Preparation and structural characterization of simple and donor-substituted triorganostannyl 1′-(diphenylphosphino)-1-ferrocenecarboxylates and their P-chalcogenide derivatives

Article abstract of DOI:10.1016/j.jorganchem.2009.09.042

Triorganotin chlorides Me₃SnCl and (L^NC)Me₂SnCl (L^NC = 2-[(dimethylamino)methyl]phenyl) reacted with potassium 1′-(diphenylphosphino)-1-ferrocenecarboxylate to give the respective carboxylates, Ph₂Pfc

Full text of DOI:10.1016/j.jorganchem.2009.09.042

Journal of Organometallic Chemistry 695 (2010) 271–279
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Preparation and structural characterization of simple
and donor-substituted triorganostannyl 10-(diphenylphosphino)-1-
ferrocenecarboxylates and their P-chalcogenide derivatives
a,
a
b
*
ˇ
ˇ
ˇ
ˇ ˇ
Petr Štepnicka , Ivana Císarová , Aleš Ru˚ zicka
a Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 40 Prague 2, Czech Republic
b Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 53210 Pardubice, Czech Republic
a r t i c l e i n f o
a b s t r a c t
Triorganotin chlorides Me3SnCl and (LNC)Me2SnCl (LNC = 2-[(dimethylamino)methyl]phenyl) reacted with
potassium 10-(diphenylphosphino)-1-ferrocenecarboxylate to give the respective carboxylates,
Ph2PfcCO2SnMe3 (1) and Ph2PfcCO2SnMe2(LNC) (2; fc = ferrocene-1,10-diyl), while the analogous triphe-
nylstannyl derivative 3 resulted by condensation of Ph3SnOH with 10-(diphenylphosphino)-1-ferrocene-
carboxylic acid (Hdpf). Compounds 1 and 2 were smoothly oxidized with hydrogen peroxide or elemental
sulfur to afford the corresponding P-chalcogen derivatives (P-oxides 1a and 2a; P-sulfides 1b and 2b). All
compounds were characterized by multinuclear NMR, IR and mass spectroscopy, and the solid-state
structures of 1, 1a, 2, 2a and 2b were determined by single-crystal X-ray diffraction. In the crystal struc-
tures of 1 and 1a, the tin atoms were found with distorted trigonal bipyramidal coordination environ-
ments completed by the C@O or P@O oxygens, respectively, from adjacent molecules, which in turn
resulted in the formation of infinite linear assemblies. Tin atoms in 2, 2a, and 2b were found with trigonal
bipyramidal surrounding as well, though with the donor substituent LNC assuming one of the axial donor
sites. Compounds 2 and 2a crystallized as stoichiometric hydrates (2ꢀ1/2H2O, 2aꢀH2O), in which the water
molecules served as hydrogen bond donors for the polar groups (C@O and P@O) and thus aided the for-
mation of closed H-bonded assemblies; the structure of 2b was essentially molecular.
Article history:
Received 29 July 2009
Received in revised form 5 September 2009
Accepted 26 September 2009
Available online 5 October 2009
Keywords:
Ferrocene
Phosphinocarboxylic ligands
Organotin esters
Phosphine chalcogenides
Structure elucidation
Cyclic voltammetry
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
recently prepared trimethylstannyl (diphenylphosphino)acetate
and studied this compound in reactions with transition metal pre-
Organotin(IV) carboxylates attracted considerable attention in
both academia and industry because of their massive use as PVC
stabilizers, biocides, catalysts, and also due to their newly discov-
ered biological activity [1]. Apart from numerous application-di-
rected studies, considerable attention has been devoted also to
their structures that were shown to change broadly from simple
discrete species to complicated supramolecular networks depend-
ing on the nature of tin and carboxylate substituents, tin-to-car-
boxylate stoichiometry, and with the presence of additional
components such as donors or solvent of crystallization [2].
Stimulated by the seminal work of Ng and Zuckerman dealing
with triorganostannyl esters of phosphorus-substituted acetic
acids, Ph2P(E)CH2CO2SnR3 (E/R = O/alkyls and Ph, S/Ph) and
(Ph2P(O)CH2CO2)2SnR2 (R = Me, Ph) [3], their related phosphonium
salts [Ph3P(CH2)2CO2SnR3]X (R = Me and Ph; X = various anions)
[4], and also by the work of Cross et al. reporting the synthesis of
[CH3CH(P(O)Ph2)CO2]4ꢁnSnRn (R = Me, Ph; n = 2, 3) [5,6], we have
cursors leading to phosphinocarboxylate complexes [7]. Later, we
expanded our study towards the synthesis and structural
characterization of the related compounds possessing donor-func-
tionalized (LNC)R2Sn groups (R = Me and Ph; LNC = 2-[(dimethyl-
amino)-methyl]phenyl) [8]. This follow-up study extends our
previous work, reporting on the preparation and structural charac-
terization of simple (SnR3, R = Me and Ph) and (LNC)Me2Sn triorga-
notin carboxylates prepared from an organometallic carboxylic
acid, viz 10-(diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf)
[9,10], and their P-chalcogenide derivatives (P@O and P@S).
2. Results and discussion
2.1. Syntheses and spectroscopic characterization
Metathesis reaction between stoichiometric amounts of triorga-
notin chloride and potassium 10-(diphenylphosphino)-1-
ferrocenecarboxylate, which was generated in situ from
10-(diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf) and
potassium tert-butoxide, followed by a removal of the formed
* Corresponding author. Fax: +420 221 951 253.
ˇ
ˇ
E-mail address: stepnic@natur.cuni.cz (P. Štepnicka).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.09.042

ˇ ˇ
P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
272
KCl cleanly afforded the respective stannyl esters. The reaction
proceeded equally well with trimethyltin chloride to give the
1H and 13C{1H} NMR spectra of 1 displayed signals typical for
phosphinoferrocenyl moiety, while the 31P{1H} NMR spectrum
confirmed the presence of an uncoordinated phosphine group (dP
ꢁ17.6, cf. dP ꢁ17.6 for Hdpf [9]). The trimethylstannyl moiety gave
rise to singlets in both H-1 and C-13 spectra, flanked with diagnos-
tic 117Sn and 117Sn satellites. Ratios of the observed spin–spin
simple ester
1
as well as with dimethyl[2-((dimethyl-
amino)methyl)phenyl]tin chloride to provide the donor-functionalized
carboxylate 2 (Scheme 1). Analogous triphenyltin ester 3 was con-
veniently prepared by condensation of Hdpf with triphenyltin
hydroxide under azeotropic conditions (Scheme 1; see Refs.
