Coordination and reactivity of white phosphorus and tetraphosphorus trisulphide in the presence of the fragment CpFe(dppe) [dppe = 1,2-bis(diphenylphosphino)ethane]

Article abstract of DOI:10.1016/j.jorganchem.2009.12.022

The reaction of [CpFe(dppe)Cl] (1) [dppe = 1,2-bis(diphenylphosphino)ethane] with one equivalent of P₄ or P₄S₃ in the presence of a chloride scavenger, TlPF₆ or AgOTf (OTf = triflate, OSO₂CF₃), affords the complexes [CpFe(dppe)(η¹-P₄)]PF₆ (2) and [CpFe(dppe)(η¹-P_basal-P₄S₃)]OTf (3) which contain the tetrahedral P₄ and the mixed P₄S₃ cage molecule η¹-bound to the metal. Both P₄ and P₄S₃ yield furthermore the dimetal compounds [{CpFe(dppe)}₂(μ,η^1:1-P₄)](PF₆)₂ (4) and [{CpFe(dppe)}₂(μ,η^1:1-P_apical-P_basal-P₄S₃)](OTf)₂ (5), which contain the tetrahedral P₄ or the mixed-cage P₄S₃ molecule tethering two ruthenium fragments via two phosphorus atoms. All the compounds have been characterized by elemental analyses and NMR measurements. The crystal structure of 4 has been determined by X-ray diffraction methods. The complexes readily react with excess water under mild reaction conditions and the outcoming products have been identified.

Full text of DOI:10.1016/j.jorganchem.2009.12.022

Journal of Organometallic Chemistry 695 (2010) 816–820
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Coordination and reactivity of white phosphorus
and tetraphosphorus trisulphide in the presence of the fragment CpFe(dppe)
[dppe = 1,2-bis(diphenylphosphino)ethane]
Massimo Di Vaira a, Maurizio Peruzzini b, Stefano Seniori Costantini a, Piero Stoppioni a,
*
a Dipartimento di Chimica, Università di Firenze, via della Lastruccia n. 3, 50019 Sesto Fiorentino, Firenze, Italy
b ICCOM CNR, via Madonna del Piano n. 10, 50019 Sesto Fiorentino, Firenze, Italy
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of [CpFe(dppe)Cl] (1) [dppe = 1,2-bis(diphenylphosphino)ethane] with one equivalent of P4 or
Received 27 November 2009
Received in revised form 17 December 2009
Accepted 18 December 2009
Available online 28 December 2009
P4S3 in the presence of a chloride scavenger, TlPF6 or AgOTf (OTf = triflate, OSO2CF3), affords the complexes
[CpFe(dppe)(
the mixed P4S3 cage molecule
pounds [{CpFe(dppe)}2( l,g
1:1-P4)](PF6)2 (4) and [{CpFe(dppe)}2(
g g
1-P4)]PF6 (2) and [CpFe(dppe)( 1-Pbasal-P4S3)]OTf (3) which contain the tetrahedral P4 and
g
1-bound to the metal. Both P4 and P4S3 yield furthermore the dimetal com-
1:1-Papical-Pbasal-P4S3)](OTf)2 (5), which
l
,g
contain the tetrahedral P4 or the mixed-cage P4S3 molecule tethering two ruthenium fragments via two
phosphorus atoms. All the compounds have been characterized by elemental analyses and NMR measure-
ments. The crystal structure of 4 has been determined by X-ray diffraction methods. The complexes readily
react with excess water under mild reaction conditions and the outcoming products have been identified.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Iron cyclopentadienyl complexes
Bidendate ligands
White phosphorus
Tetraphosphorus trisulfide
Crystal structure
1. Introduction
P4S3 derivative yields thiophosphinous acid, PH2SH [4], and the
P4 dimetal compound yields diphosphane, P2H4 [4], 1-hydroxotri-
It has been recently found that P4 [1–5], AsP3 [6] and P4S3 [7–9]
readily bind to 16e fragments yielding mono- and bimetallic com-
pounds which contain the intact cage molecules either g1 coordi-
nated to the metal or tethering two metal fragments. Such
complexes, at variance with the few unstable P4 and P4S3 com-
pounds previously described [10–17], possess good stability and
most of them are easily obtained in gram amounts; accordingly,
they are potentially useful for investigating the reactivity of the
coordinated molecules. Among all compounds, the cyclopentadi-
phosphane, PH(OH)PHPH2 [18] and 1,1,4-tris(hydroxy)tetraphos-
phane, P(OH)2PHPHPH(OH) [19], according to the relative
amounts of the complex and water employed. It is worthwhile to
point out that such molecules, which are stabilized through coor-
dination to the metal fragments, are either unknown as free enti-
ties or very difficult to be obtained [20]; the outcomings
furthermore allow to trace some hypotheses on the steps of the
degradation process [19].
