Synthesis and reactions of the ferrocene derived hydroxymethyl phosphine FcCH(CH3)P(CH2OH)2 and its sulfide: Crystal structures of [FcCH(CH3)P(S)R2] R=CH2OH, CH2CH2CN

Article abstract of DOI:10.1016/S0022-328X(00)00137-6

The racemic ferrocene derived hydroxymethyl phosphine FcCH(CH₃)P(CH₂OH)₂ (1) (Fc=ferrocenyl) was prepared by the reaction of P(CH₂OH)₃ with [FcCH(CH₃) NEt₂Me]⁺I^-<

Full text of DOI:10.1016/S0022-328X(00)00137-6

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 602 (2000) 125–132
Synthesis and reactions of the ferrocene derived hydroxymethyl
phosphine FcCH(CH3)P(CH2OH)2 and its sulfide: crystal
structures of [FcCH(CH3)P(S)R2] R=CH2OH, CH2CH2CN and
FcCH(CH3)P(S)(CH2O)2PPh (Fc=ferrocenyl)
T.V.V. Ramakrishna a, Anil J. Elias a,*, Ashwani Vij b
a Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India
b Single Crystal X-ray Diffraction Laboratory, Uni6ersity of Idaho, Moscow, ID 83843, USA
Received 7 January 2000; received in revised form 18 February 2000
Dedicated to Professor S.S. Krishnamurthy on the occasion of his 60th birthday
Abstract
The racemic ferrocene derived hydroxymethyl phosphine FcCH(CH3)P(CH2OH)2 (1) (Fc=ferrocenyl) was prepared by the
reaction of P(CH2OH)3 with [FcCH(CH3) NEt2Me]+I−. The latter was prepared by the reduction of acetyl ferrocene to the
corresponding alcohol, which was converted into its acetate and reacted further with diethylamine, followed by methyl iodide.
Reaction of 1 with acrylonitrile yielded the phosphine FcCH(CH3)P(CH2CH2CN)2 (2), while reaction of 1 with morpholine
yielded FcCH(CH3)P[CH2(NC4H8O)]2 (3). Reactions of compounds 1–3 with elemental sulfur yielded the corresponding
phosphine sulfides 4–6. The hydroxymethyl groups of the phosphine sulfide FcCHCH3P(S)(CH2OH)2 (4) reacted readily with
PhPCl2 and O(SiMe2Cl)2 forming six- and eight-membered heterocycles FcCH(CH3)P(S)(CH2O)2PPh (7) and
FcCH(CH3)P(S)(CH2OSiMe2)2O (8), respectively. The crystal structures of compounds 4, 5 and 7 were determined. © 2000
Elsevier Science S.A. All rights reserved.
Keywords: Aminoethyl ferrocene; Hydroxymethyl phosphines; Phosphine sulfide; Racemic phosphine
are potential candidates for biphasic catalysis and in
the development of site specific radiopharmaceuticals
1. Introduction
[2]. Henderson and co-workers have prepared
ferrocene derived hydroxymethyl phosphine,
a
The synthesis and coordination chemistry of stable
hydroxymethyl phosphines and diphosphines have at-
tracted a lot of attention in recent years [1]. Katti and
co-workers have shown that water soluble, chelating
hydroxymethyl diphosphines coordinated to metals
such as technetium, palladium, platinum and rhenium
FcCH2P(CH2OH)2 [3] (Fc=ferrocenyl), which has
been found to be an excellent precursor for a variety of
other ferrocene derived phosphines including the highly
stable primary phosphine FcCH2PH2 [3c]. The rele-
vance of ferrocene based phosphines stems from the
fact that a large number of chiral aminoethyl and
phosphinoethyl ferrocenes have been found to be highly
efficient chiral ligands for homogeneous catalysts in
assymmetric transformations [4]. Many of these have
been derived primarily from [1-(N,N-dimethyl-
amino)ethyl] ferrocene with the further substitution of
the substituted cyclopentadienyl group by a phosphine
moiety [5]. Such compounds possess a planar chirality
in addition to the central element of chirality resulting
Scheme 1.
* Corresponding author. Fax: +91-512-590007.
