New phosphathiamacrocycles containing polypypiridine units

Article abstract of DOI:10.1016/j.poly.2005.08.006

A new 2,2′-bipyridine-based phosphadithiamacrocycle: 3,3′-5-phenyl-2,8-dithia-5-phospha[9]-2,2′-bipyridinophane (L) has been synthesized by reacting 6,6′-bis(bromomethyl)-2,2′-bipyridine and dilithium 3-phenyl-3-phosphapenta-1,5-dithiolate. The phosphoryl derivative: 3,3′-5-oxo-5-phenyl-2,8-dithia-5-phospha[9]-2,2′-bipyridinophane (Lox) synthesized by direct oxidation of L at open atmosphere. Both compounds have been isolated as white solids containing different amounts of LiBr. The reaction of acetonitrile solutions of these solids with Fe(II) perchlorate gave the complexes [FeBr(L)](ClO₄) ? 2H₂O and [FeBr(Lox)](ClO₄) ? 3H₂O, which were crystallized as [FeBr(L)]Br ? H₂O and [FeBr(Lox)](ClO4)·116MeOH salts from nitromethane or methanol, respectively. Both compounds were characterized by X-ray diffraction analysis. In both cases, a distorted octahedral environment is achieved at the Fe(II), with five sites occupied by the macrocycles L and Lox and the sixth by a monodentate bromine ligand. The bond distances found in the complex cation [FeBr(Lox)]⁺ are compatible with a high-spin configuration. However, the same parameters for [FeBr(L)]⁺ and their magnetic character are only compatible with a low-spin configuration.

Full text of DOI:10.1016/j.poly.2005.08.006

Polyhedron 25 (2006) 801–808
www.elsevier.com/locate/poly
New phosphathiamacrocycles containing polypypiridine units
a,
a
a
b
c
*
´
Lluis Escriche , Jaume Casabo , Vicens Muns , Raikko Kivekas , Reijo Sillanpaa
¨ ¨
¨
a
Departmento de Qu´ımica, Universitat Auto´noma de Barcelona, Campus de Bellaterra, 08193 Cerdanyola del Valle´s, Barcelona, Spain
b
Department of Chemistry, P.O. Box 55, University of Helsinki, FIN 00014, Finland
c
Department of Chemistry, University of Jyva¨skyla¨, 40351 Jyva¨skyla¨, Finland
Received 8 June 2005; accepted 3 August 2005
Available online 30 September 2005
Abstract
A new 2,20-bipyridine-based phosphadithiamacrocycle: 3,30-5-phenyl-2,8-dithia-5-phospha[9]-2,20-bipyridinophane (L) has been
synthesized by reacting 6,60-bis(bromomethyl)-2,20-bipyridine and dilithium 3-phenyl-3-phosphapenta-1,5-dithiolate. The phos-
phoryl derivative: 3,30-5-oxo-5-phenyl-2,8-dithia-5-phospha[9]-2,20-bipyridinophane (Lox) synthesized by direct oxidation of L at
open atmosphere. Both compounds have been isolated as white solids containing different amounts of LiBr.
The reaction of acetonitrile solutions of these solids with Fe(II) perchlorate gave the complexes [FeBr(L)](ClO4) Æ 2H2O and
[FeBr(Lox)](ClO4) Æ 3H2O, which were crystallized as [FeBr(L)]Br Æ H2O and ½FeBrðLoxÞꢀðClO4Þ ꢁ 1 16 MeOH salts from nitromethane
or methanol, respectively. Both compounds were characterized by X-ray diffraction analysis. In both cases, a distorted octahedral
environment is achieved at the Fe(II), with five sites occupied by the macrocycles L and Lox and the sixth by a monodentate bro-
mine ligand. The bond distances found in the complex cation [FeBr(Lox)]+ are compatible with a high-spin configuration. However,
the same parameters for [FeBr(L)]+ and their magnetic character are only compatible with a low-spin configuration.
