic thermal parameters for 3d
/
C5H5), 4.83 (q, 1H, C(11)Ã
C(15)ÃH, C(19)ÃH, Jꢀ8.4 Hz), 6.83 (d, 2H, C(16)Ã
C(18)ÃH, Jꢀ8.4 Hz) ppm.
3b, yellow rod. Yield 65%. m.p. 58Á
Found: C, 71.82; H, 6.95; N, 4.10. Calc. for C20H23FeN:
C, 72.08; H, 6.96; N, 4.20%. IR (KBr pellet): 1614, 1516,
1469, 1450, 1425, 1297, 1103, 1026, 998, 823, 814, 499
/
H, Jꢀ
/
6.8 Hz), 6.78 (d, 2H,
Atom
x
y
z
Beq
/
/
/
/H,
/
/
Fe
Cl
0.01206(4)
0.2075(1)
0.2729(2)
0.1584(3)
0.1987(3)
0.2049(3)
0.1691(3)
0.1415(3)
0.2250(3)
0.1771(4)
0.1677(4)
0.2037(3)
0.2364(3)
0.1350(3)
0.0925(4)
0.4148(4)
0.2557(2)
0.3872(3)
0.3729(3)
0.2275(3)
0.0966(3)
0.1100(3)
0.15932(2)
0.53016(6)
0.1100(2)
0.0546(2)
0.1358(2)
0.2212(2)
0.1934(2)
0.0910(2)
0.0958(2)
0.1668(3)
0.2573(2)
0.2415(2)
0.1425(3)
0.0508(2)
0.0626(2)
0.0741(3)
0.2093(2)
0.2663(2)
0.3637(2)
0.4073(2)
0.3549(2)
0.2576(2)
0.15497(2)
0.02498(7)
0.1122(2)
0.1300(1)
0.1794(2)
0.1218(2)
0.0365(2)
0.0410(1)
0.2275(2)
0.2857(2)
0.2387(2)
0.1516(2)
0.1451(2)
0.1626(2)
0.2720(2)
0.1182(3)
0.0975(1)
0.0949(2)
0.0279(2)
0.0544(2)
0.1029(2)
0.1251(2)
3.526(8)
6.88(2)
4.63(5)
3.63(4)
4.39(5)
4.91(6)
4.62(5)
3.82(5)
6.08(7)
6.07(7)
5.94(7)
5.63(7)
5.87(7)
3.98(5)
6.15(7)
7.65(10)
3.76(5)
4.51(5)
4.69(6)
4.41(5)
4.48(5)
4.21(5)
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
/
ꢁ
ꢁ
/
/
59 8C. Anal.
N
/
/
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
/
/
/
1
cmꢁ1. H-NMR: d 1.46 (d, 3H, CH3, Jꢀ
/
6.8 Hz), 2.45
CH3), 2.27 (s, 3H, p-CH3), 4.08Á4.19 (m, 4H,
substituted Cp ring), 4.13 (m, 5H, C5H5), 4.98 (q, 1H,
C(11)ÃH, Jꢀ6.8 Hz), 6.74 (d, 2H, C(15)ÃH, C(19)ÃH,
Jꢀ8.0 Hz), 7.06 (d, 2H, C(16)ÃH, C(18)ÃH, Jꢀ8.0
Hz) ppm.
3c, yellow rod. Yield 62%. m.p. 76Á
/
/
(s, 3H, NÃ
/
/
/
/
/
/
/
/
/
/
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
/
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
/
/
77 8C. Anal.
/
/
Found: C, 71.28; H, 6.30; N, 4.35. Calc. for C19H21FeN:
C, 71.48; H, 6.63; N, 4.39%. IR (KBr pellet): 1594, 1500,
1449, 1310, 1104, 1027, 992, 823, 754, 692, 505 cmꢁ1
/
/
/
/
.
/
/
1H-NMR: d 1.48 (d, 3H, CH3, Jꢀ
NÃCH3), 4.10Á4.21 (m, 4H, substituted Cp ring), 4.14
(m, 5H, C5H5), 5.06 (q, 1H, C(11)ÃH, Jꢀ6.8 Hz), 6.72
(t, 2H, C(15)ÃH, C(19)ÃH, Jꢀ7.2 Hz), 6.82 (d, 2H,
C(16)ÃH, C(18)ÃH, Jꢀ8.4 Hz), 7.25 (m, 1H, C(17)ÃH)
ppm.
3d, yellow rod. Yield 30%. m.p. 96Á
/6.8 Hz), 2.49 (s, 3H,
/
/
/
/
/
/
/
/
/
/
ꢁ
/
ꢁ
/
/
/
/
/
/
/
/
solvent was removed to give the crude products.