E-mail address: elias@iitk.ac.in (A.J. Elias)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 0 ) 0 0 1 3 7 - 6

126
T.V.V. Ramakrishna et al. / Journal of Organometallic Chemistry 602 (2000) 125–132
[3]. Unlike the previously reported achiral phosphine
FcCH2P(CH2OH)2, phosphines 1–3 were viscous liq-
uids and posed considerable difficulty in their purifica-
tion. Attempts to purify these phosphines by high
vacuum distillation using a kugelrohr apparatus were
unsuccessful. The hydroxymethyl phosphine 1 could
not be purified to obtain a reasonable level of purity for
elemental analysis by various attempts of column chro-
matography. However, its identity was conclusively
proved by NMR, mass spectral studies and by conver-
sion to the crystalline phosphine sulfide 4. Phosphines 2
and 3 were purified by column chromatography under a
nitrogen atmosphere over silica gel by using a mixture
of hexane–ethyl acetate and dichloromethane–
methanol as the eluants, respectively.
The phosphine sulfides 4–6, obtained by the reaction
of compounds 1–3 with elemental sulfur, were crys-
talline solids and were purified by chromatography
(Scheme 2). The EIMS spectra of 1–4 gave the molecu-
lar ion peak and the base peak was 213, indicating the
ferrocenylethyl cation FcCH(Me)+. The electrospray
mass spectra of compounds 5 and 6 gave MH+. The
chemical shifts of the proton NMR spectra of all the
phosphines showed agreement with similar chiral com-
pounds reported by Togni et al. [5b]. The 31P-NMR
chemical shifts of compounds 1–3 were observed in the
range −38 to −4 ppm and the sulfides 4–6 in the
range 53–62 ppm.
As addition of formaldehyde to PH3 is a reversible
process [10], one can expect considerable differences in
the reactivity of a hydroxymethyl group bonded to
trivalent phosphorus in comparison with one bonded to
a pentavalent phosphorus atom. The PIII(CH2OH)2
group of 1 was found to behave as a masked PIIIH2
group, as indicated by the addition reaction to acryloni-
trile. However, our attempts to react the hydroxy-
methyl group of the phosphine 1 with organophospho-
rus and organosilicon halides were found to result in
mixtures of products that could not be easily separated
and identified. In contrast, the hydroxymethyl groups
of the phosphine sulfide 4 were found to react readily
with PhPCl2 in the presence of triethylamine as an HCl
scavenger to yield the six-membered heterocyclic phos-
phite 7 (Scheme 3). Reaction of 4 with O(SiMe2Cl)2 in
the presence of triethylamine also proceeded smoothly
yielding the eight-membered heterocycle 8. A similar
substitution was observed when FcCH2P(S)(CH2OH)2
was dilithiated and reacted with the carbaphosphazene
(Me2NCN)2(Cl2PN) [11]. These results indicate that
the P(CH2OH)2 group in the phosphine sulfide 4
behaves like a simple diol and undergoes deprotona-
tion readily. In contrast, the high nucleophilicity of
the trivalent phosphorus site of 1 makes it an easy
target for metallation and phosphonium salt forma-
tion. The EIMS of compounds 7 and 8 gave the molec-
ular ion peak. For compound 7, a pair of dou-
Scheme 2.
from a chiral carbon [6]. Further, ferrocenyl diphosphi-
nes as well as substituted phosphaferrocene ligands
belonging to this category have been synthesized and
their metal complexes prepared [7].
It is of interest to note that ferrocene derived hydrox-
ymethyl phosphines having an assymmetric carbon
atom linking the cyclopentadienyl group and the phos-
phorus atom have not been reported so far. Such
compounds are potential precursors for a wide variety
of novel chiral phosphines, diphosphines and metal
complexes that can be used in assymmetric transforma-
tions. In this paper we report the synthesis of the
ferrocene derived racemic hydroxymethyl phosphine
FcCH(CH3)P(CH2OH)2
(1)
and
its
sulfide
FcCH(CH3)P(S)(CH2OH)2 (4). Reactions of 1 and 4
with other reagents have been carried out with a view
to compare the reactivity of the hydroxymethyl groups.
The crystal structures of the phosphine sulfides 4, 5 and
the cyclic phosphite FcCH(CH3)P(S)(CH2O)2PPh (7)
have also been determined.
2. Results and discussion
Sodium borohydride reduction of acetyl ferrocene,
followed by acetylation of the alcohol and reaction with
diethyl amine gave the aminoethyl ferrocene
FcCH(CH3)NEt2 in 92% yield [8]. Reaction of the
amine with methyl iodide [9], followed by reaction with
P(CH2OH)4Cl and KOH along with excess of NEt3
gave the hydroxymethyl phosphine FcCH(CH3)P-
(CH2OH)2 (1) (Scheme 1). Reaction of 1 with acryloni-
trile and morpholine was found to proceed in a similar
manner to reactions carried out by Henderson and
co-workers to yield the phosphines 2 and 3 (Scheme 2)

T.V.V. Ramakrishna et al. / Journal of Organometallic Chemistry 602 (2000) 125–132
127
blets was observed in the 31P-NMR spectrum at l 35.82
and 149.00 ppm, the latter being due to the trivalent
phosphorus atom. For compound 8, the peak in the
Fig. 3. Molecular structure of FcCH(CH3)P(S)(CH2CH2CN)2 (5).