ꢀ 2005 Elsevier Ltd. All rights reserved.
Keywords: Phosphathiamacrocycles; Polypyridine; Iron(II) complexes
1. Introduction
trend, the interest in the chemistry of asymmetric phos-
phorus–sulfur donor ligands is mainly focused on the
phenomenon of their hemilability and their potential
use in catalytic processes [7,8]. Other possibilities are
found when these P–S donor systems are integrated in
macrocyclic systems, such as the documented ability of
their phosphoryl [9,10], and thiophosphoryl [11] deriva-
tives to interact selectively with ionic species that act as
chemical sensors for anions.
On the other hand, the introduction of heteroaromatic
subunits, such as bipyridine or 1,10-phenantroline into
the macrocyclic structures generates different families of
compounds which combine the special complexation
features of these macrocycles [12] with the well-known
photophysical, photochemical or electrochemical prop-
erties exhibited by the metal complexes of these heterocy-
cles [13]. In this context, several 1,10-phenantroline
containing polyaza and polythiamacrocycles have recently
The chemistry of macrocyclic ligands containing
phosphane groups as donor atoms has been less devel-
oped than those of their oxygen or nitrogen equivalents
[1]. This fact has been mainly attributed to the air-sensi-
tivity behavior of these compounds and the poor yields
obtained in their preparations by high-dilution or tem-
plate methods, although several high yield synthesis of
homoleptic triphosphamacrocycles have recently been
reported [2]. However, phosphathiamacrocycles seem
to be more accessible as free ligands, and several exam-
ples can be found in the literature [3–6]. As a general
*
Corresponding author. Tel.: +34935811369; fax: +34935812947.
E-mail address: lluis.escriche@uab.es (L. Escriche), jaume.casabo@
´
uab.es (J. Casabo).
0277-5387/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.08.006

802
L. Escriche et al. / Polyhedron 25 (2006) 801–808
been reported and their complexing [14], luminescent [15]
and sensing [16] properties studied.
phonium derivatives are present in the final product ob-
tained via this procedure.
1
Examples may be found of similar studies on polyaza
and polyamidamacrocycles containing 2,20-bipyridene
units [14a,17], but less information is available on mono
or polybipyridine-containing macrocycles [18], including
the softer donor atoms.
As a part of our work in this field, we report herein on
the synthesis of the new bipyridine-based phosphadithia-
macrocycle: 3,30-5-phenyl-2,8-dithia-5-phospha[9]-2,20-
bipyridinophane (L) and their phosphoryl derivative:
3,30-5-oxo-5-phenyl-2,8-dithia-5-phospha[9]-2,20-bipyri-
dinophane (Lox). The reactivity of these systems in the
presence of Fe(II) salts is also investigated. At present,
this is the first example of a phosphathmacrocycles con-
taining polypyridine units.
The H NMR spectrum displays a complex pattern
due to the high inversion barrier of the phosphane group
[23], which makes non-equivalent the geminal methylene
protons. The S–CH2-bipy protons appear as a pair of
doublets centered at 4.0 ppm (AB system), and three
groups of signals attributed to the —S–CH2–CH2–P–
methylene protons coupled with the phosphorus atom
are observed in the interval 2.4–3.1 ppm. The COSY
spectrum shows coupling between three multiplets,
which evidences that all four methylene protons and
the phosphorus atom define an ABMNX system similar
to those found in related macrocyclic molecules [24,6].
The 13C{1H} NMR spectrum shows a singlet for each
different carbon atom in the molecule, split in some cases
by the P–C coupling, thus indicating the conformational
flexibility of the ligand L. The assignation of this spec-
trum was made on the basis of the literature data for
the P–C coupling constants [25] and the observed chem-
ical shifts of related phosphane macrocycles [5b,6]. Alkyl
phosphanes are easily oxidized to their phosphoryl deriv-
atives [26] and ligand L is no exception to this behavior.