[3,11]). All compounds were isolated essentially pure and in excel-
lent yields simply by evaporation. However, if appropriate, their
further purification could be effected by crystallization, albeit with
a considerable loss of the materials owing to a high solubility and
general reluctance to crystallize.
coupling
1J(119Sn, 13C)/1J(117Sn, 13C) = 1.05, were very close to the theoretical
value determined by the ratio of magnetogyric factors (
119Sn)/
117Sn) = 1.05). The 119Sn{1H} spectrum of 1 showed a single
constants,
2J(119Sn, 1H)/2J(117Sn, 1H) = 1.04
and
c(
c(
broad resonance at dSn = +130, thus suggesting the tin atom to re-
main tetracoordinate in the solution (cf. MeCO2SnMe3 in CDCl3:
dSn = 129 [12]; see also Ref. [13]). NMR spectra of ester 3 were also
not unexpected, indicating the presence of free phosphine group
and tetracoordinate tin centers (cf. MeCO2SnPh3 in CDCl3:
dSn = ꢁ121 [12]). Likewise, NMR spectra of 2 fully supported the
formulation, showing additional bands due to the LNC substituent,
while the P-31 and Sn-119 NMR spectra suggested the presence of
uncoordinated phosphine group (dP = ꢁ16.7) and pentacoordinate
tin centers (dSn = ꢁ79) in the solution [14]. In IR spectra, esters 1
PPh
PPh
2
2
1. t-BuOK
2. R SnCl
3
- t-BuOH, - KCl
Fe
Fe
O
O
C
C
OH
OSnR
3
Hdpf
1 (SnR = SnMe
)
3
3
2
and 3 displayed characteristic carboxylate bands (mas) at 1579
NC
2 (SnR = SnMe (L ))
3
and 1535 cmꢁ1, respectively (cf. mC@O 1666 cmꢁ1 for Hdpf, and
1710 cmꢁ1 for its methyl ester [9]). The corresponding Sn(LNC)Me2
ester showed the same vibration as a strong composite band at
PPh
2
1612/1601/1583 cmꢁ1
.
Ph SnOH
3
Fe
Oxidations of phosphinocarboxylic esters 1 and 2 with aqueous
hydrogen peroxide or sulfur cleanly produced the respective P-
chalcogen derivatives (Scheme 2). Whereas the former reaction
was advantageously performed in the biphasic toluene–hydrogen
peroxide system, from which the product precipitated in essen-
tially pure form, the sulfidation was accomplished by heating the
stoichiometric amounts of the respective phosphine–ester with
elemental sulfur in toluene.
- H O
2
O
(azetropic water removal)
C
OSnPh
3
3
Scheme 1. Preparation of stannyl esters 1–3 (LNC = 2-[(dimethylamino)-
methyl]phenyl).
NMR spectra of the chalcogenide derivatives confirmed the oxi-
dation to affect only the phosphine moiety. The 31P{1H} NMR sig-
nals appeared shifted to lower fields (1a/2a: dP 29.4/29.6 and 1b/
2b: dP 41.5/41.9) to positions similar to the corresponding Hdpf
derivatives (HdpfO: dP 32.9 [9] and HdpfS: dP 41.3 [15]). Besides,
the oxidation was manifested also in the 13C{1H} NMR spectra,
namely by shifts of the signals due to carbon atoms within the
phosphorus-substituted rings and, particularly, by an increase in
the JPC coupling constants [16]. On the other hand, the 119Sn{1H}
NMR response did not change much, indicating that the environ-
ments of the tin atoms remained unaltered upon oxidation. The
carboxylate bands in IR spectra of the trimethylstannyl derivatives
PPh
P(E)Ph
2
2
3
H O /toluene
2
2
Fe
Fe
or S /toluene
8
O
O
C
OSnR
C
OSnR
3
1 or 2
E
O
S
O
S
SnR
3
1a
1b
2a
2b
SnMe
SnMe
3
3
NC
NC
SnMe (L
)
)
2
SnMe (L
2
were observed slightly shifted when compared to parent 1 (mC@O
1a > 1 > 1b) and were composite. By contrast, the mC@O bands in
:
Scheme 2. Preparation of P-chalcogenide derivatives from 1 and 2.
Fig. 1. (a) A view of the repeating unit in the structure of 1 showing the atom labeling scheme (displacement ellipsoids at the 30% probability level). (b) Section of the infinite
chain in the structure of 1. Symmetry operations: A = (x, y, z), B = (x, 1/2 ꢁ y, 1/2 + z), C = (x, 1/2 ꢁ y, ꢁ1/2 + z), D = (x, y, 1 + z). The arrows indicate the propagation of the
molecular assembly.

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P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
273
Fig. 2. (a) A view of the repeating unit in the crystal structure of 1a. Displacement ellipsoids correspond to the 30% probability level. (b) Section of the infinite chain in the
structure of 1a. Symmetry operations: A = (x, y, z), B = (x ꢁ 1, y, z), and C = (x + 1, y, z).
the spectra of P-chalcogenides obtained from 2 were not split (only
shoulders being seen) and showed a different trend (2a > 2b > 2).
The solid-state structures of 1, 1a, 2, 2a, and 2b have been
established by single-crystal X-ray diffraction analysis. X-ray qual-
ity crystals were all obtained by crystallization from ethyl acetate/
hexane. Attempted crystallization of 1b afforded only few crystals
by the C@O oxygen (O10) from a molecule related by the crystallo-
graphic glide plane. The bridging carboxylate is situated between
the zig-zag distributed SnMe3 units, whereas the phosphinoferr-
ocenyl moieties are located at the exterior of the infinite coordina-
tion chain (Fig. 1). It should be noted that such bridging
coordination of the carboxylate moiety that coordinatively satu-
rates the tin centers and simultaneously leads to a formation of
supramolecular aggregates is relatively common among simple tri-
organotin carboxylates. The polymeric trimethyltin acetate [17] and
2-methoxybenzoate [18] may serve as representative examples.
The trigonal bipyramid around tin in 1 is severely distorted as
evidenced by the structural descriptor introduced by Addison,
Reedijk et al. being 0.77° [19], which can be accounted for by a pro-
trusion of the non-bonded carboxylate oxygen atom into the coor-
dination sphere of tin (Snꢀ ꢀ ꢀO1 3.133(2) Å) [20]. The carboxyl plane
is practically perpendicular to the plane defined by the tin-bound
methyl carbons (the dihedral angle of the C(24–26) and
{C11, O1, O2} planes being 86.8(3)°) and is directed in between
the Sn–C24 and Sn–C25 bonds, bisecting the C24–Sn–C25 angle
(N.B. As a consequence, the C26–Sn–O2 angle is more acute than
the C(24/25)–Sn–O2 angles). In contrast, the three C(24–26)–Sn–
O10 angles differ considerably less (by ca. 2°) and the ‘axial’ angle
O2–Sn–O10 (ca. 174°) does not depart much from the ideal 180°.
Whereas the Sn–C bond lengths in 1 vary only negligibly, the
two Sn–O distances differ by as much as 0.25 Å in accordance with
the different nature of the Sn O interactions. Accordingly, the tin
is displaced by 0.124(1) Å from the plane of its bonding methyl
groups towards the covalently attached O2.
of [Fe(g g
5-C5H4P(S)Ph2)( 5-C5H4CO2H)] [15] as a product of acci-
dental O–Sn bond cleavage.
