New 1,2-disubstituted ferrocenyl stibines containing N-heterocyclic pendant arm: Sb-N hypervalent compounds

Article abstract of DOI:10.1016/j.jorganchem.2009.01.051

New 1,2-disubstituted ferrocenyl stibines viz. containing -CH₂NR or -CH₂NHR pendant arm at the ortho-position have been synthesized and characterized by various physicochemical methods. These new ferrocenylstibines were prepared by t

Full text of DOI:10.1016/j.jorganchem.2009.01.051

Journal of Organometallic Chemistry 694 (2009) 2037–2042
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Journal of Organometallic Chemistry
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New 1,2-disubstituted ferrocenyl stibines containing N-heterocyclic pendant
arm: Sb–N hypervalent compounds
*
A.M. Ortiz, P. Sharma , D. Pérez, Noé Rosas, A. Cabrera, L. Velasco, A. Toscano, S. Hernández
Instituto de Química, Universidad Nacional Autonoma de México, 04510 México D.F., Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
New 1,2-disubstituted ferrocenyl stibines viz. containing -CH2NR or -CH2NHR pendant arm at the ortho-
position have been synthesized and characterized by various physicochemical methods. These new ferr-
ocenylstibines were prepared by the nucleophilic substitution reaction of diphenyl[(N,N,N-trimethylam-
inomethylferrocenyl)iodide]stibine by different primary amines and secondary heterocyclic amines viz.
furan-2-ylmethylamine, p-aminoacetophenone, 3-(1-hydroxyethyl)-aniline, 4-hydroxypiperidine, 1-eth-
ylpiperazine and 4-(4-bromophenyl)-4-hydroxypiperidine. Molecular structure of stibine (2), (3), (5) and
(7) have been determined by X-ray crystallography. Stibine (2), (5) and (7) show a weak hypervalent Sb–
N interaction while stibine (3) does not show this interaction in solid state.
Received 1 September 2008
Received in revised form 27 January 2009
Accepted 28 January 2009
Available online 5 February 2009
Keywords:
Stibine
Ferrocenyl
N-heterocyclic
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
dimethylaminomethyl ferrocenyl)] stibine with excess of MeI, a
very stable N-methylated product was isolated. Considering the
Recently, the chemistry of hypervalent compounds bearing hea-
vier pnictogens (in particular Sb, Bi) has attracted interest [1–6].
Intramolecular interactions between antimony and sp3-nitrogen
atoms have been widely reported in the literature [7–13]. Very re-
cently, ferrocenylstibines containing 2-dimethylaminomethyl and
2-dimethylaminoethyl side chains have been reported. In the
molecular structures of these ferrocenylstibines, Sb–N hypervalent
interactions were observed [14–16].
On the other side, for the introduction of ferrocenylmethyl
group in nucleophilic substrates, most of the attention was paid
to quaternary ammonium salts of N,N,N-trimethylaminomethylfer-
rocene. In particular, new reactions of N-, C-, S- and P-ferro-
cenylmethylation of different compounds were performed with
the use of *(N,N,N-trimethylaminomethylferrocenyl)iodide (1a)
[17,18]. Also there appears only one report on the one-pot alkyl-
ation of [1-N,N-dimethylaminomethyl-2-diphenylphosphino]fer-
rocene (1b) with benzyl bromide and subsequent replacement of
the ammonium group with a nucleophile [19] but on the other
hand, reaction of ferrocenyl phosphine (1b) with 1 equiv. of methyl
iodide gives preferably an unstable N-methylated product, which
further reacts with O- and N-nucleophiles in a manner analogous
to that for the nonphosphinylated salt [FcCH2NMe3]I,[20,21]. Reac-
tion of 1b with excess of MeI yields the respective P,N-dimethylat-
ed salt. It was noted that either protection of phosphorus group or
use of benzyl bromide as an alkylating agent is advantageous to get
the N-methylated product. But in the reaction of diphenyl[(N,N-
vast number of ferrocene ligands, the unique stereoelectronic
properties of the ferrocene framework, existence of a very few re-
ports on ferrocene bonded antimony in the literature and our inter-
est in stibine ligands, this work was undertaken.