Exposing stirred chloroformic solutions of L to air yields
almost quantitatively the phosphorylic macrocycle Lox.
2. Results and discussion
The synthetic pathway leading to the ligand L (Scheme
1) starts with the bromination of the 2-amino-6-picoline,
followed by the reaction of the 2-bromo-6-picoline with
Raney-Ni to afford the 6,60-dimethyl-2,20-bipyridine,
which was finally halogenated with NBS to produce the
6,60-bis(bromomethyl)-2,20-bipyridine in an overall 10%
yield [19,20]. Subsequent cyclisation of equimolar
amounts of this dibromo derivative under high dilution
conditions with the dilithium 3-phenyl-3-phosphapenta-
1,5-dithiolate (obtained by previously reported methods
[21]) produced low yields of the required macrocycle.
The 31P{1H} NMR spectrum of L shows a single sig-
nal at ꢂ21.29 ppm, which is in the range observed for
similar dialkylarylphosphane-containing macrocyclic
molecules [2d,5b,5d,22]. No additional downfield signals
were observed, indicating that no phosphoryl or phos-
1
The patterns of the H and 13C{1H} NMR spectra of
Lox are very similar to that described for L, whereas
the 31P{1H} NMR spectrum again shows a single signal
at 37.21 ppm, which is in the expected position for a dial-
kyl aryl phosphine oxide [25,27].
The spectroscopic properties of the ligands L and
Lox, including mass spectra, were consistent with the
proposed structure; however, the elemental analyses of
the two compounds were not coincident with those cal-
culated from their empirical formulas. Taking into ac-
count that there was no spectroscopic evidence for the
presence of additional organic compounds and no insol-
uble residues remained when L and Lox were dissolved
in organic solvents, we proceeded with the study of their
complexing abilities.
The reaction of the ligands L and Lox with equimolar
amounts of hydrated Fe(ClO4)2 in a CH2Cl2–CH3CN
mixture affords red–purple microcrystalline materials
corresponding to the respective iron (II) complexes. As
in the case of the free ligands, elemental analysis of both
complexes did not fit any empirical formula derived from
simple metal to ligand to perchlorate counteranion rela-
tions. Hopefully, these complexes may easily crystallize,
producing suitable materials for X-ray diffraction analy-
sis, which could reveal (Figs. 1 and 2) the presence of the
monocationic complex units [1]+ and [2]+, which contain
one ligand (L and Lox, respectively), and one bromine
atom bound to a Fe(II) atom in an octahedral environ-
ment. The presence of bromine in both compounds could
only be explained if some of the LiBr generated in the
synthesis of L is not completely removed by the purifica-
Br
N
N
i -iv
N
NH2
Br
S
v
S
S
N
N
N
N
P
Ph
O
P
Ph
vi
S
L
Lox
Scheme 1. Reagents and conditions: (i) NaNO2 1 M, Br2 and HBr
98%; (ii) Ni-Raney, toluene; (iii) H2O, 40 ꢁC, 2 h; (iv) NBS, CCl4, 3 h;
(v) Ph–P(–CH2–CH2–SꢂLi+)2, thf; (vi) stirring at open atmosphere,
24 h.

L. Escriche et al. / Polyhedron 25 (2006) 801–808
803
showing a different degree of solubility in organic sol-
vents. The [1]+ perchlorate salt was sufficiently soluble
in acetonitrile to be fully studied by NMR spectroscopy,
a fact which reflects diamagnetic character, whereas the
low solubility of [2]+ perchlorate salt prevented further
solution studies. The 31P{1H} NMR spectrum of
[1](ClO4) shows a single signal at 132.52 ppm which sug-
gests the presence of only one species in solution. These
low-field shifts are characteristic of co-ordinated phos-
phanes in fused five-membered chelate rings [28] and
several Fe(II)–triphosphamacrocyclic complexes show-
ing similar shifts in the 31P NMR spectra have recently
been reported [2a,2c]. Between 4.8 and 2.4 ppm, the
1H NMR spectrum presents the same groups of multi-
plets, corresponding to the methylene protons found in
the free ligand, but low-field shifted. However, the num-
ber of signals of the bipyridine rings increases with re-
spect to the ligand L, which reflects the loss of the
local symmetry by the effect of the co-ordination to
the metal centre.