2.2. Crystal structures of trimethylstannyl esters 1 and 1a
Solid-state structures of esters 1 and 1a are depicted in Figs. 1
and 2. Pertinent geometric data for both compounds are summa-
rized in Table 1. In the structure of 1, the tin atom is found with tri-
gonal bipyramidal environment, made up from the covalently
bonded methyl groups and carboxylate oxygen O2, and completed
Table 1
Selected geometric data for trimethylstannyl esters 1 and 1a (in Å and °).a
Parameter
1 (E = O1)
1a (E = O3)
Sn–O2
2.183(2)
2.436(2)
2.123(3)
2.115(3)
2.117(3)
174.04(6)
113.9(1)–127.7(1)
88.72(9)–95.31(9)
85.32(9)–87.41(9)
1.644(1)
1.655(1)
3.0(1)
2.135(2)
2.397(2)
2.121(3)
2.127(3)
2.113(3)
175.68(8)
116.2(1)–123.2(1)
90.5(1)–98.4(1)
84.3(1)–85.3(1)
1.639(1)
1.644(2)
4.4(2)
Sn–Eb
Sn–C24
Sn–C25
Sn–C26
O2–Sn–Ec
C–Sn–Cd
O2–Sn–Ce
E–Sn–Cf
Fe–Cg1
Fe–Cg2
\Cp1, Cp2
sg
Oxidation at phosphorus brings in another good donor atom
into the structure of 1a, which replaces the C@O oxygen in the
coordination sphere of tin [21]. Thus, individual molecules in the
crystal of 1a assemble into infinite chains featuring pentacoordi-
nate tin atoms but via coordination of the phosphoryl oxygen O3
from the molecule related by elemental translation. In this regard,
the structures of 1 and 1a parallel hydrogen bonding patterns ob-
served for Hdpf and its phosphine oxide in case of which the oxi-
dation at phosphorus resulted into the breakage of the ordinary
carboxylic dimers and formation of infinite chains via O–Hꢀ ꢀ ꢀO@P
hydrogen bonds [9].
85
124
P–C1
P–C12
P–C18
P–O3
C6–C11
C11–O1
C11–O2
O1–C11–O2
C11–O2–Sn
uh
1.820(2)
1.834(3)
1.835(3)
n.a.
1.475(3)
1.248(3)
1.290(3)
122.6(2)
118.7(1)
19.7(3)
1.766(3)
1.799(3)
1.807(3)
1.500(2)
1.490(5)
1.234(4)
1.301(4)
125.1(3)
118.4(2)
6.4(4)
The Sn–O30 bond length in 1a is similar to those reported for,
e.g., the polymeric carboxylate (EtO)2P(O)CH2CO2SnPh3 (Sn–O
a
The ring planes are defined as follows: Cp1 = C(1–5), Cp2 = C(6–10); Cg1 and
Cg2 are the respective ring centroids.
2.397(3) Å)
[22],
or
molecular
adducts
2-[C6H5C(O)]
b
Sn–O1i distance for 1, Sn–O3ii distance for 1a: i = (x, 1/2 ꢁ y, zꢁ1/2) and
C6H4CO2SnPh3ꢀPh3PO (Sn–O 2.402(3) Å) [23] and 1,2,3,4-
F4C6HCO2SnPh3ꢀPh3PO (Sn–O 2.386(3) Å) [24]. On the other hand,
both Sn–O bond in 1a are somewhat shorter than those in 1 (by
ca. 0.05 Å for the carboxylate oxygen O2 and by ca. 0.04 Å for the
other oxygen atom (O10/O3)), indicating a better donating ability
of the phosphoryl oxygen or a reduced steric congestion (the struc-
tural descriptor mentioned above being 0.87). Similarly to 1, the tin
ii = (x ꢁ 1, y, z).
c
O2–Sn–O1i angle for 1 and O2–Sn–O3ii angle for 1a.
The range of C24–Sn–C(25, 26) and C25–Sn–C26 angles.
d
e
The range of O2–Sn–C(24–26) angles.
f
The range of O1i–Sn–C(24–26) angles for 1, the range of O3ii–Sn–C(24–26)
angles for 1a.
g
Torsion angle C1–Cg1–Cg2–C6.
Dihedral angle of the Cp2 and {C11, O1, O2} planes.
h

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P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
274
atom in 1a is moved out of the plane of the methyl groups towards
O2 (by 0.196(1) Å) and the carboxyl plane is nearly perpendicular
to the equatorial plane (dihedral angle 86.5(3)°), pointing into
the C24–Sn–C26 wedge (cf. the trend in the O2–Sn–C(24–26) an-
gles: C26 ꢂ C24 > C25; the O30–Sn–C(24–26) angles differ by only
1°).
The ferrocene units in the structures of 1 and 1a do not exert
any unexpected features when compared with the structures of
the parent acids [9]. The carboxyl group in 1a retains some local-
ized bond character (
tion in the case of 1 ensues in a partial leveling of the C–O bond
lengths ( = 0.042 Å; cf. 0.129 Å for Hdpf methyl ester [9], and
<0.001 Å for [(
5-C5HMe4)2Ti(dpf-j2O,O0)] [25]). Finally, the ferro-
cene moiety in 1a assumes a more opened conformation than that
in 1 (cf. = 85° for 1, and 124° for 1a), which brings the attached
D = 0.067 Å), whereas the bridging coordina-
D
g
s
donor moieties into a position more appropriate for linear propa-
gation of the coordination array.
Fig. 5. A view of the molecular structure of 2b at the 30% probability level.
2.3. Crystal structures of the dimethyl[2-
((dimethylamino)methyl)phenyl]stannyl esters 2, 2a, and 2b
Table 2
Selected geometric data for 2, 2a and 2b (in Å and °).a
Views of the molecular structures of 2, 2a, and 2b are presented
in Figs. 3–5 and the selected geometric data are given in Table 2.
Parameter
2 (E = void)
2a (E = O3)
2b (E = S)
Sn–O2
Sn–N
2.142(2)
2.515(3)
2.121(3)
2.128(4)
2.139(3)
170.29(8)
90.4(1)–96.5(1)
75.32(9)– 93.7(1)
112.5(1)–128.8(1)
1.642(1)
1.649(1)
2.8(2)
2.147(3)
2.508(3)
2.115(4)
2.127(4)
2.135(4)
167.86(9)
88.4(1)–99.8(2)
74.7(1)–91.5(2)
114.6(2)–122.0(2)
1.644(2)
1.648(2)
3.5(2)
2.135(2)
2.498(3)
2.121(3)
2.126(4)
2.140(3)
169.41(8)
87.9(1)–99.4(1)
74.90(9)–91.5(1)
115.2(2)–125.7(1)
1.643(1)
1.642(1)
2.6(2)
Sn–C24
Sn–C25
Sn–C26
O2–Sn–N
O2–Sn–Cb
N–Sn–Cc
C–Sn–Cd
Fe–Cg1
Fe–Cg2
\Cp1, Cp2
se
143
169
160
P–C1
P–C12
P–C18
P–E
C6–C11
C11–O1
C11–O2
O1–C11–O2
C11–O2–Sn
uf
1.812(3)
1.841(3)
1.833(4)
n.a.
1.475(4)
1.234(3)
1.297(4)
124.4(3)
121.8(2)
5.2(4)
1.780(4)
1.806(4)
1.808(3)
1.497(3)
1.476(5)
1.231(5)
1.302(4)
123.4(3)
115.1(2)
11.3(4)
1.795(3)
1.817(3)
1.817(3)
1.953(1)
1.486(4)
1.232(3)
1.299(3)
124.1(2)
116.8(2)
12.2(3)
a
The ring planes are defined as follows: Cp1 = C(1–5), Cp2 = C(6–10); Cg1 and
Fig. 3. A view of the molecular structure of 2 showing the atom labeling scheme.
Displacement ellipsoids enclose the 30% probability level. For clarity, only one
orientation of the disordered CH2NMe2 arm is shown (see Section 4).
Cg2 denote the respective ring centroids.
b
The range of O2–Sn–C(24–26) angles.
The range of N–Sn–C(24–26) angles.
The range of C24–Sn–C(25, 26) and C25–Sn–C26 angles.