2. Results and discussion
All the compounds were synthesized by the nucleophilic substi-
tution reaction of diphenyl[(N,N,N-trimethylaminomethylferroce-
nyl)iodide]stibine salt with different amines in acetonitrile
(Scheme 1). All these stibines (2)–(7) are soluble in polar organic
solvents e.g. chloroform, dichloromethane and are insoluble in
water and show little solubility in non polar solvents e.g. hexane,
pentane.
Primary amines used in this work, on reaction with trimethyl-
ammonium salt, in equimolar ratio give secondary ferrocenyl
amines. These secondary ferrocenyl amines do not react further
with trimethylammonium salt and no tertiary diferrocenyl amine
was obtained. The formation of monoferrocenyl derivatives may
be interpreted because of the bulkiness of ferrocenyl moiety. In
the far IR spectra of these compounds, Sb–C and C–N vibrations
were observed. For all these compounds, in the FAB+ spectra
molecular ion peaks were observed along with fragments corre-
sponding to the successive loss of organic entities attached to anti-
mony atom. Fragmentation pattern in all these compounds are
similar. For compounds 4 and 6 high resolution mass spectra were
also obtained, and molecular ion peaks at 609.0712 (Calc. m/z
609.0715) and 586.1031 (Calc. m/z 586.1031) respectively, were
observed, confirming the molecular formulas for these compounds.
* Corresponding author. Fax: +52 555 6162217.
E-mail address: pankajsh@servidor.unam.mx (P. Sharma).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.01.051

2038
A.M. Ortiz et al. / Journal of Organometallic Chemistry 694 (2009) 2037–2042
NHR
SbPh2
R-NH2
Fe
NMe
3I
SbPh2
K2CO3 / CH3CN
Fe
NR2'
SbPh2
R2'-NH
Fe
k'
l
m
p
k'
j'
i'
k`
o
j'
i'
n
m
n
j`
i`
O
NH
O
n
g
m
h'
l
o
l
i
NH
c
g
h
n`
h'
b
f
Sb
p
NH
h`
g
j
d
e
i
i
c
o
h
b
f
m' n'
Sb
h
c
q
n``
b
f
Sb
j
d
q
j
d
e
k
p
Fe
e
HO
k
k
r
Fe
Fe
a
a
a
(2)
(3)
(4)
k'
k'
k'
j'
i'
j'
i'
s
r
j'
t
Br
m
l
N
l
m
g
h'
Sb
i'
h
l
N
q
N
p
g
g
'
h'
s
i
'
r
h'
c
m´
h
b
f
i
l'
OH
c
i
m'
N
h
j
d
c
b
f
p
Sb
b
f
l'
Sb
p
j
j
d
d
e
OH
k
o
e
e
Fe
k
k
Fe
Fe
a
a
a
(5)
(6)
(7)
Scheme 1.
In all the compounds, the assignment of individual proton sig-
nals in the 1H NMR spectra was based on JHH coupling constant val-
ues and was confirmed by COSY and HETCOR experiments. Though
Sb–N interactions were observed in the structural characteriza-
tions, evidence for such interactions could not be detected in 1H
NMR spectra of these stibines. In the 1H spectra of all these com-
pounds similar chemical shifts pattern was observed for ferrocene
fraction and phenyl rings. A singlet observed at approximately
4.0 ppm in the 1H spectra of all these stibines, can be assigned to
the un substituted Cp ring protons. The methylene protons of the
FcN moiety are not magnetically equivalent. This phenomenon
has been observed in the 1H NMR spectra of complexes containing
both mono dentate and bi dentate 1,2-disubstituted ferrocenyl li-
gands [22,23]. This is also a consequence of the asymmetry of
the bi substituted Cp ring. The stereoheterotopic methylene pro-
tons give rise to two AB doublets. The 1H NMR data of (4) show
the presence of only one set of enantiomers out of two possible
set of enantiomers. It was not possible to assign the signal to the
appropriate diastereomer and the X-ray crystal structure would
be of interest. Similarly in the 13C NMR spectra non existence of
two sets of signals were observed confirming the presence of one
Fig. 1. ORTEP diagram of diphenyl[2-(furan-2-ylmethylamino)methylferrocen-1-yl]-
stibine (2), showing 40% probability ellipsoids.

A.M. Ortiz et al. / Journal of Organometallic Chemistry 694 (2009) 2037–2042
2039
Fig. 2. ORTEP diagram of diphenyl[2-(4-acetylaniline)methylferrocen-1-yl] stibine (3) showing 40% probability ellipsoids.
diastereomer. The two phenyl groups of SbPh2 fraction are magnet-
ically non equivalent and appear at different chemical shifts.