Fig. 1. Perspective view of the complex cation [1]+ showing 30%
displacement ellipsoids. Hydrogen atoms are omitted for clarity.
The 13C{1H} NMR spectrum also shows the same
number of signals as the free ligand, but in this latter case
the most important differences are found in the region
corresponding to the methylene groups, where the pair
of doublets corresponding to the –S–CH2–CH2–P– car-
bon atoms (22.4 and 33.5 ppm) appears high and low
field displaced with respect to the L ligand (27.7 and
28.7 ppm). These data suggest that in solution the com-
plex cation [1]+ maintains its monomeric character,
which is in agreement with the well-known kinetic stabil-
ity of the low-spin octahedral Fe(II) complexes [29].
The crystal structures of the L and Lox Fe(II) com-
plexes, which crystallize as [1]Br Æ H2O and ½2ꢀðClO4Þꢁ
1 16 MeOH salts, showed the presence of the aforemen-
tioned [1]+ and [2]+ complex cations without significant
interactions with the counter-anions and the solvate
molecules. The diagrams for these complex cations are
shown in Figs. 1 and 2, respectively. Crystallographic
data for the structures are listed in Table 1; selected
bond distances and angles for [1]+ and [2]+ are summa-
rized in Tables 2 and 3, respectively.
Fig. 2. Perspective view of complex cation [2]+ showing 30%
As was mentioned above, the co-ordination geometry
at the Fe(II) atoms in both complex cations is a dis-
torted octahedron defined by the five donor atoms of
the ligands and an additional bromine atom which is
placed in a trans position with respect to the phosphorus-
phophane atom for [1]+ or to the oxygen-phosphoryl
atom for [2]+. The major distortion in both octahedral
environments is observed in the value of the S–Fe–S
bond angles (105.30(6)ꢁ and 120.99(9)ꢁ for [1]+ and
[2]+, respectively), and this can be attributed to the geo-
metric constraint imposed by the simultaneous co-
ordination of the two bipyridine nitrogen atoms and
the two thioether sulfur atoms, thus defining three
contiguous five-membered chelate rings. These four
donor atoms and the metal ion are almost coplanar in
displacement ellipsoids. Hydrogen atoms are omitted for clarity.
tion procedures used in the isolation of L and Lox. This
assumption was confirmed by the Li analysis of both
ligands using atomic emission spectrometry. The LiBr
present in the Lox ligand can be easily removed by treat-
ing its chloroformic solutions with water. However, all
the attempts made to purify L by the same or other pro-
cedures gave rise to its partial oxidation, and the separa-
tion of these L and Lox mixtures was unsuccessful.
Furthermore, all attempts to synthesize Fe(II) complexes
with the purified Lox ligand were also unsuccessful.