Torsion angle C1–Cg1–Cg2–C6.
c
d
e
f
Dihedral angle of the Cp2 and {C11, O1, O2} planes.
Whereas compound 2b resulted unsolvated, forming an essentially
molecular crystal assembly [26], its corresponding phosphine and
phosphine oxide separated as defined hydrates, 2ꢀ1/2H2O and
2aꢀH2O [27]. In the case of of 2ꢀ1/2H2O, the water molecules are
disordered over two equally populated sites lying across the crys-
tallographic inversion centers and form a closed hydrogen-bonded
array with carbonyl oxygens from two inversion-related molecules
of the ester (Fig. 6a) [28]. The crystal assembly of 2aꢀH2O (Fig. 6b) is
rather similar. However, it is generated through interactions be-
tween the phosphoryl oxygen atoms and two molecules of solvating
water [29].
Molecular parameters of 2, 2a, and 2b do not depart much from
those of the (diphenylphosphino)acetate derivatives studied ear-
lier [8]. The tin atoms are found with distorted trigonal bipyrami-
dal environments, showing unlike Sn–donor bond lengths (Sn–
N ꢂ Sn–C ꢃ Sn–O) and pronounced angular deformation due to
Fig. 4. A view of the molecular structure of 2a at the 30% probability level.

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P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
275
opened intermediate conformations in the P-chalcogenides 2a
and 2b that possess the bulkier phosphorus substituents.
3. Conclusions
Triorganostannyl 10-(diphenylphosphino)-1-ferrocenecarboxy-
lates, Ph2PfcCO2SnR3, are readily accessible via salt metathesis be-
tween potassium 10-(diphenylphosphino)-1-ferrocenecarboxylate
and the corresponding triorganotin chloride or, alternatively, from
condensation of a triorganotin hydroxide with 10-(diphenylphos-
phino)-1-ferrocenecarboxylic acid. Subsequent oxidation of the
phosphine moiety affords the corresponding phosphine–oxides
and sulfides. Compounds with simple ester groups (R = Me and
Ph) are monomeric in solution featuring tetracoordinate tin centers
whereas, in the solid state, they aggregate to increase the coordina-
tion number of tin via interactions with donor atoms from adjacent
molecules (see the crystal structures of 1 and 1a). On the other
hand, compounds bearing the LCN substituent at tin remain penta-
coordinate in both solution and the solid state. Their uncoordi-
nated polar atoms, however, may draw water molecules into
their crystals, with which they form hydrogen-bonded assemblies.
4. Experimental
4.1. Materials and methods
The preparations of 1–3 were carried out under argon atmo-
sphere. Other syntheses (oxidations) were performed in the air.
Solvents used for the syntheses were dried over the appropriate
drying agents (CH2Cl2: anhydrous potassium carbonate and tolu-
ene: potassium metal) and distilled under argon. Solvents utilized
during the work-up and in crystallizations were used without any
purification. Hdpf [9], dimethyl[2-((dimethylamino)methyl)phenyl]tin
chloride [30], and triphenyltin hydroxide [31] were prepared as de-
scribed elsewhere. Other chemicals were used as received (Fluka,
Aldrich; solvents from Lach-ner).
Fig. 6. The basic hydrogen-bonded assemblies in the crystal structures of (a)
phosphine–ester 2 and (b) phosphine oxide–ester 2a. Irrelevant hydrogens and
some phenyl ring carbons atoms were omitted for clarity. Hydrogen bond
parameters for 2: O1W–H1Wꢀ ꢀ ꢀO10, O1Wꢀ ꢀ ꢀO10 = 2.808(7) Å, angle at H1W =
156(10)°; O1W–H2Wꢀ ꢀ ꢀO1, O1Wꢀ ꢀ ꢀO1 = 2.891(7) Å, angle at H2W = 128(7)°.
Hydrogen bond parameters for 2a: O1W–H1Wꢀ ꢀ ꢀO3, O1Wꢀ ꢀ ꢀO3 = 2.806(4) Å, angle
at H1W = 164°; O1W–H2Wꢀ ꢀ ꢀO30, O1Wꢀ ꢀ ꢀO30 = 2.887(4) Å, angle at H2W = 162°.
Prime-labeled atoms related by crystallographic inversion operations.
NMR spectra were recorded with a Varian Unity Inova 400 spec-
trometer at 25 °C (1H, 399.95; 13C, 100.58; 31P, 161.90; and 119Sn,
149.14 MHz). Proton decoupled tin-119 NMR spectra were re-
corded in inverse gated broadband decoupling mode. Chemical
an interference of the second carboxylate oxygen (Snꢀ ꢀ ꢀO1 3.0–
3.2 Å in the series) and, mainly, the small size of the (LNC)Sn ring.
The aforementioned structural descriptor [19] takes the values
0.69, 0.76, and 0.73 for 2, 2a, and 2b, respectively. In all cases,
the nitrogen atom deviates from the axis of the trigonal bipyramid
around tin, being inclined towards the metallacycle (cf. N–Sn–O2
angles in Table 2, and the angles subtended by the Sn–O2/Sn–N
vectors: 9.71(6)° for 2, 12.15(7)° for 2a, and 10.59(6)° for 2b). Sim-
ilarly to simple esters, the tin atoms are displaced from the planes
of their bonding carbon atoms (C24–C26) towards O2 (by 0.154(1)
Å for 2, 0.167(1) Å for 2a, and 0.172(1) Å for 2b), which indeed cor-
responds with the bond strengths (Sn–O vs. Sn–N). The metallacy-
cles assume approximate envelope conformation with the
methylene carbon C32 projecting out of the plane of the remaining
ring atoms. The C(26–31) phenyl ring is directed away from the
ferrocene unit and almost perpendicular to the Cp2 plane (the
dihedral angles of the C(26–31) and Cp2 ring planes being
87.8(2), 83.0(2), and 78.9(2) for 2, 2a, and 2b, respectively).
The ferrocenyl moieties adopt regular geometries with negligi-
ble tilts (below 4°) and exert practically identical Fe-ring centroid
distances. The overall geometries compare well with those of Hdpf
and its respective P-chalcogenides [9,15]. In all cases, the carboxyl
groups deviate slightly from coplanarity with the planes of their
parent cyclopentadienyl ring (2 < 2a ꢂ 2b; dihedral angle max.
ca. 12°). The phosphorus substituents, not interacting with the
organotin residue, are rotated away from the carboxyl groups to
assume an ideal anti-eclipsed conformation in 2 and even more
shifts (d/ppm) are given relative to internal SiMe4
to external 85% aqueous H3PO4
31P), or to external neat SnMe4
119Sn). In addition to the standard notation of the signal multiplic-
(
13C and 1H),
(
(
ity, vt and vq are used to distinguish virtual multiplets arising from
the spin systems of the substituted cyclopentadienyl rings (AA0BB0
for C5H4CO2 and AA0BB0X for C5H4PPh2); fc = ferrocene-1,10-diyl.
(Note: Tin satellites in the 13C{1H} NMR spectra of SnMe2(LNC) es-
ters could not be all unequivocally identified and, hence, the JSnC
coupling constants are not given.) IR spectra were measured with
an FT-IR Nicolet Magna 650 spectrometer in the range 4000–
400 cmꢁ1. Electron impact (EI) and electrospray (ESI) mass spectra
were recorded with a GCT Premier (Waters) and a LTQ Orbitrap XL
(Thermo Fisher Scientific) instruments, respectively. Samples for
ESI measurements were dissolved in methanol. Composition of
the fragment ions was confirmed by a comparison of the experi-
mental isotopic distributions with the calculated patterns.