Scheme 3.
Fig. 4. Molecular structure of FcCH(CH3)P(S)(CH2O)2PPh (7).
31P-NMR spectrum was observed at 53.39 ppm for the
phosphine sulfide group.
The X ray structures of compounds 4, 5 and 7 are
given in Figs. 1–4. Tables 2–4 gives the selected bond
distances and angles for compounds 4, 5 and 7, respec-
tively. In the case of 4, the OH group attached to C14
was found to be disordered. It was modelled using the
PART command in SHELXTL 5.03 and the occupancies
were refined as a free variable [15]. The major compo-
nent of this disorder was refined to 90% occupancy.
The hydrogen atoms were added at the calculated
positions on O2 and O2%. In all the phosphine sulfide
structures determined in this study, the PꢀCHR (R=H
or Me) distances were observed shorter in comparison
with those reported for the similar phosphines
Fig. 1. Molecular structure of FcCH(CH3)P(S)(CH2OH)2 (4).
,
FcCH2P(CH2OH)2 (average 1.857 A) [3] and
,
FcCH2PH2 (1.850 A) [3c]. The shortest PꢀCHR dis-
tance has been observed for the cyanoethyl phosphine
,
sulfide 5 (average 1.805 A). The bond distances and
angles of 4 show similarities to that of the phosphine
sulfide FcCH2P(S)(CH2OH)2 [3]. The sulfur atom of 4
,
shows bifurcated hydrogen bonding of 2.760 A to H2%A
,
and 2.480 A to H11 (Fig. 2). This is supported by the
,
S1–O1 and S1–O2% distances of 3.215 and 3.040 A. The
Fig. 2. Packing diagram of 4 showing hydrogen bonds.

128
T.V.V. Ramakrishna et al. / Journal of Organometallic Chemistry 602 (2000) 125–132
Table 1
Crystallographic data for compounds 4, 5 and 7
Compound
4
5
7
Empirical formula
Formula weight
Crystal system
C14H19FeO2PS
338.17
Monoclinic
P21/c
C
384.25
Monoclinic
P21/n
18H21FeN2PS
C20H22FeO2P2S
444.23
Monoclinic
P21/c
Space group
Unit cell dimensions
,
a (A)
14.200(3)
8.5594(13)
11.9206(17)
90
90.83(2)
90
1448.7(4)
4
1.550
704
1.289
213(2)
23.25
9.700(4)
20.094(10)
10.527(3)
90
116.75(2)
90
1832.2(13)
4
1.393
800
1.024
213(2)
23.26
13.604
7.299
20.626
90
90.91
90
2047.7
4
1.441
920
1.006
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
V (A )
3
,
Z
Dcalc (g cm−3
F(000)
)
Absorption coefficient (mm−1
Temperature (K)
2q (max) (°)
)
293(2)
24.97
Index ranges
−155h55,
−95k58,
−135l513
2816
−95h510,
−225k522,
−115l58
7822
05h516,
05k58,
−245l524
3766
Reflections collected
Unique data (Rint
Parameters refined
)
0.0451
180
0.0738
209
0.0320
236
Final indices (2| data), R1 (wR2)
0.0492 (0.1019)
0.0625 (0.118)
1.161
0.381
−0.341
0.0683 (0.1486)
0.0931 (0.1618)
1.079
0.617
−0.317
0.0373 (0.1073)
0.0820 (0.1349)
0.879
0.360
−0.332
All data, R1 (wR2) a
Goodness-of-fit
Largest difference peak (e A
Largest difference hole (e A
−3
,
)
−3
,
)
a R=ꢀꢁFoꢂ−ꢂFoꢁ/ꢀꢂFoꢂ; wR2=[ꢀ[w(F2o−Fc2)2]/ꢀ[w(Fo2)2]]1/2
.