Recrystallization of the crude products from chloroform
and ethanol afforded 3.
/
98 8C. Anal.
Found: C, 64.39; H, 5.51; N, 3.88. Calc. for
C19H20ClFeN: C, 64.52; H, 5.70; N, 3.96%. IR (KBr
pellet): 1593, 1495, 1470, 1428, 1303, 1105, 1022, 998,
828, 814, 501 cmꢁ1. 1H-NMR: d 1.47 (d, 3H, CH3, Jꢀ
3a, yellow rod. Yield 79%. m.p. 83Á84 8C. Anal.
/
Found: C, 68.57; H, 6.67; N, 4.22. Calc. for
C20H23FeNO: C, 68.78; H, 6.64; N, 4.01%. IR (KBr
pellet): 1511, 1475, 1462, 1440, 1303, 1247, 1104, 1036,
999, 818, 796, 509 cmꢁ1. 1H-NMR: d 1.45 (d, 3H, CH3,
/
6.8 Hz), 2.46 (s, 3H, NÃ
substituted Cp ring), 4.14 (m, 5H, C5H5), 4.97 (q, 1H,
C(11)ÃH, Jꢀ6.8 Hz), 6.72 (d, 2H, C(15)ÃH, C(19)ÃH,
/
CH3), 4.06Á/4.19 (m, 4H,
/
/
/
/

H.X. Wang et al. / Journal of Organometallic Chemistry 679 (2003) 130Á
/134
133
Table 2
3.3. Crystal structure determination for 3d
3.3.1. Crystal data of 3d
˚
Selected bond lengths (A) and bond angles (8) for 3d
Bond lengths
C19H20ClFeN, Mrꢀ357.67, monoclinic, P21/n (No.
/
FeÃ
FeÃ
FeÃ
FeÃ
FeÃ
Cl(1)Ã
N(1)ÃC(13)
C(1)Ã
C(1)Ã
C(3)Ã
C(6)Ã
C(7)Ã
C(9)Ã
C(14)Ã
C(15)Ã
C(17Ã
/
C(1)
C(3)
C(5)
C(7)
C(9)
2.041(2) FeÃ
2.037(3) FeÃ
2.039(2) FeÃ
2.031(3) FeÃ
2.050(3) FeÃ
1.750(3) N(1)Ã
1.465(4) N(1)Ã
1.420(3) C(1)Ã
1.507(3) C(2)Ã
1.418(4) C(4)Ã
1.410(5) C(6)Ã
1.400(4) C(8)Ã
1.390(4) C(11)Ã
1.409(3) C(14)Ã
1.378(4) C(16)Ã
1.372(3) C(18)Ã
/
C(2)
C(4)
C(6)
C(8)
C(10)
2.040(2)
2.039(2)
2.036(2)
2.046(3)
2.053(3)
1.473(3)
1.385(3)
1.434(3)
1.424(4)
1.414(4)
1.367(4)
1.408(4)
1.528(3)
1.405(3)
1.374(4)
1.379(3)
˚
˚
˚
/
/
14), aꢀ
107.03(2)8, Vꢀ
cmꢁ3, F(0 0 0)ꢀ
10.48 cmꢁ1
/
8.908(2) A, bꢀ
/
13.63(1) A, cꢀ
/
14.510(3) A, bꢀ
4, Dcꢀ1.395 g
Ka)ꢀ
/
3
/
/
˚
/
1684.4000 A , Zꢀ
/
/
/
/
˚
/
736.00, lꢀ
/
0.71070 A, m(MoÁ
/
/
/
/
.