4.2. Preparation of trimethylstannyl 10-(diphenylphosphino)-1-
ferrocenecarboxylate (1)
Potassium tert-butoxide (224 mg, 2.0 mmol) was added to a
solution of 10-(diphenylphosphino)-1-ferrocenecarboxylic acid
(Hdpf; 828 mg, 2.0 mmol) in dry dichloromethane (30 mL). The
mixture was stirred at room temperature for 30 min, whereupon
it deposited potassium salt of Hdpf as a yellow orange precipitate.

ˇ ˇ
P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
276
Then, a solution of trimethyltin chloride (400 mg, 2.0 mmol) in
dichloromethane (10 mL) was introduced. The most of the precip-
itated salt quickly dissolved and some fine precipitate (KCl) began
to form. After stirring overnight, the reaction mixture was diluted
with pentane (30 mL), allowed to stand for 30 min, and filtered
through a pad of diatomaceous earth (Celite). Subsequent evapora-
tion afforded 1 as a rusty orange-brown solid. Yield: 1.078 g (93%).
The product is essentially pure. However, if necessary, it can be
crystallized from hot heptane or from ethyl acetate–hexane.
1H NMR (CDCl3): d 0.59 (s with tin satellites: 2J(119Sn, H) = 58.4,
2J(117Sn, H) = 56.0 Hz; 9H, SnMe3), 4.12 (vq, J0 = 1.8 Hz, 2H), 4.21 (vt,
J0 = 1.9 Hz, 2H), 4.35 (vt, J0 = 1.8 Hz, 2H), 4.67 (vt, J0 = 1.9 Hz, 2H) (fc);
7.28–7.39 (m, 10H, PPh2). 13C{1H} NMR (CDCl3): d ꢁ2.09 (s with tin
satellites: 1J(119Sn, C) = 400, 2J(117Sn, H) = 382 Hz; SnMe3), 71.51 (s),
72.45 (d, JPC ꢂ 2 Hz), 73.04 (d, JPC = 4 Hz) (CH of fc); 73.29 (C-CO of
fc), 74.04 (d, JPC = 14 Hz, CH of fc), 77.49 (d, 1JPC = 8 Hz, C-PPh2 of fc),
128.16 (d, JPC = 7 Hz), 128.53 (s), 133.45 (d, JPC = 20 Hz) (CH of
4.4. Preparation of triphenylstannyl 10-(diphenylphosphino)-1-
ferrocenecarboxylate (3)
Triphenylstannyl hydroxide (367 mg, 1.0 mmol) and Hdpf
(414 mg, 1.0 mmol) were suspended in dry toluene (20 mL) and
the mixture was heated under Dean-Stark trap, yielding quickly a
clear solution. After refluxing for 3 h, the reaction mixture was
cooled, filtered and evaporated under vacuum to give ester 3 in
quantitative yield. The product is essentially pure but has a strong
tendency to hold the reaction solvent.
1H NMR (CDCl3): d 4.00 (vq, J0 = 1.8 Hz, 2H), 4.13 (br vt, 2H), 4.24
(vt, J0 = 2.0 Hz, 2H), 4.77 (vt, J0 = 2.0 Hz, 2H) (fc); 7.27–7.92 (m, 25H,
PPh2 and SnPh3). 13C{1H} NMR (CDCl3): d 71.89 (s), 72.87 (d,
JPC ꢂ 1 Hz), 73.03 (d, JPC = 4 Hz), 74.05 (d, JPC = 14 Hz) (CH of fc);
1
77.53 (d, JPC = 9 Hz, C-PPh2 of fc), 128.13 (d, JPC = 7 Hz, CH of
PPh2), 128.52 (s, CH of PPh2), 128.84 (s with Sn satellites:
JSnC = 64 Hz, CH of SnPh3), 130.06 (s with Sn satellites: JSnC = 13 Hz,
CH of SnPh3), 133.41 (d, JPC = 20 Hz, CH of PPh2), 136.97 (s with Sn
satellites: JSnC = 48 Hz, CH of SnPh3), 138.64 (d, 1JPC = 10 Hz, Cipso of
PPh2), 138.64 (s, Cipso of SnPh3; Sn satellites not found), 177.78 (br
s, C@O). The resonance due C-CO of fc was not observed. 31P{1H}
NMR (CDCl3): d ꢁ17.3 (s). 119Sn{1H} NMR (CDCl3): d ꢁ115.0 (s).
1
PPh2); 138.68 (d, JPC = 10 Hz, Cipso of PPh2), 176.28 (s, C@O).
31P{1H} NMR (CDCl3): d ꢁ17.6 (s). 119Sn{1H} NMR (CDCl3): d 130.0
(s). IR (Nujol):
m 1579 vs (with a shoulder), 1337 s, 1183 s,
1159 m, 1093 w, 1068 w, 1027 s, 998 w, 921 w, 889 w, 834 m,
826 m, 786 br s, 753 m, 738 m, 702 w, 695 s, 633 w, 610 m, 594
w, 575 m, 552 m, 525 m, 511 w, 502 m, 487 s, 457 w, 449 m cmꢁ1
.
IR (Nujol): m 1535 s br, 1317 s br, 1193 m, 1160 s, 1096 w,
MS (ESI+): 579 ([M+H]+), 601 ([M+Na]+), 617 ([M+K]+), 741
([M+SnMe3]+). HR MS (ESI+) calc. for C26H2856FeO2P120Sn
([M+H]+): 579.0193, found: 579.0194. Anal. Calc. for
C26H27FeO2PSn: C, 54.12; H, 4.72. Found: C, 54.15; H, 4.73%.
1076 m, 1026 s, 997 m, 922 m, 834 m, 817 m, 788 m, 729 vs, 696
vs, 679 w, 568 w, 503 s br, 449 s cmꢁ1. MS (EI+): m/z (relative abun-
dance) 764 (28, M+ꢀ), 735 (36), 687 (19, [MꢁPh]+), 659 (100,
[MꢁPhꢁCO]+), 414 (97, Hdpf+ꢀ), 370 (27, FcPPhþ2 ꢀ), 321 (59,
[Ph2PC5H4FeO]+). HR MS (EI+) calc. for C41H3356FeO2P120Sn (M+ꢀ):
764.0590, found: 764.0599.
4.3. Preparation of dimethyl[2-((dimethylamino)methyl)phenyl]stannyl
10-(diphenylphosphino)-1-ferrocenecarboxylate (2)
4.5. Preparation of trimethylstannyl 10-(diphenylphosphinoyl)-1-
ferrocenecarboxylate (1a)
Potassium tert-butoxide (112 mg, 1.0 mmol) was added to a
solution of Hdpf (414 mg, 1.0 mmol) in dry dichloromethane
(15 mL). The resulting mixture was sonicated for 5 min and then
stirred for 30 min. To the suspension of the in situ formed carbox-
Compound 1 (57.5 mg, 0.10 mmol) was dissolved in warm tolu-
ene (5 mL). After cooling to room temperature, 30% aqueous hydro-
gen peroxide (3 drops) was added and the heterogeneous mixture
was vigorously stirred for 2 days. The precipitated product was fil-
tered off, washed with water and pentane, and dried under vacuum
to give 1a as an orange solid. Yield: 48 mg (81%).
ylate salt (Kdpf),
a
solution of dimethyl[2-((dimethyl-
amino)methyl)phenyl]tin chloride (319 mg, 1.0 mmol) in
dichloromethane (10 mL) was introduced. The precipitated salt
dissolved to give a cloudy orange solution, which was stirred for
20 h at room temperature and then diluted with pentane
(25 mL). The resulting mixture was allowed to stand for 30 min
and filtered through diatomaceous earth (Celite). The filtrate was
evaporated and the residue dried under vacuum to afford 2 as an
orange glassy solid. Yield: 0.632 g (91%).