The molecular structures of (2), (3), (5) and (7) have been con-
firmed by X-ray crystallography and are shown in Figs. 1–4. Crystal
data for all structural analyses are given in Table 1. Selected bond
lengths and angles for all compounds are listed in Table 2. The
average Sb–C(ferrocenyl) bond length found in these ferrocenylsti-
bines is 2.123 Å, which is slightly shorter than that Sb–C(phenyl)
bond length, the same observation was reported earlier also
[14,15]. All these compounds possess planar chirality. In the struc-
ture of compound (3), although the space group is non centrosym-
metric, it contains symmetry elements of 2nd order and so the unit
cell contains a pair of enantiomers (S,R) The compound (3) crystal-
lizes with 0.25 mol of hexane as solvent of crystallization and the
solvent was modeled in three major contributions in 0.10:0.10:
0.05 molar ratio.
In the molecular structure of compound (3) the two phenyl
groups attached to antimony atom are disordered. In both the
compounds, the distance between nitrogen atom of NMe2 group
and the central antimony atom is 2.989(3) Å and 3.287 Å, respec-
tively, which is shorter than the sum of their Van der Walls Radii
(3.74 Å) and longer than a covalent bond (2.11 Å). Taking into con-
sideration Sb–N interaction, the geometry around antimony in
compound (2) is distorted pseudo trigonal bipyramid with a lone
Fig. 3. ORTEP diagram of diphenyl[2-(4-hydroxypiperidin-1-yl)methylferrocen-1-
yl] stibine (5) showing 40% probability ellipsoids.
Fig. 4. ORTEP diagram of diphenyl[2-(4-(4-bromophenyl))-4-hydroxypiperidin-1-yl] methylferrocen-1-yl}stibine (7) showing 40% probability ellipsoids.

2040
A.M. Ortiz et al. / Journal of Organometallic Chemistry 694 (2009) 2037–2042
Table 1
Crystallographic data for compounds 2, 3, 5 and 7.
Compounds
2
3
5
7
Empirical formula
Formula weight
Crystal color
Crystal system
Space group
Crystal size (mm)
a (Å)
C28H26FeNOSb
570.10
C32.5H31.5FeNOSb
629.29
Yellow prism
Orthorhombic
Iba2
0.472 ꢂ 0.128 ꢂ 0.052
15.457(1)
42.469(1)
8.6561(5)
90
90
90
5682.3(6)
8
1.472
C29H34FeNO2Sb
606.17
C34 H33BrFeNOSb
729.12
Yellow prism
Triclinic
Yellow prism
Triclinic
Yellow prism
Triclinic
ꢀ
ꢀ
ꢀ
P1
P1
P1
0.144 ꢂ 0.088 ꢂ 0.082
11.644(1)
11.713(1)
11.732(1)
60.877(1)
61.427(1)
84.462(1)
1208.04(18)
2
0.33 ꢂ 0.16 ꢂ 0.07
7.9390(10)
11.946(2)
15.006(2)
80.525(3)
88.537(2)
77.301(2)
1369.3 (3)
2
0.38 ꢂ 0.20 ꢂ 0.18
9.7572(8)
11.168(1)
14.6486(13)
80.199(1)
76.433(1)
78.197(1)
1506.3(2)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (g/cm3)
1.567
1.738
1.470
1.541
1.608
2.732
l
(mmꢃ1
)
1.486
2h (°)
2.02–25.37
1.92–2534
0.01
30588
5190
0.0528
0.0384
0.0828
1.040
0.659/ꢃ0.276
25.36
25.33
Flacks parameter
Reflections collected
Independent reflections
Rint
R1 [I > 2
wR2 [all data]
13629
4403
0.0348
0.0335
0.0759
0.992
11421
5010
0.0490
0.0403
0.0609
0.843
12516
5505
0.0397
0.0321
0.0574
0.849
r
(I)]
Goodness-of-fit
Max./min.
D
q
(e Åꢃ3
)
0.0623/–0.265
0.825/ꢃ0.591
0.789/ꢃ0.429
Table 2
lecular Sbꢀ ꢀ ꢀN [3.287(3)] interaction. Taking in account this inter-
action, the geometry around antimony is distorted trigonal
bipyramidal.