/C(17)
/C(11)
/
/C(14)
/
C(2)
C(11)
C(4)
C(7)
C(8)
C(10)
/
C(5)
C(3)
C(5)
C(10)
C(9)
3.3.2. Data collection for 3d
Yellow prismatic crystal of 3d with approx. dimension
of 0.60ꢂ0.50ꢂ
0.20 mm3 was mounted on a Rigaku
RAXIS-IV imaging plate area detector. Unit cell para-
meters were determined with 2u 555.18 and refined
with the least-squares method. 22/58 oscillation frames
in the range 1Á1108 and exposure of 10 min per frame
/
/
/
/
/
/
/
/
/
/
/
/
C(12)
C(19)
C(17)
C(19)
/
/C(15)
/
/C(16)
/
/
/)C(18)
/
were measured. The distance between the crystal and the
board was 105 mm. Intensities were collected with
Bond angles
C(11)ÃN(1)Ã
C(2)ÃC(1)Ã
C(1)ÃC(2)Ã
C(3)ÃC(4)Ã
C(7)ÃC(6)Ã
C(7)ÃC(8)Ã
C(6)Ã
N(1)Ã
N(1)Ã
C(15)Ã
C(15)Ã
Cl(1)ÃC(17)Ã
C(17)ÃC(18)Ã
C(14)ÃC(19)Ã
/
/
C(14)
119.9(2) C(11)Ã
128.1(2) C(13)Ã
108.3(2) C(2)ÃC(1)Ã
107.7(2) C(5)ÃC(1)Ã
108.3(3) C(2)ÃC(3)Ã
107.8(3) C(1)ÃC(5)Ã
107.9(3) C(6)ÃC(7)Ã
112.0(2) C(8)ÃC(9)Ã
120.1(2) N(1)Ã
116.6(2) C(1)ÃC(11)Ã
119.7(2) N(1)ÃC(14)Ã
119.4(2) C(14)ÃC(15)Ã
120.2(2) Cl(1)ÃC(17)ÃC(16)
121.3(2) C(16)ÃC(17)ÃC(18)
/
N(1)Ã
N(1)Ã
/
C(13)
120.2(2)
118.7(2)
107.1(2)
124.8(2)
108.3(2)
108.6(2)
107.5(3)
108.5(3)
110.4(2)
113.3(2)
123.2(2)
121.6(2)
120.0(2)
120.5(2)
graphite monochromated MoÁ
v Á2u scan technique. A total of 3386 reflections were
measured, 2802 reflections were considered as observed
applying the condition I ꢀ3s(I). Data were corrected
/
Ka radiation by using
/
/
C(11)
/
/C(14)
/
/
/
C(3)
/
/
C(5)
/
/
C(5)
/
/
C(11)
/
/
C(10)
/
/
C(4)
/
/
/
C(9)
/
/
C(4)
for Lorentz and polarization effects and also for
absorption by an empirical method using the program
DIFABS [10].
/
C(10)Ã
C(11)Ã
C(14)Ã
/C(9)
/
/
C(8)
/
/
C(12)
C(15)
/
/
C(10)
/
/
/
C(11)Ã
C(12)
C(19)
C(16)
/C(1)
/
C(14)Ã
/C(19)
/
/
/
C(16)Ã
/C(17)
/
/
3.3.3. Structure solution and refinement
/
/C(18)
/
/
The structure was solved by heavy-atom Patterson
methods and expanded by using Fourier techniques. All
calculations were performed by using the teXsan soft-
ware package [11]. The non-hydrogen atoms were
refined anisotropically. Hydrogen atoms were included
/
/C(19)
/
/
/
/C(18)
/
/
but not refined. The final R factors were 0.036 (Rwꢀ
/
0.051). The ratio of reflection/parameter was approxi-
mately 14. The maximum peak on the final difference
Jꢀ
Hz) ppm.
3e, yellow rod. Yield 30%. m.p. 91Á
/
8.8 Hz), 7.18 (d, 2H, C(16)Ã
/
H, C(18)Ã
/
H, Jꢀ
/
8.8
ꢁ3
˚
Fourier map corresponded to 0.19 e A
.
/
93 8C. Anal.
Found: C, 57.32; H, 4.84; N, 3.70. Calc. for
C19H20BrFeN: C, 57.32; H, 5. 06; N, 3.52%. IR (KBr
pellet): 1587, 1494, 1428, 1303, 1104, 1022, 998, 828, 811,
Acknowledgements
1
501 cmꢁ1. H-NMR: d 1.47 (d, 3H, CH3, Jꢀ
/
6.8 Hz),
4.19 (m, 4H, substituted Cp
ring), 4.14 (m, 5H, C5H5), 4.97 (q, 1H, C(11)ÃH, Jꢀ6.8
Hz), 6.67 (d, 2H, C(15)ÃH, C(19)ÃH, Jꢀ8.8 Hz), 7.30
(d, 2H, C(16)ÃH, C(18)ÃH, Jꢀ9.2 Hz) ppm.
3f, yellow rod. Yield 57%. m.p. 78Á79 8C. Anal.
We are grateful to the National Natural Science
Foundation of China for financial support of this
project. The Postdoctoral Fellowship of China (1999)
is also acknowledged.
2.46 (s, 3H, NÃ
/
CH3), 4.06Á
/
/
/
/
/
/
/
/
/
/
References
Found: C, 72.26; H, 7.12; N, 4.33. Calc. for
C20H23FeN: C, 72.08; H, 6.96; N, 4.20%. IR (KBr
pellet): 1599, 1586, 1495, 1474, 1459, 1294, 1105, 1023,
996, 830, 813, 501 cmꢁ1. 1H-NMR: d 1.46 (d, 3H, CH3,
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