The above results have shown that the reactivity of coordinated
P4 and P4S3 is highly affected by the electronic and/or steric prop-
erties of both the metal and its coligands [1]. With the aim to ob-
tain more information in this field, we have investigated the
behaviour of the cage molecules in the presence of the CpFe(dppe)
fragment (dppe = 1,2-bis(diphenylphosphino)ethane), which bears
ligands analogous to those employed with the ruthenium and os-
mium moieties and, in view of the easy access of iron to different
oxidation states, could promote red-ox reactions of the coordi-
nated molecules in the course of their degradation.
enyl mono-[CpM(PPh3)2(
CF3SO3) and bimetallic [{CpRu(PPh3)2}2(
[{CpRu(PPh3)2}2(
1:1-Papical-Pbasal-P4S3)](OTf)2 [4] complexes
g
1-P4)]Y (M = Ru [2], Os [5]; Y = PF6,
1:1-P4)](PF6)2 and
l,g
l,g
have been found to undergo hydrolysis in exceedingly mild condi-
tions exhibiting a spectacular change in reactivity of the coordi-
nated molecules with respect to the free molecules. The
hydrolysis of the monometal P4 derivatives yields PH3 and phos-
phorus oxygenated species which are the final products along the
degradation pathway of the P4 molecule [2,3]. The hydrolysis of the
bimetallic compounds has been found to be particularly interesting
for the metal platform(s) stabilize molecules that are intermediate
species along the P4 and P4S3 degradation. The hydrolysis of the
2. Results and discussion
The reaction of the dppe iron complex [CpFe(dppe)Cl] (1)
[dppe = 1,2-bis(diphenylphosphino)ethane] with one equivalent
of P4 or P4S3 in the presence of a chloride scavenger (TlPF6 or
* Corresponding author.
E-mail addresses: mperuzzini@iccom.cnr.it (M. Peruzzini), piero.stoppioni
@unifi.it (P. Stoppioni).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.12.022

M. Di Vaira et al. / Journal of Organometallic Chemistry 695 (2010) 816–820
817
AgCF3SO3 = AgOTf) readily yields the compounds [CpFe(dppe)-
1-P4)]PF6 (2) and [CpFe(dppe)( 1-Pbasal-P4S3)]OTf (3) with a good
yield (Scheme 1). Compounds 2 and 3 are stable under an inert
coordinated through one of the basal phosphorus atoms. The pres-
ent iron fragment accordingly appears to be highly regioselective
for the basal phosphorus of the P4S3.
(g
g
atmosphere and in this regard they behave as the related
A CH2Cl2 solution of 2 overnight yields 4, which crystallizes
with CH2Cl2 and toluene solvate molecules; the complex is stable
under an inert atmosphere as the related homo-
[CpM(PPh3)2(g -
1-P4)]Y (M = Ru [2], Os [5]) and [CpRu(dppe)(g1
P4)]Y derivatives [3]. The complexes are soluble in common organ-
ic solvents; 2 dissolved in CH2Cl2 undergoes transformation to
[{CpRu(PPh3)2}2(l,g
1:1-P4)]Y2 (Y = PF6, OTf) [4] and hetero-bime-
afford the dimetallic compound [{CpFe(dppe)}2(
l
,
g
1:1-P4)](PF6)2
tallic [{CpRu(PPh3)2}{CpOs(PPh3)2}(l,g
1:1-P4)](OTf)2 derivatives
(4), see below. The 31P NMR spectrum of 2 in (CD3)2CO yields a
first-order A2FM3, spin pattern (see Scheme 1 for labels). The four
phosphorus atoms of the cage yield the FM3 part of the resonances
which are downfield shifted with respect to the signal of the free
P4. This shift, as found for the analogous ruthenium and osmium
[5]. The complex is soluble in common organic solvents. The 31P
NMR spectrum of 4 in (CD3)2CO yields, as the ruthenium bimetallic
derivative [{CpRu(PPh3)2}2(l,g
1:1-P4)]Y2 [4], an A2A02FF0M2 spin
pattern (Scheme 1 for labels); where A and A0 are the dppe phos-
phorus atoms, F and F0 are the P4 atoms bound to the metal and
M the two atoms of the tetraphosphorus tetrahedron not involved
in the coordination. The signals of the coordinated atoms are sig-
nificantly downfield shifted with respect to that of the free mole-
cule and such shift is similar to those observed for the previous
homo- and hetero-bimetallic compounds [4,5].