X-ray structure of 7 shows the cyclic six-membered
phosphite group in a chair conformation. The sum of
the angles around the trivalent phosphorus P(2) is
305.3°, indicating a pyramidal phosphorus. In compari-
son to the PꢀO bonds in a similar six-membered hetero-
cycle formed from the reaction of FcCH2P(S)-
(CH2OLi)2 with the carbaphosphazene (Me2NCN)2-
(Cl2PN) [11], the PꢀO bonds in 7 are found to be
crystalline solids and structurally characterized. The
hydroxy groups of the phosphine sulfide were found to
behave like a simple diol undergoing dehydrohalogena-
tion with phosphorus and silicon dichlorides, leading to
the ferrocene derived heterocycles 7 and 8. We are
currently exploring the reaction potential of these phos-
phines and phosphine sulfides.
,
elongated to an extent of 0.04 A. For all the phosphine
sulfides, the torsion angles between the PꢁS group and
the methyl group attached to the chiral carbon were
found to range from −57.8 to +53.2°.
Table 2
,
Selected bond distances (A) and bond angles (°) for compound 4
Bond lengths
FeꢀC a
2.0375(5)
1.4990(7)
1.8319(5)
CꢀC a
P(1)ꢀC(11)
O(2)ꢀC(14)
1.4015(8)
1.842(5)
1.430(7)
av
av
3. Conclusions
C(6)ꢀC(11)
P(1)ꢀC(13)
We have synthesized the first example of ferrocene
derived hydroxymethyl phosphine and phosphine
sulfide having an assymmetric carbon atom linking the
cyclopentadienyl group and the phosphorus atom. The
hydroxymethyl groups of the phosphine reacts with
acrylonitrile forming cyanoethyl groups and with mor-
pholine forming morpholinomethyl groups. The phos-
phines were converted into the sulfides, which were
Bond angles
CꢀCꢀC b
108.3(5)
CꢀCꢀC c
C(6)ꢀC(11)ꢀP(1)
C(11)ꢀP(1)ꢀC(13)
C(6)ꢀC(11)ꢀC(12)
107.95(5)
109.3(3)
105.8(2)
115.2(5)
av
av
C(14)ꢀP(1)ꢀC(13) 103.6(2)
O(2)ꢀC(14)ꢀP(1)
C(7)ꢀC(6)ꢀC(11)
109.8(4)
126.1(5)
a In cyclopentadienyl ring.
b In substituted cyclopentadienyl ring.
c In unsubstituted cyclopentadienyl ring.

T.V.V. Ramakrishna et al. / Journal of Organometallic Chemistry 602 (2000) 125–132
129
Table 3
erences and the mass spectra on a Jeol D-300 (EI/CI)
spectrometer in the EI mode. Analyses were carried out
on Carlo Erba CHNS-O 1108 elemental analyzer. Atom
,
Selected bond distances (A) and bond angles (°) for compound 5
Bond lengths
1
labeling used in H- and 13C-NMR of the cyclopentadi-
FeꢀC a
2.030(6)
1.503(8)
1.809(7)
1.397(10)
CꢀC a
P(1)ꢀC(13)
N(1)ꢀC(15)
C(14)ꢀC(15)
1.411(11)
1.801(7)
1.098(8)
1.476(10)
av
av
enyl ring is in accordance with the standard format used
by previous authors [3d].
C(1)ꢀC(11)
P(1)ꢀC(16)
C(16)ꢀC(17)
4.3. X-ray diffraction studies
Bond angles
C(1)ꢀC(11)ꢀP(1) 111.7(4)
C(2)ꢀC(1)ꢀC(11) 127.5(5)
C(14)ꢀC(13)ꢀP(1)
C(13)ꢀP(1)ꢀC(16)
av
116.7(5)
104.7(4)
108.3(8)
A Siemens SMART diffractometer with a CCD detector
at −54°C was employed for data collection of com-
pounds 4 and 5. The frame data for these were acquired
using Siemens SMART software and processed on SGI-
Indy/Indigo 2 workstation by using SAINT software [13].
The structures of compounds 4 and 5 were solved by di-
rect methods using the SHELX 90 [14] program and
refined by the full-matrix least-squares method on F2 us-
ing SHELXL 93, incorporated in SHELXTL-PC V 5.03 [15].
Data collection of 7 was carried out on an Enraf–Non-
ius CAD4 diffractometer and structure solved by direct
methods using the WINGX program [16] and refined on
F2 using full-matrix least-squares (SHELXL-97) [17]. All
non-hydrogen atoms were refined anisotropically. The
hydrogen atoms were located from the difference elec-
tron-density maps and were included in the refinement
process in an isotropic manner. Table 1 lists the crystal
data and data collection parameters for compounds 4, 5
and 7.