1H NMR (CDCl3): d 0.58 (s with tin satellites: 2J(119Sn, H) = 58.7,
2J(117Sn, H) = 56.3 Hz; 9H, SnMe3), 4.42 (m, 4H), 4.45 (br m, 2H),
4.73 (br s, 2H) (fc); 7.42–7.71 (m, 10 H, PPh2). 13C{1H} NMR
(CDCl3):
d
ꢁ2.03 (s, SnMe3), 71.95 (s), 73.00 (s), 73.38 (d,
JPC = 12 Hz), 74.20 (d, JPC = 10 Hz) (CH of fc); 128.28 (d, JPC = 13 Hz),
131.41 (d, JPC = 10 Hz), 131.65 (d, JPC = 2 Hz) (CH of P(O)Ph2);
133.98 (br d, 1JPC ꢂ 110 Hz, Cipso of P(O)Ph2), 175.8 (br s, C@O). Res-
onances due to ferrocene Cipso were not found due to overlaps or
broadening. 31P{1H} NMR (CDCl3): d 29.4 (s). 119Sn{1H} NMR
1H NMR (CDCl3): d 0.69 (s with tin satellites: 2J(119Sn, H) = 67.1,
2J(117Sn, H) = 62.9 Hz; 6H, SnMe2), 2.30 (s, 6H, NMe2), 3.61 (s with
unresolved tin satellites, 2H, NCH2), 4.14–4.17 (m, 4H), 4.41 (vt,
J0 = 1.8 Hz, 2H), 4.71 (vt, J0 = 1.8 Hz, 2H) (fc); 7.08–8.17 (m, 14 H,
C6H4 + PPh2). 13C{1H} NMR (CDCl3): d ꢁ2.91 (s with tin satellites:
1J(119Sn, C) = 541, 2J(117Sn, H) = 513 Hz; SnMe2), 45.27 (s, NMe2),
65.05 (s, NCH2), 71.27 (s), 71.74 (s), 73.05 (d, JPC = 4 Hz), 73.81 (d,
JPC = 15 Hz) (CH of fc); 126.66 (s, CH of C6H4), 127.81 (s, CH of
C6H4), 128.10 (d, JPC = 7 Hz, CH of PPh2), 128.42 (s, CH of PPh2),
129.08 (CH of C6H4), 133.46 (d, JPC = 20 Hz, CH of PPh2), 137.58
(CDCl3): d 132.1 (s). IR (Nujol):
m 3524 br w, 3200 br w, 1614 vs,
1590 vs, 1331 vs, 1308 m, 1197 s, 1183 vs, 1165 vs, 1119 m,
1100 m, 1071 w, 1058 w, 1040 w, 1028 s, 997 w, 922 w, 935 m,
824 m, 800 m, 777 s, 754 m, 740 m, 724 s, 704 s, 696 m, 633 w,
617 w, 569 vs, 546 m, 529 s, 508 s, 501 m, 484 m, 448 m cmꢁ1
.
MS (ESI+): 595 ([M+H]+), 617 ([M+Na]+), 757 ([M+SnMe3]+). HR
MS (ESI+) calc. for C26H2756FeO3P120SnNa ([M+Na]+): 616.9961,
found: 616.9971.
1
(CH of C6H4), 139.03 (d, JPC = 10 Hz, Cipso of PPh2), 141.70 (s, Cipso
of C6H4), 142.50 (s, Cipso of C6H4), 175.26 (s, C@O). The Cipso of fc
were not found. 31P{1H} NMR (CDCl3): d ꢁ16.7 (s). 119Sn{1H}
4.6. Preparation of trimethylstannyl 10-(diphenylthiophosphoryl)-1-
ferrocenecarboxylate (1b)
NMR (CDCl3): d ꢁ79.0 (s). IR (Nujol):
m
3520 w, 1707 w, 1612 s,
1601 s, 1583 m, 1349 m, 1326 vs, 1180 m, 1158 m, 1096 w,
1031 m, 1025 m, 1008 w, 979 w, 918 w, 832 s, 798 s, 774 s, 746
vs, 700vs, 633w, 609 w, 578 m, 543 m, 517 m, 508 s, 491 s,
467 m, 450 m, 421 w cmꢁ1. MS (EI+): m/z (relative abundance)
713 ([M+O]+ꢀ), 697 (20, M+ꢀ), 682 (40, [MꢁMe]+), 654 (7), 414 (19,
Hdpf+ꢀ), 284 (100, [SnMe2(LNC)]+). HR MS (EI+) calc. for C34H3656Fe-
NO2P120Sn (M+ꢀ): 697.0855, found: 697.0859.
Compound
1 (57.5 mg, 0.10 mmol) and elemental sulfur
(3.5 mg, 0.11 mmol) were dissolved in dry toluene (5 mL). The
mixture was heated at reflux for 3 h and then allowed to stand at
room temperature for 24 h. The reaction solution was treated with
a little charcoal, filtered, and evaporated under vacuum to afford
1b as an orange solid. Yield: 60 mg (81%).

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P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
277
1H NMR (CDCl3): d 0.59 (s with tin satellites: 2J(119Sn, H) = 57.0,
2J(117Sn, H) = 55.9 Hz; 9H, SnMe3), 4.36 (vt, J0 = 2.0 Hz, 2H), 4.45
(vq, J0 = 1.8 Hz, 2H), 4.49 (vq, J0 = 2.0 Hz, 2H), 4.67 (vt, J0 = 2.0 Hz,
2H) (fc); 7.39-7.75 (m, 10 H, PPh2). 13C{1H} NMR (CDCl3): d
ꢁ2.17 (s, SnMe3), 72.12 (s), 73.64 (s), 74.00 (d, JPC = 12 Hz), 74.27
(d, JPC = 10 Hz) (CH of fc); 128.24 (d, JPC = 12 Hz), 131.29 (d,
JPC = 3 Hz), 131.59 (d, JPC = 11 Hz) (CH of P(S)Ph2); 134.35 (d,
1JPC = 87 Hz, Cipso of P(S)Ph2), 175.72 (s, C@O). The signals due to
ferrocene Cipso were not found. 31P{1H} NMR (CDCl3): d +41.5 (s).