The complex cations [1]+ and [2]+ were initially
obtained as purple microcrystalline perchlorate salts

804
L. Escriche et al. / Polyhedron 25 (2006) 801–808
Table 1
Table 3
Crystallographic data for [1]Br Æ H2O and ½2ꢀðClO4Þ ꢁ 1 16 MeOH
Selected bond distances (A) and angles (ꢁ) for compound
˚
½2ꢀðClO4Þ ꢁ 1 16 MeOH
[1]Br Æ H2O
½2ꢀðClO4Þ ꢁ 1 16 MeOH
Br–Fe
2.4887(15)
2.107(5)
2.113(7)
2.134(7)
2.558(3)
2.579(3)
1.502(5)
Formula
C22H25Br2FeN2OPS2 C23.17H27.67BrClFeN2O6.17-
Fe–O(1)
Fe–N(2)
Fe–N(1)
Fe–S(1)
Fe–S(2)
P–O(1)
PS2
M
Crystal system
Space group
644.20
triclinic
699.11
trigonal
ꢀ
ꢀ
P1 ðno: 2Þ
R3 ðno: 148Þ
˚
a (A)
10.1594(15)
14.376(2)
9.2397(15)
92.537(15)
110.820(12)
76.067(13)
1223.0(3)
2
30.855(4)
30.855(4)
16.083(4)
90
90
120
˚
b (A)
˚
c (A)
O(1)–Fe–N(2)
O(1)–Fe–N(1)
N(2)–Fe–N(1)
O(1)–Fe–Br
N(2)–Fe–Br
N(1)–Fe–Br
O(1)–Fe–S(1)
N(2)–Fe–S(1)
N(1)–Fe–S(1)
Br–Fe–S(1)
O(1)–Fe–S(2)
N(2)–Fe–S(2)
N(1)–Fe–S(2)
Br–Fe–S(2)
S(1)–Fe–S(2)
P–O(1)–Fe
86.3(2)
84.9(2)
77.5(3)
a (ꢁ)
b (ꢁ)
c (ꢁ)
167.55(15)
102.41(8)
105.56(18)
86.00(15)
156.9(2)
80.1(2)
89.07(7)
84.55(16)
79.9(2)
155.5(2)
88.23(7)
120.99(9)
124.3(3)
3
˚
V (A )
13260(4)
18
Z
T (K)
294(2)
1.749
294(2)
1.576
Dc (g cmꢂ3
)
l (mmꢂ1
)
4.138
2.194
a
R1 (I > 2r(I))
0.0397
0.0643
0.1590
b
wR2 (I > 2r(I)) 0.0962
P
P
a
R1 = iFoj ꢂ jFci/ jFoj.
P
P
2
2 1=2
b
wR2 ¼ ½ wðjF 2oj ꢂ jF c2jÞ = wjF 2oj ꢀ
.
Table 2
Selected bond distances (A) and angles (ꢁ) for compound [1]Br Æ H2O
˚
bond distance for [1]+ (2.1780(13) A) is somewhat less
when compared with those observed in other low-spin
Fe(II) complexes with aryl-dialkyl phosphines [32,33].
The Fe–N(bipyridine) distances for [1]+ (1.918(4) and
Br(1)–Fe
Fe–N(1)
Fe–N(2)
Fe–P
Fe–S(1)
Fe–S(2)
2.5108(9)
1.918(4)
1.921(4)
2.1780(13)
2.2604(15)
2.2667(14)
˚
˚
1.921(4) A) are also slightly less than the average Fe–N
bond length (ca. 2.00 A) obtained through a Cambridge
Crystallographic Data Base (CCDB) search [34] on octa-
hedral Fe(II) complexes containing bipyridine as ligand
and covering 47 structures. However, the same distances
˚
N(1)–Fe–N(2)
N(1)–Fe–P
N(2)–Fe–P
N(1)–Fe–S(1)
N(2)–Fe–S(1)
P–Fe–S(1)
N(1)–Fe–S(2)
N(2)–Fe–S(2)
P–Fe–S(2)
S(1)–Fe–S(2)
N(1)–Fe–Br(1)
N(2)–Fe–Br(1)
P–Fe–Br(1)
S(1)–Fe–Br(1)
S(2)–Fe–Br(1)
81.42(16)
91.35(11)
93.46(11)
86.71(13)
168.12(12)
86.73(5)
167.92(13)
86.57(12)
88.10(5)
105.30(6)
93.52(11)
93.28(10)
172.21(4)
87.49(4)
for [2]+ (2.134(7) and 2.113(7) A) are ca. 0.20 A longer
than those found in [1]+ and similar to those reported
for related octahedral high-spin Fe(II)–bipyridine com-
plexes [35]. The same trends are also observed for the
Fe–S(thioether) distances, which in the case of [1]+
˚
˚
˚
(2.2604(15) and 2.2667(14) A) are very close to the Fe–
S bond lengths observed in low-spin Fe(II) complexes
of homoleptic polythiamacrocycles [36] and azathiamac-
rocycles [37] whereas in the complex cation [2]+ these dis-
88.40(4)
˚
tances are noticeably longer (2.558(3) and 2.579(3) A)
and similar to those reported for high-spin Fe(II) com-
plexes with different thioether containing ligands
[32,38]. These structural data confirm the low-spin nat-
ure of the Fe(II) metal ion in the complex [1]+. However
the bond distances and angles in the complex cation [2]+
are only compatible with a high-spin electronic configu-
ration for the Fe(II) metal ion, a fact that can be attrib-
uted to the increase in the macrocyclic ligand hardness
when the phosphane group in L is replaced by their phos-
phoryl derivative. Only the Br–Fe distance is slightly
short in [2]+ than in [1]+, which may be due to the
trans-effect of the P(phosphane) atom in [1]+ in compar-
ison with the O(phosphoryl) atom in [2] [2].