[CpM(PPh3)2(g
1-P4)]Y (M = Ru, Os) derivatives [2,5], is particularly
enhanced for the atom bound to the metal centre; furthermore,
both signals are significantly downfield shifted with respect to
the corresponding ones of the ruthenium and osmium derivatives.
The 31P NMR spectrum of 3 in (CD3)2CO yields an A2FM2Q spin sys-
tem, see Scheme 1 for labels; the signals of dppe occur in the ex-
pected region and the four phosphorus atoms of the heptatomic
cage form the FM2Q part of the spin system. The coordinated phos-
phorus, PQ, exhibits a notable downfield shift with respect to the
three equivalent P atoms of the free cage, whereas the PM and PF
are only moderately deshielded. Other metal complexes containing
one P4S3 cage coordinated to one 16e metal fragment have been
described by our group and they present invariantly a pair of coor-
dination isomers which differ for the bonding mode of the P4S3
molecule to the metal, i.e. through the apical or through one of
the basal P atoms; furthermore, the relative amounts of each iso-
mer are significantly affected by the geometry and the electronic
properties of the metal fragments [7–9]. The NMR data of 3 are
consistent with the formation of one isomer where the cage is
The structure of compound 4 comprises dimetallic cations, PF6ꢀ
anions and solvate toluene and dichloromethane molecules, the lat-
ter being disorderly arranged. The overall coordination geometry
(Fig. 1) is grossly similar to that found for the dimetal cations
[{CpRu(PPh3)2}2(
(l,g
l,g
1:1-P4)]2+ [4] and [{CpRu(PPh3)2}{CpOs(PPh3)2}
1:1-P4)]2+ [5], although there are differences due to the presence
of the bidentate phosphane ligand in 4 instead of a pair of monoden-
tate PPh3 ligands and to lower crowding around the dimetal core in 4
than in the other two structures, due to a smaller number of phenyl
groups in 4. The metal–phosphorus distances in 4 (Table 1) are ca.
0.13 Å shorter, in the mean, than those in the diruthenium or in
the mixed ruthenium–osmium dication, in line with the differences
between covalent metal radii [20,21]. The differences between the
metal–Cp(centroid) distances in 4 (1.713 Å, mean value) and those
PF6
2PF6
CH2Cl2
Fe
Fe
Ph2P
Ph2P
PM
PM
PM
P
P
Ph2
PA'
A
A
n-hexane
F
F
PPh2
PPh2
P
A
A
P
P
F'
M
PPh2
M
Fe
A'
P4
+ TlPF
2
6
4
- TlCl
OTf
+ AgOTf
P4S3
Fe
PPh2
Fe
QP
P
Ph2P
Ph2P
A
Cl
M
- AgCl
S
PPh2
S
A
P
M
PF
S
1
3
1/2 P4S3
+ AgOTf
2OTf
- AgCl
Fe
P
Ph2P
A
QP
M
S
PPh2
Ph2
B
S
A
P
P
M
P
S
PPh2
F
Fe
B
5
-
OTf = CF3SO3
Scheme 1.

818
M. Di Vaira et al. / Journal of Organometallic Chemistry 695 (2010) 816–820
TheP4S3 derivatives3 and5 yieldbasicallythesameproductsi.e. free
phophorous, H3PO3, and hypophosphorous, H3PO2, acids and the
new cations [CpFe(dppe){RP(OH)2}]+ (R = H (6), OH (7)) where the
unstable HP(OH)2 and P(OH)3 tautomers of the two acids are bound
to the metal fragment. The cationic species have been characterized
by comparing the 1H and 31P NMR data of the hydrolysed mixture
with those of the pure samples that have been independently syn-
thesized (see below). The outcomings of the P4 derivatives 2 and 4
are characterized by the presence of a large amount of free P4 (ca.
80% of that in the parent complex) and of the cations [CpFe(dppe){H-
P(OH)2}]+ 6 and [CpFe(dppe)(PH3)]+ 8, the latter containing phos-
phine coordinated to the iron moiety.
The [CpFe(dppe){RP(OH)2}]OTf [R = H (6), OH (7)] and [CpFe(dp-
pe)(PH3)]OTf (8) derivatives are easily obtained by reacting 1 and
the chloride scavenger with the appropriate molecule (PH3,
H3PO2 and H3PO3). All the complexes yield a 31P{1H} NMR A2F spin
system where A and F are the phosphorus atoms of the dppe and of
the added molecule, respectively. The resonances of the biphos-
phane occur in the typical region of pseudoctahedral CpFe(dppe)
moieties; the shifts and the coupling constants (P–P and P–H) of
the coordinated molecules parallel those observed for the analo-
gous ruthenium and osmium derivatives [4,5,22]. Accordingly they
are assigned the same geometry where the phosphorus atom of
each molecule, PH3, H3PO2 or H3PO3, is bound to the metal frag-
ment. As found for the ruthenium [22] and osmium derivatives
[5], the phosphane tautomers of hypophosphorous and phospho-
rous acid, i.e. HP(OH)2 and P(OH)3, are stabilized through
coordination.