Selected bond length (Å) and selected bond angles (°) for compounds 2, 3, 5 and 7.
Compound (2)
Compound (3)
Sb–C(8)
Sb–C(17)
Sb–C(23)
2.135(3)
2.154(4)
2.176(3)
2.989(3)
93.42 (11)
93.56(11)
97.17(11)
C(1)–Sb
Sb–C(20)
Sb–C(26)
2.135(4)
2.154(12)
2.155(9)
The molecule is monomeric in compound (7), and piperidine
ring exists in chair conformation with the hydroxyl group at the
axial position. Similar to compound (5), the puckering amplitudes
of the piperidine ring describe a slightly distorted chair conforma-
tion with q3 ꢁ q2 and the total puckering amplitude Q [0.573(5) Å]
lies only slightly under the Q value of an ideal cyclohexane chair
(0.63 Å) [25]. The molecule presents both inter and intramolecular
interactions. There exists a weak Sb–N interaction and Sb–N hyper-
valent bond is long [3.59(2) Å]. Taking in account this interaction
the geometry around antimony is distorted trigonal bipyramidal.
An intermolecular hydrogen bonding O–Hꢀ ꢀ ꢀO [2.922(4) Å] was ob-
served in the crystal structure, forming a pseudo dimer in the solid
state.
Sbꢀ ꢀ ꢀN(1)
C(8)–Sb–C(17)
C(8)–Sb–C(23)
C(17)–Sb–C(23)
C(1)–Sb–C(20)
C(1)–Sb–C(26)
C(20)–Sb–C(26)
96(2)
93.2(7)
97.4(17)
Compound (5)
Compound (7)
Sb–C(2)
Sb–C(23)
Sb–C(17)
2.118(4)
2.124(4)
2.160(4)
3.287(3)
97.06(15)
95.27(14)
94.99(15)
Sb–C(2)
Sb–C(23)
Sb–C(29)
2.128(3)
2.165(3)
2.150(3)
3.59(2)
99.36(12)
93.21(11)
95.70(12)
Sbꢀ ꢀ ꢀN
Sbꢀ ꢀ ꢀN
C(2)–Sb–C(23)
C(2)–Sb–C(17)
C(23)–Sb–C(17)
C(2)–Sb–C(29)
C(2)–Sb–C(23)
C(29)–Sb–C(23)
In conclusion, new 1,2-disubstituted ferrocenyl stibines viz.
containing -CH2NR or -CH2NHR pendant arm at the ortho-position
have been synthesized and characterized and crystal structures of
some of these new stibines are reported.. The existence of strong
interactions between antimony and nitrogen, transcending the oc-
tet theory, and classified as the hypervalent bonding, was shown
not only in tri aryl stibines but also in ferrocenylstibines. This
hypervalent Sb–N bonding was demonstrated by single crystal X-
ray analysis.
pair of electron along with two carbon atoms (1Ph and 1Fc) occu-
pying the equatorial position. Nitrogen atom and one of the C (phe-
nyl group) atom are on the axial position with a C–Sb–N angle
161.03(10)°. The C23–Sb (Sb–Ph) bond [2.176(3) Å] trans to the
nitrogen atom is slightly longer than the other Sb–C (Sb–Ph) bonds,
2.154(4) Å. A similar structure and lengthening of one of the Sb–C
bond length were reported earlier in similar compounds [14]. In
compound (3) the geometry around antimony atom is pyramidal.
The average C–Sb–C bond angle is 95.53° which is similar to the
average bond angles found in triphenylstibine or tris(2-thienyl)sti-
bine [24,25]. There exists intermolecular hydrogen bonding
N–Hꢀ ꢀ ꢀO [2.29(5) Å] in the crystal structure.
3. General synthesis
In a Schlenk tube, to a solution of 0.3 mmol of Rac-diphenyl[(N,N,N-
trimethylaminomethylferrocenyl)iodide]stibine and 3 mmol of K2CO3,
in CH3CN (15 ml), 0.35 mmol of corresponding amine was added
under nitrogen atmosphere. The mixture was refluxed at 85–
90 °C with continuous stirring for about 72 h. After extraction with
dichloromethane or chloroform (3 ꢂ 15 ml) and drying over so-
dium sulfate, solvent was removed under vacuum and crude prod-
uct was obtained. The crude product was purified by column
chromatography and the product was re-crystallized from a chlo-
roform–hexane mixture.