the complex cation [1]+ whereas in [2]+ the iron atom
deviates 0.191(2) A from the N2S2 plane.
˚
The Fe–Br bond distances observed for both com-
+
˚
plexes are similar (2.5108(9) and 2.4887(15) A for [1]
and [2]+, respectively), and lie in the same range as those
reported for related octahedral Fe(II) complexes con-
taining non-bridging bromine ligands [30]. This situa-
tion is similar for the Fe–O(phosphoryl) bond distance
+
˚
in [2] , which shows a value (2.107(5) A) comparable
to that observed in the few reported structures contain-
ing octahedral Fe(II) complexes with coordinated phos-
phoryl ligands [31]. However, the Fe–P(phosphine)

L. Escriche et al. / Polyhedron 25 (2006) 801–808
805
3. Experimental
7.42–7.77 (m, 11, Ar). 13C{1H} NMR (100 MHz,
CDCl3): d 27.71 (d, S–CH2–CH2–P–, J = 10.5 Hz),
28.72 (d, –S–CH2–CH2–P–, J = 20.9 Hz), 37.92 (–S–
CH2–Ph), 119.32, 124.62, 139.31 (Bipy), 128.08 (d, P–
Ph, J = 7.0 Hz), 128.54 (d, P–Ph, J = 15.7 Hz), 131.45
(d, P–Ph, J = 19.2 Hz), 131.86 (d, P–Ph, J = 19.4 Hz),
152.45, 158.58 (Bipy). 31P{1H} NMR (101 MHz,
CDCl3): d ꢂ 21.29. Mass spectrum (EI); m/z 410 (M+).
The syntheses were carried out using standard
Schlenk techniques under dry dinitrogen atmosphere.
The solvents were dried by conventional methods and
distilled under dinitrogen before use. Dilithium 3-phe-
nyl-3-phosphapenta-1,5-dithiolate and 6,60-bis(bromo-
methyl)-2,20-bipyridine [20,21] were prepared according
to published procedures. Chemical analyses were per-
formed in the Chemical Analysis Service of the Univer-
4.2. 3,30-5-oxo-5-phenyl-2,8-dithia-5-phospha[9]-2,20-
bipyridinophane (Lox)
`
sitat Autonoma de Barcelona. Elemental analyses were
carried out using a Carlo Erba EA-1108 instrument. Li
determinations were made by atomic emission spec-
trometry (AES) using a Perkin–Elmer 2100 instrument;
the samples were previously prepared treating them
with HNO3/H2O (1:1) at 180 psi during 40 min in a
microwaves digestor (CEM2000). The NMR spectra
A solution of L Æ 2LiBr (0.200 g, 0.34 mmol) in
CHCl3 (30 cm3) was stirred at open atmosphere and
room temperature for 24 h. The resulting solution was
evaporated to dryness and the resulting solid collected.
Yield (calculated for Lox Æ 2LiBr) 0.198 g, 97%. Anal.