The above results show that the present CpFe(dppe) fragment is
suitable to bind the cage molecules. The reactivity of P4S3 is signif-
icantly modified, upon coordination, with respect to that of the free
molecule. The P4 compounds are characterized by the easy detach-
ment of the coordinated molecule. At variance with the outcom-
ings from the hydrolysis of the ruthenium derivatives, the
products contain one atom from the parent coordinated P4 and
P4S3; thus only the species which are at the final step of the degra-
dation of the molecules are observed.
Fig. 1. A view of the dication in the structure of 4, with 30% probability ellipsoids.
Hydrogen atoms are omitted for clarity.
Table 1
Selected bond lengths (Å) and angles (°) for 4.
Fe1–P1
Fe1–P2
Fe1–P5
P5–P6
P5–P7
P5–P8
2.224(1)
2.223(1)
2.151(1)
2.160(2)
2.185(2)
2.186(2)
Fe2–P3
Fe2–P4
Fe2–P6
P7–P8
P6–P7
P6–P8
2.213(1)
2.237(1)
2.174(1)
2.229(2)
2.193(2)
2.190(2)
P1–Fe1–P2
P1–Fe1–P5
P2–Fe1–P5
Fe1–P5–P6
85.74(5)
90.91(5)
99.14(5)
153.16(7)
P3–Fe2–P4
P3–Fe2–P6
P4–Fe2–P6
Fe2–P6–P5
85.62(5)
92.43(5)
93.45(5)
157.33(7)
of the other two cations (1.878 Å [4], 1.880 Å [5]) are still larger than
the above difference between the metal–phosphorus distances. The
P4 cageexhibits thetypeof distortionalreadyfound for theother two
structures, where the P–P bond between the atoms bound to the
metals is the shortest of those in the cage and the P–P bond between
the other two atoms is the longest one. The Fe1–P5–P6–Fe2 8.1(3)°
torsion angle differs from those (ꢀ27.4(6)° [4], ꢀ26.9(6)° [5]) of
the other two compounds, possibly as a result of the release of steric
hindrances in 4 between the ligands on the two sides of the cation.
Compound 5 is obtained in a good yield (Scheme 1) by reacting
1 in THF/CH2Cl2 with half equivalent of P4S3 in the presence of
AgOTf. The complex, poorly soluble in common organic solvents,
is stable under an inert atmosphere. The 31P{1H} NMR spectrum
of 5 in (CD3)2CO yields a first-order A2B2FM2Q spin system, see
the Scheme 1 for labels. Both the chemical shifts and the coupling
constants of PA and PB nuclei show values in the range expected for
cationic iron half-sandwich compounds. The four phosphorus
atoms of the cage form the FM2Q part of the spectrum: all
resonances are downfield shifted with respect to the free P4S3
molecule, and such shift is consistent with the trend observed for
3. Experimental
3.1. General
All reactions and manipulations were performed under an
atmosphere of dry oxygen-free nitrogen. The solvents were puri-
fied according to standard procedures [23]. The 1H, 19F and 31P
NMR spectra were run on a Bruker Avance 400 plus spectrometer.
19F and 31P chemical shifts are relative to external CFCl3 and to 85%
H3PO4, respectively. 1H chemical shifts are relative to tetramethyl-
silane as external reference and were calibrated against the resid-
ual solvent resonance. Downfield values are reported as positive,
coupling constants are in Hertz. 19F NMR spectra of the triflate
derivatives yielded a singlet at ꢀ75.5 ppm for the anion. Coupling
constants of 4 were obtained from 1D 31P{1H} NMR spectrum with
the aid of computer simulation using the GNMR program [24].
Microanalyses were done by the Microanalytical Laboratory of
the Department of Chemistry of the University of Firenze.
[CpFe(dppe)Cl] 1 was prepared according to the literature method
[25].
the cations [{(triphos)Re(CO)2}2(
[{Cp*Ru(L2)}2(
1:1-Papical-Pbasal-P4S3)]2+ [9] and [{CpRu(PPh3)}2
1:1-Papical-Pbasal-P4S3)]2+ previously described, which contain
l,g
1:1-Papical-Pbasal-P4S3)]2+ [7],
l,g
(l,g
the P4S3 bridging ligand [4].