CꢀCꢀC b
108.0(5)
CꢀCꢀC c
av
a In cyclopentadienyl ring.
b In substituted cyclopentadienyl ring.
c In unsubstituted cyclopentadienyl ring.
Table 4
,
Selected bond distances (A) and bond angles (°) for compound 7
Bond lengths
FeꢀC a
C(1)ꢀC(11)
O(1)ꢀC(13)
P(2)ꢀO(2)
2.0255(4)
1.501(5)
1.436(4)
1.635(3)
CꢀC a
1.381(8)
1.824(4)
1.836(4)
av
av
P(1)ꢀC(13)
P(2)ꢀC(15)
Bond angles
C(14)ꢀP(1)ꢀC(13) 100.18(18)
C(1)ꢀC(11)ꢀP(1)
C(11)ꢀP(1)ꢀC(13) 107.34(18)
O(2)ꢀP(2)ꢀC(15) 100.74(17)
110.5.(3)
O(1)ꢀC(13)ꢀP(1)
O(1)ꢀP(2)ꢀO(2)
112.8(3)
102.45(14)
a In cyclopentadienyl ring.
4. Experimental
4.4. Synthesis
4.4.1. FcCH(CH3)P(CH2OH)2 (1)
4.1. Materials
A solution of [P(CH2OH)4]Cl (1.00 g, 4.20 mmol) in
methanol (5 ml) was deoxygenated and under nitrogen
atmosphere KOH (0.24 g, 4.30 mmol) was added. The
mixture was stirred for 1 h and was added dropwise to
the solution of [FcCH(CH3)NEt2Me]+I− (0.60 g, 1.40
mmol) in methanol (10 ml) under nitrogen with stirring.
The reaction mixture was refluxed for 24 h and the sol-
vent was removed under vacuum. To the precipitate ob-
tained, water (3 ml), Et2O (10 ml) and Et3N (3 ml) were
added and stirred for 1 h. The aqueous layer was ex-
tracted with Et2O (15 ml) and both the extracts were
washed with water (3×5 ml), dried over anhydrous
sodium sulfate and filtered. Removal of Et2O under re-
duced pressure yielded a viscous orange liquid, which
was characterized as FcCH(CH3)P(CH2OH)2 (1) (0.25 g,
60%). IR (cm−1): 3340vs (Br), 3060s, 2960s, 2920s,
1440s, 1360s, 1100s, 1050s, 1000vs, 890w, 865w and 810s
(neat); 1H-NMR (CDCl3): l 1.49 (dd, C5H4CHCH3,
3H), 3.29 (m, C5H4CHCH3, 1H) and 3.86–4.33 (m, CA
H, CB H, CD H, PCH2, 13H); 13C{1H}-NMR (CDCl3): l
17.13 (d, C5H4CHCH3), 21.87 (d, C5H4CHCH3), 60.66
(t, PCH2), 65.55, 67.00 (CA), 67.45, 67.85 (CB), 68.41
(CD) and 91.72 (CC); 31P{1H}-NMR (CDCl3): l −4.76;
(MS) EI: m/e (frag-ment) intensity: 306 [M+] 10, 276
[M+−CH2O] 50, 246 [M+−2CH2O] 70 and 213
[FcCH(CH3)] 100.
Acrylonitrile, morpholine, acetic anhydride, diethyl-
amine, and triethylamine (E. Merck) were dried and dis-
tilled
prior
to
use.
Tetrakis(hydroxymethyl)-
phosphonium chloride (80% w/w aqueous solution),
methyl iodide, ferrocene, dichlorophenyl phosphine
(Fluka) and 1,3 dichloro-1,1,3,3-tetramethyl disiloxane
(Lancaster) were used as such. Acetyl ferrocene was pre-
pared by reported procedures and purified by recrystal-
lization [12]. FcCH(CH3)NEt2 was prepared by the
procedure of Kang and co-workers [8] in about 92%
yield. Methanol, ethyl acetate, diethyl ether and light
petroleum (66–68°C) were distilled and dried using stan-
dard procedures.