Calc. for C22H23N2OPS2Li2Br2: C, 44.02; H, 3.86; N,
4.67; S, 10.68; Li, 2.31. Found: C, 43.8; H, 3.4; N, 4.6;
S, 10.3%; Li (determined by AES), 24.8 mg Li/1 g sam-
`
were run in the NMR Service of the Universitat Auto-
noma de Barcelona. 1H and 13C{1H} NMR spectra
were recorded using a Bruker 400 MHz AM instrument
and the 31P{1H} NMR spectra were recorded using a
Bruker 250 MHz AC instrument with chemical shifts
given as ppm relative to 85% H3PO4. COSY and
HNQC experiments were made in order to assign the
1H and 13C spectra by using general standard parame-
ters. Mass spectra were recorded using a HP298S GC/
MS system.
1
ple, 2.5%. H NMR (400 MHz, CDCl3): d 2.35 (m, 2,
–S–CH2–CH2–P–), 2.80 (m, 6, –S–CH2–CH2–P–), 3.81
(d, 2, –S–CH2–Ph, J = 13.9 Hz), 3.92 (d, 2, –S–CH2–
Ph, J = 13.9 Hz), 7.38–7.89 (m, 11, Ar). 13C{1H}
NMR (100 MHz, CDCl3): d 30.98 (d, –S–CH2–CH2–
P–, J = 14.8 Hz), 31.95 (d, S–CH2–CH2–P–, J =
18.5 Hz), 36.27 (–S–CH2–Ph), 120.60, 123.66 (Bipy),
128.81 (d, P–Ph, J = 11.09 Hz), 130.09 (d, P–Ph,
J = 9.2 Hz), 130.50 (d, P–Ph, J = 9.4 Hz), 132.04 (s,
P–Ph), 138.78, 138.93, 160.46 (Bipy). 31P{1H} NMR
(101 MHz, CDCl3): d 37.21. Mass spectrum (EI); m/z
426 (M+).
4. Syntheses
4.1. 3,30-5-phenyl-2,8-dithia-5-phospha[9]-2,20-
bipyridinophane (L)
4.3. [FeBr(L)](ClO4) Æ 2H2O Æ [1](ClO4) Æ 2H2O
Under a dinitrogen atmosphere, a solution of dili-
thium 3-phenyl-3-phosphapenta-1,5-dithiolate in thf
(100 cm3, 0.09 M) and a solution of 6,60-bis(bromom-
ethyl)-2,20-bipyridine (3.10 g, 9 mmol) in thf (100 cm3)
were added simultaneously to thf (500 cm3) over a peri-
od of 5 h at room temperature. After the addition, the
mixture was stirred for a further 48 h. The thf was re-
moved under vacuum and the resulting oily yellow resi-
due was extracted with diethyl ether (3 · 60 cm3). The
ethereal layer was separated, evaporated under vacuum,
and the residue was dissolved in the minimum amount
of CH2Cl2. After slow addition of petroleum ether
(40–60ꢁ) to this solution a white precipitate appeared
which was filtered off and vacuum dried. Yield (calcu-
lated for L Æ 2LiBr) 0.54 g, 10%. Anal. Calc. for
C22H23N2PS2Li2Br2: C, 45.23; H, 3.97; N, 4.79; S,
10.98; Li, 2.38. Found: C, 44.4; H, 3.8; N, 4.1; S,
10.2%; Li (determined by AES), 21.7 mg Li/1 g sample,
2.2%. 1H NMR (400 MHz, CDCl3): d 2.07 (m, 2,
–S–CH2–CH2–P–), 2.45 (m, 2, –S–CH2–CH2–P–), 2.84
(m, 4, –S–CH2–CH2–), 3.90 (d, 2, –S–CH2–Ph,
J = 13.9 Hz), 4.02 (d, 2, –S–CH2–Ph, J = 13.9 Hz),
A solution of Fe(ClO4)2 Æ 6H2O (44 mg, 0.122 mmol)
in acetonitrile (5 cm3) was slowly added to a solution
of L Æ 2LiBr (50 mg, 0.086 mmol) in dichloromethane
(2 cm3). The solution changed immediately to red–pur-