Compound (5) crystallizes with one molecule of methanol as a
solvent of crystallization piperidine ring exists in chair conforma-
tion with the hydroxyl group at the equatorial position. Puckering
amplitudes of the piperidine ring describe a slightly distorted chair
with q3 ꢁ q2. Indeed, the total puckering amplitude Q [0.571(3) Å]
lies only slightly under the Q value of an ideal cyclohexane chair
(0.63 Å) [26]. The molecule is monomeric and presents an intramo-

A.M. Ortiz et al. / Journal of Organometallic Chemistry 694 (2009) 2037–2042
2041
3.1. X-ray crystallography
3.1.4. Diphenyl[2-(4-hydroxypiperidin-1-yl)methylferrocen-1-yl]
stibine (5)
The X-ray intensity data were measured at 293 K on a Bruker
SMART APEX CCD-based X-ray diffractometer using a monochro-
4-Hydroxypiperidine was used for the reaction. Yellow Solid
(20%); Empirical formula: C28H30FeNOSb; m.p: 126 °C (dec.); IR
matized Mo K
a
radiation (K
a
0.71073 Å). The detector was placed
(m
cmꢃ1): 3476 (O–H), 3057 (C–H aromatic), 1428 (O–H), 1063
at a distance of 4.837 cm from the crystals in all cases. Analysis of
the data showed in all cases negligible decays during data collec-
tions. An analytical face indexed absorption correction was ap-
plied. Crystal structures were refined by full-matrix least squares.
SMART software (data collection and data reduction) and SHELXTL
were used for solution and refinement of the structures.
(C–O), 452 (Sb–C) FAB+ m/z 573 (58%) [M]+, 440 (50%)
[Mꢃ56]+, 397 (100%) [FcCH2SbPh]+, 275 (13%) [SbPh2]+; 1H
NMR (CDCl3, d ppm) 1.20 (m, 4H, -CH2CH2), 1.40 (m, 1H, OH),
1.83–1.99 (m, 2H, CH2), 2.43–2.63 (m, 2H, CH2), 3.01 (d2 JHH
,
12.9 Hz, 1H, CH2N), 3.79 (d2 1H JHH, 12.9 Hz,, CH2N), 3.79 (m,
1H, C5H3), 3.39 (m, 1H, CH), 4.0 (s, 5H, C5H5), 4.20 (t, 1H,
C5H3), 4.30 (m, 1H, C5H3), 7.25–7.31 (m, 5H, Ph), 7.45–7.56 (m,
5H, Ph); 13C NMR (CDCl3, ppm) 33.2 (Cm), 34.0 (Cm ), 49.6 (Cl),
0
3.1.1. Diphenyl[2-(furan-2-ylmethylamino)methylferrocen-1-
yl]stibine (2)
0
51.1 (Cl ), 58.7 (Cg), 67.8 (Cp), 69.1 (Ca), 69.5 (Cf), 72.3 (Cd),
0
0
72.3 (Cb), 74.1 (Ce), 90.5 (Cc), 128.0, 128.3 (Cj, Cj ,Ck, Ck ), 135.7,
The compound was synthesized by a similar procedure to gen-
eral synthesis and furfuryl amine was used for the reaction. The
single crystals of the compound were grown in pentane. Yield;
0
0
136.6 (Ci, Ci ) 138.6, 140.4(Ch, Ch ).