4.2. General procedures
A conventional vacuum line equipped with dry nitro-
gen facility and Schlenk glassware were used for all reac-
tions. Reactions were carried out under an atmosphere
of dry nitrogen wherever required. IR spectra were
recorded on a Perkin–Elmer 1320 spectrometer as Nujol
mulls or as such. 1H-, 13C-, 31P-NMR spectra were
recorded using a Jeol JNM-LA400 FT-NMR spectrome-
ter with CDCl3 as a solvent and TMS and H3PO4 as ref-

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T.V.V. Ramakrishna et al. / Journal of Organometallic Chemistry 602 (2000) 125–132
4.4.2. FcCH(CH3)P(CH2CH2CN)2 (2)
orange solid obtained was purified over silica gel using
3:2 hexane–ethyl acetate as eluant yielding orange crys-
tals, which were identified as FcCH(CH3)P(S)-
(CH2OH)2 (4) (0.33 g, 60%), m.p. 90°C. IR (cm−1):
3485s, 1270w, 1215w, 1150s, 1100s, 1020vs, 875s, 825s,
800s, 765vs, 705vs and 625vs (Nujol); 1H-NMR
(CDCl3): l 1.73 (dd, C5H4CHCH3, 3H), 2.57 (d, OH,
br, 2H), 3.22 (m, C5H4CHCH3, 1H), 3.81 (m, PCH2,
4H) and 4.13–4.25 (m, CA H, CB H, CD H, 9H);
13C{1H}-NMR (CDCl3): l 14.17 (d, C5H4CHCH3),
32.21 (d, C5H4CHCH3), 56.75–58.67 (dd, PCH2),
66.38, 68.10 (CA), 68.38, 68.60 (CB), 68.85 (CD) and
85.05 (CC); 31P{1H}-NMR (CDCl3): l +61.84, (t);
(MS) EI: m/e (fragment) intensity: 338 [M+] 74, 308
[M+−CH2O] 32, 278 [M+−2CH2O] 20, and 213
[FcCH(CH3)] 100; Anal. Calc. for C14H19O2FePS: C,
49.72; H, 5.66. Found: C, 49.64; H, 5.69%.
Compound 1 (0.50 g, 1.63 mmol) was dissolved in
methanol (25 ml) and acrylonitrile (0.43 g, 8.10 mmol)
was added. The solution was stirred for 5 h at room
temperature (r.t.) and the solvent was removed in vac-
uum. The semi-solid obtained was purified by column
chromatography over silica gel using 2:3 hexane–ethyl
acetate as eluant under nitrogen, yielding a viscous
orange
liquid,
which
was
characterized
as
FcCH(CH3)P(CH2CH2CN)2 (2) (0.37 g, 65%). IR
(cm−1): 2985s, 2960s, 2920s, 2225s, 1450s, 1420vs,
1360w, 1315w, 1210w, 1150w, 1100vs, 1050s, 1020s,
1
1000s, 895s, 810vs and 720w (neat); H-NMR (CDCl3):
l 1.38–1.80 (m, C5H4CHCH3, CH2CN, 7H), 2.04–2.64
(m, C5H4CH, PCH2, 5H) and 3.94–4.22 (m, CA H,, CB
H, CD H, 9H); 13C{1H}-NMR (CDCl3): l 14.73 (dd,
PCH2), 17.32 (d, C5H4CHCH3), 20.09 (dd, CH2CN),
30.95 (d, C5H4CH), 65.44, 67.51 (CA), 67.62, 67.77
(CB), 68.58 (CD), 89.90 (CC) and 119.24 (CN); 31P{1H}-
NMR (CDCl3): l −7.31; (MS) EI: m/e (fragment)
intensity: 352 [M+] 30, 213 [FcCH(CH3)] 100, 186
(CpFeC5H5) 30 and 121 (CpFe) 68; Anal. Calc. for
C18H21N2PFe: C, 61.38; H, 6.01; N, 7.9. Found: C,
61.45; H, 5.91; N, 8.00%.
4.4.5. FcCH(CH3)P(S)(CH2CH2CN)2 (5)
Compound 2 (0.21 g, 0.60 mmol) and elemental
sulfur (0.04 g, 1.25 mmol) were reacted as given for the
preparation of 4 to give FcCH(CH3) P(S)-(CH2-
CH2CN)2 (5) (0.14 g, 64%), m.p. 143°C. IR (cm−1):
2220s, 1225w, 1270w, 1220s, 1160s, 1100s, 1150s,
1020vs, 1000s, 1080w, 950s, 900s, 850w, 815vs, 780s,
4.4.3. FcCH(CH3)P[CH2(NC4H8O)]2 (3)
1
735s, 685w, and 620w (Nujol); H-NMR (CDCl3): l
Compound 1 (0.30 g, 0.98 mmol) was dissolved in
methanol (20 ml) and morpholine (0.42 g, 4.82 mmol)
was added and stirred for 5 h. After removing the
solvent under vacuum, the residue obtained was
purified under nitrogen by column chromatography
over silica gel using 24:1 dichloromethane–methanol as
eluant, yielding an orange liquid, which was character-
ized as FcCH(CH3)P[CH2(NC4H8O)]2 (3) (0.30 g, 70%).