72.31 (s), 73.04 (d, JPC = 13 Hz) (3 ꢄ CH of fc); 73.28 (d,
1JPC = 117 Hz, C-PPh2 of fc), 74.17 (d, JPC = 10 Hz, CH of fc), 77.74
(C-CO of fc), 126.71 (s, CH of C6H4), 127.84 (s, CH of C6H4),
128.22 (d, JPC = 12 Hz, CH of P(O)Ph2), 129.16 (CH of C6H4),
131.42 (d, JPC = 10 Hz, CH of P(O)Ph2), 131.54 (d, JPC = 2 Hz, CH of
1
P(O)Ph2), 134.16 (d, JPC = 107 Hz, Cipso of P(O)Ph2), 137.42 (CH of
C6H4), 141.54 (s, Cipso of C6H4), 142.47 (s, Cipso of C6H4), 174.79 (s,
C@O). 31P{1H} NMR (CDCl3): d 29.6 (s). 119Sn{1H} NMR (CDCl3): d
ꢁ78.5 (s). IR (Nujol):
m 3510 m, 3435 w, 1715 w, 1629 vs, 1321
119Sn{1H} NMR (CDCl3): d 133.9 (s). IR (Nujol):
m
1572 vs, 1557
vs, 1184 s, 1177 s, 1156 s, 1122 m, 1101 m, 1075 w, 1031 m,
1010 w, 839 m, 789 m, 753 s, 726 s, 708 s, 697 m, 570 s, 550 w,
527 s, 507 s, 488 m, 478 w cmꢁ1. MS (ESI+): m/z 736 ([M+Na]+),
714 ([M+H]+), 453 ([HdpfO+Na]+), 284 (Me2LNCSn+). HR MS (ESI)
calc. for C34H3656FeNO3P120Sn ([M+Na]+): 736.0696, found:
736.0720.
vs, 1339 vs, 1187 m, 1171 s, 1101 s, 1073 w, 1055 w, 1027 s, 921
w, 834 m, 795 m, 774 m, 758 m, 745 m, 719 vs, 698 m, 659 s, 615
w, 602 w, 573 m, 550 w, 540 s, 520 m, 503 s, 485 m, 458 w, 451
w cmꢁ1. MS (EI+): m/z (relative abundance) 610 (100, M+ꢀ), 595
(53,
[MꢁMe]+),
518
(30,
[MꢁC5H4CO]+),
503
(59,
[MꢁC5H4COꢁMe]+), 473 (30, [MꢁC5H4COꢁ3Me]+), 466 (29,
HdpfS+ꢀ), 354 (33), 337 (72, [Ph2PC5H4FeS]+), 321 (65,
[Ph2PC5H4FeO]+). HR MS (ESI+) calc. for C26H2756FeO2PS120Sn
(M+ꢀ): 609.9841, found: 609.9837.
4.8. Preparation of dimethyl[2-((dimethylamino)methyl)phenyl]stannyl
10-(diphenylthiophosphoryl)-1-ferrocenecarboxylate (2b)
Ester 2 (70 mg, 0.10 mmol) and sulfur (3.5 mg, 0.11 mmol) were
dissolved in toluene (5 mL) and the solution was heated to 75 °C
for 18 h (temperature in bath). After cooling to room temperature,
the solution was treated with little charcoal, filtered and evapo-
rated under vacuum, leaving 2b as a microcrystalline, rusty orange
solid. Yield: 68 mg (96%).
4.7. Preparation of dimethyl[2-((dimethylamino)methyl)
phenyl]stannyl 10-(diphenylphosphinoyl)-1-ferrocenecarboxylate (2a)
Aqueous hydrogen peroxide (3 drops of 30% solution) was
added to a solution of ester 2 (70 mg, 0.10 mmol) in toluene
(3 mL), and the resulting mixture was vigorously stirred overnight.
The separated product was filtered off, washed thoroughly with
diethyl ether and pentane, and dried under vacuum to give 2a as
a fine ochre brown solid. Yield: 59 mg (83%).
1H NMR (CDCl3): d 0.67 (s with tin satellites: 2J(119Sn, H) = 68.6,
2J(117Sn, H) = 65.7 Hz; 6H, SnMe2), 2.30 (s, 6H, NMe2), 3.61 (s with
unresolved tin satellites, 2H, NCH2), 4.34 (vt, J0 = 1.9 Hz, 2H), 4.49–
4.53 (m, 4H), 4.70 (vt, J0 = 1.9 Hz, 2H) (fc); 7.09–8.10 (m, 14H,
C6H4 + PPh2). 13C{1H} NMR (CDCl3): d ꢁ2.94 (s, SnMe2), 45.27 (s,
NMe2), 65.03 (s, NCH2), 71.84 (s), 73.07 (s), 73.67 (d, JPC = 12 Hz),
1H NMR (CDCl3): d 0.67 (s with tin satellites: 2J(119Sn, H) = 68.6,
2J(117Sn, H) = 65.6 Hz; 6H, SnMe2), 2.30 (s, 6H, NMe2), 3.61 (s with
unresolved tin satellites, 2H, NCH2), 4.36 (vt, J0 = 1.9 Hz, 2H), 4.45
(vt, J0 = 1.8 Hz, 2H), 4.49 (vt, J0 = 1.8 Hz, 2H), 4.76 (vt, J0 = 1.9 Hz,
2H) (fc); 7.08–8.09 (m, 14H, C6H4 + PPh2). 13C{1H} NMR (CDCl3):
d ꢁ2.96 (s, SnMe2), 45.28 (s, NMe2), 65.04 (s, NCH2), 71.76 (s),
1
74.36 (d, JPC = 10 Hz) (CH of fc); 75.53 (d, JPC = 98 Hz, C-PPh2 of
fc), 77.68 (C-CO of fc), 126.70 (s, CH of C6H4), 127.85 (s, CH of
C6H4), 128.20 (d, JPC = 12 Hz, CH of P(S)Ph2), 129.15 (CH of C6H4),
131.18 (d, JPC = 3 Hz, CH of P(S)Ph2), 131.60 (d, JPC = 10 Hz, CH of
Table 3
Crystallographic data, data collection and structure refinement parameters for 1, 1a, 2, 2a and 2b.a
Compound
1
1a
2
2a
2b
Formula
C28H31FeO3PSnf
621.04
C26H27FeO3PSn
592.99
C34H37FeNO2.5PSnh
705.16
C34H38FeNO4PSni
730.16
C34H36FeNO2PSSn
728.21
M (g molꢁ1
)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Monoclinic
P21=c (no. 14)
12.3700(2)
24.3300(4)
9.9635(2)
Orthorhombic
P212121 (no. 19)g
10.8321(2)
13.3435(2)
17.4506(2)
Triclinic
Triclinic
Triclinic
ꢀ
ꢀ
ꢀ
P1 (no. 2)
P1 (no. 2)
P1 (no. 2)
8.5686(3)
13.4231(3)
13.4231(3)
83.596(2)
85.593(2)
73.454(2)
1541.02(8)
2
1.520
1.366
0.714–0.899
31 654
5.65
9.3792(4)
12.0247(3)
15.4844(7)
67.789(2)
78.636(2)
79.076(2)
1572.3(1)
2
1.542
1.345
0.835–0.961
26 147
6.09
9.1011(2)
12.3486(3)
15.3094(3)
71.704(1)
79.589(1)
78.762(2)
1589.01(6)
2
1.522
1.390
0.781–0.904
29 102
5.14
a
(°)
b (°)
101.633(1)
c
(°)
V (Å3)
2937.04(9)
4
1.404
2522.28(7)
4
1.562
Z
Dcalc (g mLꢁ1
)
l
(Mo K
a
) [mmꢁ1
]
1.423
1.653
T-rangeb
0.549–0.680
41 294
5.06
0.636–0.858
43 744
3.83
Diffractions total
c
Rint (%)
Unique diffractions
6722
5634
3.11
4.19, 7.80
0.89, ꢁ0.63
5779
5506
2.54
2.82, 5.17
0.30, ꢁ0.52
7101
5553
3.54
5.84, 7.63
0.93, ꢁ1.00
6183
4783
3.71
6.09, 7.89
0.56, ꢁ0.78
7030
5535
3.36
5.26, 7.74
0.91, ꢁ0.79
Observed diffractionsd
R (Observed diffractions)d,e (%)
R, wR (all diffractions)e (%)
Dq )
(e Åꢁ3
a
b
c
d
e
f
Common details: T = 150(2) K.