m.p.: 86–88 °C; IR (
m
cm–1): 454 (Sb–C), 2922, 2852 (C–H ali-
3.1.5. Diphenyl[2-(4-ethylpiperazin-1-yl)methylferrocen-1-yl]stibine
phatic), 3060 (C–H aromatic), 3386 (N–H hydrogen-bonded);
FAB+ m/z: 569 (75%) [M]+, 473 (100%) [M–(C4H3O)CH2NH]+, 397
(36%) [MꢃPh]+, 275 (23%) [SbPh2]+, 199 (59%) [FcCH2]+; 1H NMR
(CDCl3, d in ppm): 2.17 (br, s, 1H, NH), 3.36 (d, 1H, JHH = 13.21 Hz,
CH2), 3.45 (d, 1H, JHH = 14.58 Hz, CH2), 3.56 (d, 1H, JHH = 12.38 Hz,
CH2), 3.62 (d, 1H, JHH = 13.21 Hz, CH2), 3.72 (m, 1H, CH, C5H3),
4.07 (s, 5H, CH, C5H5), 4.23 (t, 1H, JHH = 2.20 Hz, CH, C5H3), 4.42
(m, 1H, CH, C5H3), 6.03 (d, 1H, Jln = 0.83 Hz, CH, Furan), 6.27 (m,
1H, Jlm = 1.93 Hz, CH, Furan), 7.25–7.57 (m, 11H, Ph and Furan);
13C NMR (CDCl3, d in ppm): 43.45 (Cg), 47.48 (Cp), 69.13 (Ca),
69.39 (Ce), 71.56 (Cf), 70.40 (Cb), 74.72 (Cd), 107.29 (Cc), 110.22
(6)
1-Ethylpiperazine was used for the reaction. Yellow Solid (44%);
Empirical formula: C28H30FeNOSb; m.p: 140 °C (dec.); IR (m
cmꢃ1):
3058 (C–H aromatic), 455 (Sb–C); FAB+ m/z 586 (98%) [M]+, 473
(16%) [FcCH2SbPh2]+, 397 (100%) [FcCH2SbPh]+, 275 (27%) [SbPh2]+;
1H NMR (CDCl3, d ppm) 0.91 (t, 3H, CH3), 2.21 (q, 2H, CH2), 2.26 (m,
8H, C4H8N2), 3.01 (d2 JHH, 12.9 Hz, 1H, CH2), 3.82 (d2 JHH, 12.6 Hz,
1H, CH2), 3.78 (m, 1H, C5H3), 4.0 (s, 5H, C5H5), 4.20 (t, 1H, C5H3),
4.31 (m, 1H, C5H3), 7.25–7.32 (m, 5H, Ph), 7.44–7.56 (m, 5H, Ph)
13C NMR (CDCl3, ppm) 11.6 (Cp), 51.7 (Co), 52.0 (Cl), 58.8 (Cg),
69.1 (Ca), 69.4 (Cf), 72.2 (Cd), 72.3 (Cb), 74.1 (Ce), 90.2 (Cc), 127.9,
00
0
0
0
0
(Cl), 109.70 (Cm), 110.61 (Cn) 128.29, 128.40 (Ci, Cj ) 128.55,
128.2 (Cj, Cj ,Ck, Ck ), 135.8, 136.5 (Ci, Ci ), 139.2, 140.4 (Ch, Ch ).
0
0
0
128.71 (Ck, Ck ) 135.91, 136.59 (Ci , Cj) 139.55 141.86 (Ch, Ch ).
3.1.6. Diphenyl {2-[4-(4-bromophenyl)-4-hydroxypiperidin-1-yl]
methylferrocen-1-yl}stibine (7)
4-(4-Bromophenyl)-4-hydroxypiperidine was used for the reac-
tion. Yellow solid (31%); Empirical formula: C34H33BrFeNSb; m.p:
3.1.2. Diphenyl[2-(4-Acetylaniline)methylferrocen-1-yl] stibine (3)
The compound was synthesized by a similar procedure to gen-
eral synthesis p-amino acetaphenone was used for the reaction.