IR (cm−1): 3080w, 2850s, 2800s, 1440s, 1360w, 1280s,
1250w, 1200w, 1115vs, 1065w, 1005s, 895w, 855s, 810w
1.80–2.23 (m, C5H4CHCH3, CH2CN, 7H), 2.45–2.71
(m, PCH2, 4H), 3.05 (m, C5H4CHCH3, 1H),4.15–4.31
(m, CA H, CB H, CD H, 9H); 13C{1H}-NMR (CDCl3):
l 11.27 (d, PCH2), 14.69 (C5H4CHCH3), 23.64 (d,
CH2CN), 37.73 (d, C5H4CH), 66.13, 68.56 (CA), 68.84,
68.93 (CB), 69.06 (CD), 84.82 (CC) and 118.64 (d, CN);
31P{1H}-NMR (CDCl3):
l
+60.14; ESMS, cone
voltage 20 V: m/z 383.9 [M+H]+; Anal. Calc. for
C18H21N2FePS: C, 56.26; H, 5.51; N, 7.29. Found: C,
56.22; H, 5.59; N, 7.35%.
and 725w (neat); 1H-NMR (CDCl3):
l
1.57
(dd, C5H4CHCH3, 3H), 2.05–2.65 (m, CHCH3,
PCH2NCH2, 13H), 3.61–3.68 (m, CH2O, 8H) and
3.93–4.19 (m, CA H, CB H, CD H, 9H); 13C{1H}-NMR
4.4.6. FcCH(CH3)P(S)(CH2NC4H8O)2 (6)
Compound 3 (0.33 g, 0.74 mmol) and elemental
sulfur (0.05 g, 1.56 mmol) were reacted as given for
compound 4 to yield FcCH(CH3)P(S)(CH2NC4H8O)2
(6) (0.21 g, 58%), m.p. 105°C. IR (Nujol) (cm−1):
1290s, 1220vs, 1115w, 1095w, 1080w, 1005s, 895vw,
855vs, 830s, 805s, 780s, 735w, 715w, 700w and 640s;
1H-NMR (CDCl3): l 1.74 (dd, C5H4CHCH3, 3H),
2.48–2.98 (PCH2NCH2, m, 12H), 3.07 (m,
C5H4CHCH3, 1H), 3.66 (m, OCH2, 8H), 4.15–4.24 (m,
CA H, CB H, CD H, 9H); 13C{1H}-NMR (CDCl3): l
15.16 (C5H4CHCH3), 34.31 (d, C5H4CHCH3), 56.00
(dd, NCH2), 56.93 (dd, PCH2), 66.91 (CH2O), 67.35
(CB), 68.16 (CA), 68.75 (CD) and 86.47 (CC); 31P{1H}-
NMR (CDCl3): l +53.78; ESMS, cone voltage 20 V:
m/z 477 [M+H]+; Anal. Calc. for C22H33N2O2FePS:
C, 55.47; H, 7.98; N, 5.88. Found: C, 55.50; H, 8.10; N,
5.91%.
(CDCl3):
l
18.04 (d, C5H4CHCH3), 29.29 (d,
C5H4CHCH3), 54.84 (dd, NCH2CH2O), 56.70 (dd,
CH2P), 65.90, 66.63 (CA), 66.84 (NCH2CH2O), 67.62,
68.37 (CD) and 90.76 (CC); 31P{1H}-NMR (CDCl3): l
−37.77, (d); (MS) EI: m/e (fragment) intensity: 444
[M+] 40, 345 [M+−C4H8ONCH] 20, 231
[P(CH2C4H8ON)2] 50, 213 [FcCH(CH3)] 100 and 186
(CpFeC5H5) 22; Anal. Calc. for C22H33N2O2FeP: C,
59.47; H, 7.49; N, 7.28. Found: C, 59.40; H, 7.35; N,
7.55%.
4.4.4. FcCH(CH3)P(S)(CH2OH)2 (4)
Compound 1 (0.50 g, 1.63 mmol) and elemental
sulfur (0.21 g, 6.55 mmol) were dissolved in toluene (25
ml) with methanol (5 ml). The solution was refluxed for
5 h. The solvent was removed under vacuum and the

T.V.V. Ramakrishna et al. / Journal of Organometallic Chemistry 602 (2000) 125–132
131
of charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.
cam.ac.uk).