The range of transmission coefficients.
P
P
Rint
¼
P
jFo2 ꢁ Fo2 ðmeanÞj= F2o, where F2o ðmeanÞ is the average intensity for symmetry-equivalent diffractions.
Diffractions with Io > 2
r
(Io).
P
P
P
2
2 1=2
R ¼ kFoj ꢁ jFck= Fo; wR ¼ ½ fwðF2o ꢁ Fc2Þ g= wðFo2Þ ꢅ
C25H27FeO2PSnꢀ1/2C4H8O2 (see Section 4).
Flack’s enantiomorph parameter: ꢁ0.01(2).
C34H36FeNO2PSnꢀ1/2H2O.
.
g
h
i
C34H36FeNO3PSnꢀH2O.

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P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
278
1
P(S)Ph2), 134.55 (d, JPC = 87 Hz, Cipso of P(S)Ph2), 137.50 (CH of
C6H4), 141.53 (s, Cipso of C6H4), 142.46 (s, Cipso of C6H4), 174.67 (s,
C@O). 31P{1H} NMR (CDCl3): d 41.9 (s). 119Sn{1H} NMR (CDCl3): d
be obtained free of charge from The Cambridge 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.2009.09.042.
ꢁ78.4 (s). IR (Nujol):
m 1624 vs, 1323 vs, 1171 s, 1103 s, 1051 w,
1024 m, 1010 w, 977 w, 920 w, 824 m, 805 w, 788 m, 750 s, 716
s, 699 m, 695 m, 653 s, 628 w, 615 w, 571 w, 543 s, 514 s,
503 m, 485 s, 467 w, 456 w, 427 w, 415 w cmꢁ1. MS (ESI+): m/z
752 ([M+Na]+), 469 ([HdpfS+Na]+), 284 (Me2LNCSn+). HR MS (ESI)
calc. for C34H3656FeNO2PS120Sn ([M+Na]+): 752.0468, found:
752.0492.
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5. X-ray crystallography
Crystals used for single-crystal X-ray diffraction analysis were
all grown by crystallization from ethyl acetate-hexane (1: or-
ange-brown prism, 0.16 ꢄ 0.50 ꢄ 0.62 mm3, 1a: orange-brown
plate, 0.08 ꢄ 0.25 ꢄ 0.25 mm3; 2: orange-brown plate, 0.13 ꢄ
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cluded in the diffractometer software. The ranges of the
transmission factors are given in Table 3.
ˇ
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[Co(
a
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g
Ref. [34]). The non-hydrogen atoms were refined with anisotropic
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Holecek, J. Organomet. Chem. 691 (2006) 2631, and references cited therein.
The crystals of 1 contained disordered molecules of ethyl ace-
tate. Contribution of the solvent molecules to the scattering was
numerically removed by SQUEEZE routine as incorporated in the
PLATON program [35]. Within the 2 ꢄ 372 Å3 of void space per the
unit cell, a total of 162 electrons were calculated, compared to
the 176 electrons predicted for the presence of two molecules of
ethyl acetate. In the crystal of 2, the methyl and methylene groups
in the CH2NMe2 arm adopt two positions while the phenyl ring
(C(26–31)) and the nitrogen atoms act as pivots (statistic disorder).
The disordered methyl and methyl groups were refined over two
positions with the same occupancies (50:50) and anisotropic dis-
placement parameters.
Relevant crystallographic data are given in Table 3. Geometric
parameters and structural drawings were obtained by using a re-
cent version of the PLATON program [35]. All values are presented
relative to their estimated standard deviations given with one dec-
imal. Those concerning atoms in constrained positions (hydrogens)
are given without estimated standard deviations.
ˇ
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[14] J. Chalupa, K. Handlír, Z. Padelková, M. Vejcová, V. Buchta, R. Jirásko, A.
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Ru˚ zicka, Appl. Organomet. Chem. 22 (2008) 308.
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Sn–O 2.381(4) Å at 200 K);
(b) H. Chih, B.R. Penfold, J. Cryst. Mol. Struct. 3 (1973) 285 (Sn–O 2.205(3), Sn–
O 2.391(4) Å at room temperature).
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[20] The C–O and C@O distances observed for 1 and 1a correspond well with those
reported for the related esters obtained from non-functionalized
ferrocenecarboxylic acid, FcCO2Sn(CH2C6H4X-2)3 (Fc = ferrocenyl, X = Cl and
Br; refcodes TAFNYI and ADUSIC in the Cambridge Structural Database).
However, these reference structures display distinctly shorter Sn–O and Snꢀ ꢀ ꢀO
distances (ca. 2.07 and 2.68 Å, respectively).
[21] The ‘liberated’ C@O oxygen in 1a takes part in a soft intramolecular hydrogen
bonding (C20–H20ꢀ ꢀ ꢀO10: C20ꢀ ꢀ ꢀO10 = 3.365(5) Å, angle at H20 = 157°;
symmetry operation: 1 ꢁ x, 1/2 + y, 1/2 ꢁ z).
[22] S.W. Ng, V.G.K. Das, Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 52 (1996)
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Acknowledgements
[23] C.A.K. Diop, A. Touré, L. Diop, R. Welter, Acta Crystallogr., Sect. E: Struct. Rep.
Online 62 (2006) m3338.
[24] C. Ma, J. Sun, R. Zhang, J. Organomet. Chem. 691 (2006) 5873.
This work was financially supported by the Grant Agency of the
Czech Republic (Project No. 203/07/0468) and is a part of the long-
term research project supported by the Ministry of Education,
Youth and Sports of the Czech Republic (Project No.
MSM0021620857).
ˇ
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[25] K. Mach, J. Kubišta, I. Císarová, P. Štepnicka, Acta Crystallogr., Sect. C: Cryst.
Struct. Commun. 58 (2002) m116.
[26] An intermolecular C19–H19ꢀ ꢀ ꢀO1 contact with C19ꢀ ꢀ ꢀO1 being 3.288(4) Å
between molecules related by elemental translation along x-axis was detected.
[27] Crystallisation from dry solvents was unsuccessful starting only when some
adventitious water was present.
[28] A supportive C14–H14ꢀ ꢀ ꢀO1 contact between molecules relating by translation
along the a-axis (C14ꢀ ꢀ ꢀO1 = 3.473(4) Å) was detected.
[29] An additional C23–H23ꢀ ꢀ ꢀO1 contact between molecules relating by
translation along the a-axis (C23ꢀ ꢀ ꢀO1 = 3.242(5) Å) was detected.
Appendix A. Supplementary data
ˇ ˇ
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CCDC 742131, 742132, 742133, 742134 and 742135 contain the
supplementary crystallographic data for this paper. These data can
[31] B. Kushlefsky, I. Simmons, A. Ross, Inorg. Chem. 2 (1963) 187.

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P. Štepnicka et al. / Journal of Organometallic Chemistry 695 (2010) 271–279
279
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Diffraction Data, University of Göttingen, Göttingen, 1997.
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