The compound was crystallized in hexane. Yellow Solid (42%);
145 °C (dec.); IR (
m
cmꢃ1): a 3455 cmꢃ1 (O–H), 3043 (C–H aro-
Empirical formula: C31H28FeNOSb; m.p: 147–150 °C; IR(
m
cmꢃ1):
matic), 454 (Sb–C) FAB+ m/z 728 (100%) [M]+, 650 (16%) [MꢃBr],
473 (19%) [FcCH2SbPh2]+, 397 (100%) [FcCH2SbPh]+, 275 (34%)
[SbPh2]+; 1H NMR (CDCl3, d ppm) 1.2– 2.8 (m, 8H, C5H8N), 3.01
(m, 1H, CH2), 3.80 (m, 1H, C5H3), 3.91 (d2, 1H, JHH = 12.9 Hz, CH2),
4.03 (s, 5H, C5H5), 4.21 (m, 1H, C5H3), 4.34 (m, 1H, C5H3), 6.92 (d,
2H, H–Ar), 7.56–7.31 (m, 12H); 13C NMR (CDCl3, ppm) 36.8, 38.8
3404 (N–H), 3057 (C–H aromatic), 1595(C–O), 453 (Sb–C). FAB+
m/z 607(8%) [M]+, 592 (7%) [M–CH3]+, 473 (70%) [FcCH2SbPh2]+,
397 (27%) [FcCH2SbPh]+, 275 (13%) [SbPh2]+; 1HNMR (CDCl3, d
ppm) 2.47 (s, 3H, CH3), 3.82 (m, 1H, C5H3), 3.94 (N–H), 4.01 (d2,
1H, JHH = 4.95 Hz, CH2), 4.09 (d2, 1H, JHH = 4.95 Hz, CH2), 4.15 (s,
5H, C5H5), 4.29 (t, 1H, C5H3), 4.45 (m, 1H, C5H3), 6.22 (d, 2H, H–
Ar), 6.20–6.40 (m, 10H, Ph), 7.76 (d, 2H, H–Ar); 13C NMR (CDCl3,
ppm) 25.9 (Cq), 43.6 (Cg), 69.2 (Ca), 70.5 (C, Ce), 71.9 (C, Cf), 72.16
0
0
(Cm, Cm ), 46.8,50.3 (Cl, Cl ), 58.9 (Cg), 69.1 (Ca), 70.9 (Ce), 71.0
0
0
(Cb), 72.3 (Cf), 74.2 (Cd), 120.9 (Ct), 126.4 (Cr, Cr ), 130.9 (Cs, Cs ),
0
0
0
128.0, 128.5 (Cj, Cj ,Ck, Ck ), 135.5, 136.5 (Ci, Ci ).
0
(Cb), 74.6 (Cd), 90.0 (Cc), 111.4 (Cn, Cn ), 126.9 (Co), 128.5, 128.9
0
0
0
0
(Cj, Cj , Ck, Ck ), 130.5 (Cm, Cm ), 135.9, 136.4 (Ch, Ch ), 136.6, 139.0
Acknowledgements
0
(Cj, Cj ), 151.2 (Cl), 196.2 (Cp).
Authors are thankful to DGAPA(IN206809) for financing the
work. We are also thankful to Javier Perez Flores for their assis-
tance in mass spectral studies.
3.1.3. Diphenyl {2-[3-(1-hydroxyethyl)aniline]methylferrocen-1-
yl}stibine (4)
3-(1-Hydroxyethyl)-aniline was used in place of p-aminoaceta-
phenone. Yellow Solid (35%); Empirical formula: C31H28FeNOSb;
m.p: 86–88 °C; IR (m
cmꢃ1): 3384 (O–H) y (N–H), 3057 (C–H aro-
matic), 455 (Sb–C) FAB+ m/z 609 (100%) [M]+, 532 (5%) [MꢃPh]+,
473 (38%) [FcCH2SbPh2]+, 397 (15%) [FcCH2SbPh]+, 275 (15%)
[SbPh2]+; 1H NMR (CDCl3, d ppm) 1.44 (d, 3H, CH3), 1.53 (s, 1H,
NH), 3.77 (m, 1H, C5H3), 3.94 (d, 1H, CH2), 3.86 (s, 5H, C5H5), 4.27
(m, 1H, C5H3), 4.46 (m, 1H, C5H3), 4.06 (m, 1H, CH2), 4.74 (m, 1H,
CH), 6.31 (m, 2H, H–Ar), 6.66 (m, 1H, H–Ar), 7.07 (m, 1H, H–Ar),
7.25–7.38 (m, 10H, Ph); 13C NMR (CDCl3, ppm) 24.8 (Cq), 44.2
(Cg), 69.1 (Ca), 70.3 (Ce), 71.2 (Cp), 72.5 (Cd), 74.6 (Cf), 109.7 (Cm),
Appendix A. Supplementary material
CCDC 698470, 698471, 698472 and 698473 contain the sup-
plementary crystallographic data for compound (2), (3), (5) and
(7). These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2008.07.019.
0
00
0
0
0
112.0 (Cn), 128.4, 129.8 (Cn , Cn , Ck, Ck , Cj, Cj ), 135.7,136.7 (Ci, Ci ).

2042
A.M. Ortiz et al. / Journal of Organometallic Chemistry 694 (2009) 2037–2042
[13] S. Kamepalli, C.J. Karmalt, R.D. Culp, A.H. Cowley, R.A. Jones, N.C. Norman,
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