ple and a solid of the same colour appeared which was
filtered off, washed with dichloromethane and vacuum
dried. Yield: 17 mg, 29%. Anal. Calc. for C22H27BrCl-
FeN2-O6PS2: C, 38.76; H, 3.99; N, 4.11; S, 9.45. Found:
1
C, 38.9; H, 3.6; N, 4.2; S, 9.3%. H NMR (400 MHz,
CD3NO2): d 2.37 (m, 4, –S–CH2–CH2–P–), 3.13 (m, 4,
–S–CH2–CH2–P–), 4.67 (d, 2, –S–CH2–Ph, J = 18.0 Hz),
4.81 (d, 2, –S–CH2–Ph, J = 18.0 Hz), 6.24–7.00 (m, 6,
Bipy), 7.78 (m, 5, P–Ph). 13C{1H} NMR (100 MHz,
CD3NO2): d 22.51 (d, –S–CH2–CH2–P–, J = 29.7 Hz),
33.41 (d, S–CH2–CH2–P–, J = 31.5 Hz), 44.36 (–S–
CH2–Ph), 117.18, 117.56 (Bipy), 128.81 (d, P–Ph, J =
11.09 Hz), 124.42 (d, P–Ph, J = 8.9 Hz), 124.89 (d, P–
Ph, J = 9.1 Hz), 126.53 (s, P–Ph), 130.41, 153.59,
159.14 (Bipy). 31P{1H} NMR (101 MHz, CDCl3): d
132.52.

806
L. Escriche et al. / Polyhedron 25 (2006) 801–808
4.4. [FeBr(Lox)](ClO4) Æ 3H2O Æ [2](ClO4) Æ 3H2O
tor, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax: +44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk
or www: http://www.ccdc.cam.ac.uk)
The compound was prepared as for [1](ClO4) Æ 2H2O
using Lox as ligand. Yield: 19 mg, 29%. Anal. Calc. for
C22H29BrClFeN2O8PS2: C, 36.92; H, 4.08; N, 3.91; S,
8.96. Found: C, 36.4; H, 3.9; N, 3.8; S, 8.2%.
Acknowledgements
The authors acknowledge to ‘‘Ministerio de Edu-
´
cacion y Ciencia (Spain)’’ and ‘‘Generalitat de Catalunya
5. Crystallography
(Spain)’’ for Grants CTQ20004-04134 and 2001SGR
00177, respectively.
The slow evaporation of a nitromethane solution of
[1](ClO4) Æ 2H2O and a methanol solution of [2](ClO4) Æ
3H2O produced crystalline materials corresponding to
[1]Br Æ H2O and ½2ꢀðClO4Þ ꢁ 1 16 MeOH, respectively. Single-
crystal data were performed at ambient temperature on
a Rigaku AFC5S diffractometer using graphite mono-
chromatized Mo Ka radiation. The unit cell parameters
for both compounds were determined by least-squares
refinement of 25 carefully centered reflections. All data
obtained were corrected for empirical absorption (P
scan). A total of 4563 and 5557 reflections giving 4296
and 5198 unique reflections (Rint = 0.0179 and 0.0562)
were collected by T/2 scan mode (2hmax = 50ꢁ) for
[1]Br Æ H2O and ½2ꢀðClO4Þ ꢁ 1 16 MeOH, respectively.
Both structures were solved by direct methods and
least-squares refinements were performed using the
SHELX-97 program system [39]. For [1]Br Æ H2O non-
hydrogen atoms were refined with anisotropic displace-
ment parameters. Hydrogen atoms were included in the
calculations at the fixed distances from their host atoms
and treated as riding atoms using the SHELX-97 default
parameters.
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