4.4.7. FcCH(CH3) P(S)(CH2O)2PPh (7)
Compound 4 (0.20 g, 0.59 mmol) and PhPCl2 (0.11
g, 0.61 mmol) were reacted in the presence of NEt3
(0.12 g, 1.12 mmol) in toluene (15 ml) for 15 h at r.t.
The reaction mixture was then filtered to remove
amine hydrochloride and the solvent was evaporated
under vacuum. The residue obtained was dissolved in
toluene (5 cm3) and cooled for 5 days at 4°C to yield
orange crystals of FcCH(CH3)P(S)(CH2O)2PPh (7)
(0.21 g, 80%), m.p. 133°C. IR (Nujol) (cm−1): 750m,
700vs, 675s, 800m, 875w, 915s, 950w, 980w, 1010vs,
1050w, 1100m, 1210w (Nujol); 1H-NMR (CDCl3): l
1.64 (dd, C5H4CHCH3, 3H), 3.77(m, C5H4CHCH3,
1H), 3.95–4.37 (m, CA H, CB H, CD H, PCH2, 13H),
7.33–7.45 (m, PC6H5, 5H); 13C{1H}-NMR: 13.22
(C5H4CHCH3), 28.01 (d, C5H4CHCH3), 62.60
(dd, PCH2), 67.56, 67.75 (CA), 68.51, 68.55 (CB),
68.78 (CD), 84.33 (CC), 129.19 (C16, C20), 129.27
(C17, C19), 129.76 (C18), 130.59 (C15); 31P{1H}-
NMR: +35.82 (d, PꢁS), +149.00 (d, PPh); (MS) EI:
m/e (fragment) intensity: 444 [M+] 11, 367 [M+−Ph]
27, 336 [M+−PPh] 17 and 213 [FcCH(CH3)] 100;
Anal. Calc. for C20H22O2 FeP2 S: C, 54.07; H, 4.99.
Found: C, 54.11; H, 4.90%.
Acknowledgements
A.J.E. thanks the Department of Science and Tech-
nology (DST), India and the Council of Scientific and
Industrial Research (CSIR), India for financial assis-
tance in the form of research grants. T.V.V.R. thanks
CSIR, India for a senior research fellowship.
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4.4.8. FcCH(CH3) P(S)(CH2OSiMe2)2O (8)
Compound 4 (0.20 g, 0.59 mmol) and O(SiMe2Cl)2
(0.12 g, 0.59 mmol) were reacted in the presence of
NEt3 (0.12 g, 1.12 mmol) in toluene (20 ml) for 15 h
at r.t. The mixture was filtered to remove amine hy-
drochloride and the solvent was removed under vac-
uum. The orange semi-solid obtained was dissolved in
2:3 dichloromethane–hexane and cooled at −4°C for
24 h to yield an orange crystalline product, which was
identified as FcCH(CH3)P(S)(CH2OSiMe2)2O (8) (0.24
g, 85%), m.p. 145°C. IR (cm−1): 730w, 795s, 840s,
1050w, 1085vs, 1345s; 1H-NMR: −0.5 (m, SiCH3,
12H), 1.45 (dd, C5H4CHCH3, 3H), 3.22 (m,
C5H4CHCH3, 1H), 3.69–4.07 (m, CA H, CB H, CD H,
PCH2, 13H); 13C{1H}-NMR: −2.26 (SiCH3), 13.40
(C5H4CHCH3), 28.53 (d, C5H4CHCH3), 61.1 (t,
PCH2), 67.35 (CA), 67.67 (CB), 68.78 (CD), 85.24 (CC);
31P{1H}-NMR: +53.39s; (MS) EI: m/e (fragment) in-
tensity: 468 [M+] 42, 213 [FcCH(CH3)] 100 and 121
(C5H5Fe) 50; Anal. Calc. for C18H29O3FePSSi2: C,
46.15; H, 6.24. Found: C, 46.22; H, 6.18%.
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5. Supplementary material
Crystallographic data for the structures reported in
this paper have been deposited with the Cambridge
Crystallographic Data Centre, CCDC nos. 138864,
138865 and 138866 for compounds 4, 5 and 7, respec-
tively. Copies of this information may be obtained free

132
T.V.V. Ramakrishna et al. / Journal of Organometallic Chemistry 602 (2000) 125–132
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