Compounds 2, 3, 4 and 5 in (CH3)2CO or THF undergo readily
transformation at room temperature in the presence of an excess
amount of water (1:100). 31P{1H} NMR measurements have shown
that reactions carried out on different batches are reproducible
both with respect to the amount and to the nature of the products
obtained; also, the gaseous phase does not contain phosphorus
compounds and the solid obtained after removing the solvent is
a mixture of several compounds.
3.2. Synthesis of the complexes
3.2.1. [CpFe(dppe)(g
1-P4)]PF6 (2)
Neat [CpFe(dppe)Cl] 1 (280 mg, 0.50 mmol), TlPF6 (175 mg,
0.50 mmol) and P4 (75 mg, 0.6 mmol) were suspended in a mixture
of CH2Cl2 (20 cm3) and THF (30 cm3) and the resulting slurry was
Compounds 3 and 5 complete their transformation within 2–3 h,
whereas 2 and 4 require ca. one day for completion of the hydrolysis.

M. Di Vaira et al. / Journal of Organometallic Chemistry 695 (2010) 816–820
819
Table 2
stirred for 4 h; the precipitated TlCl was filtered off and the solvent
Crystal data and structure refinement parameters for [{CpFe(dppe)}2(l, -
g1:1
P4)](PF6)2ꢁ0.66(C7H8)ꢁ0.64(CH2Cl2) (4).
evaporated under reduced pressure. The dark red solid was washed
twice with toluene (10 cm3), n-hexane and dried. Yield: 310 mg
(80%). Anal. Calc. for C31H29F6FeP7: C, 47.23; H, 3.71; P, 27.10.
Found: C, 47.10; H, 3.82; P, 26.90%. 1H NMR [d, (CD3)2CO, 20 °C]:
7.80–7.20 (20H, m, Ph), 4.94 (5H, s, Cp), 2.81 (4H, m, CH2).
31P{1H} NMR [d, (CD3)2CO, 20 °C], spin system of the anion
A2FM3: 90.5 (2P, d, 2J(PA–PF) = 55.0, PA), ꢀ147.3 (1P, sept, 1J(P–
F) = 711.5, PFꢀ6 ), ꢀ317.4 (1P, tq, 1J(PF–PM) = 233.0, PF), ꢀ492.7 (3P,
d, PM).
Empirical formula
C67.29H64.59Cl1.28F12Fe2P10
Mr
1568.01
Crystal system
Space group
T (K)
Monoclinic
P21/c
173(2)
a (Å)
b (Å)
c (Å)
20.4944(2)
14.7927(2)
23.7333(3)
90.768(1)
7194.5(2)
4
1.448
6.386
3200
b (°)
V (Å3)
Z
3.2.2. [CpFe(dppe)(g
1-Pbasal-P4S3)]OTf (3)
dcalcd (g cmꢀ3
)
The complex was prepared through the same procedure to ob-
tain 2 by adding to the slurry of [CpFe(dppe)Cl] 1 (280 mg,
0.50 mmol) and AgOTf (128 mg, 0.50 mmol) the stoichiometric
amount of P4S3 dissolved in toluene. Yield: 270 mg (60%). Anal.
Calc. for C32H29F3FeO3P6S4: C, 43.26; H, 3.29; P, 20.91. Found: C,
43.08; H, 3.40; P, 20.30%. 1H NMR [d, CD2Cl2, 20 °C]: 7.80–7.20
(20H, m, Ph), 4.70 (5H, s, Cp), 3.02 (4H, m, CH2). 31P{1H} NMR (d,
CD2Cl2, 20 °C], spin system of the anion A2FM2Q: 92.2 (2P, d,
2J(PA–PQ) = 41.5, PA), 86.5 (1P, dt, 2J(PF–PQ) = 42.0, 2J(PF–
PM) = 67.5, PF), 48.8 (1P, tq, 1J(PQ–PM) = 235.5, PQ), ꢀ138.5 (2P, dd,
PM).
Absorption coefficient (mmꢀ1
F(0 0 0)
)
h Range (°)
Reflections measured
4.12–65.08
45 725
Independent reflections
12 256
Observed reflections (I > 2
No. of parameters/restraints
Final R indices (I > 2 (I)) R1, wR2
r
(I), Rint
8835, 0.0439
886/135
0.0579, 0.1681
0.0836, 0.1839
1.083
r
Final R indices (all data) R1, wR2
Goodness-of-fit (GOF) on F2
D
qmax
,
D
qmin (e Åꢀ3
)
1.049, ꢀ0.532
3.2.3. [{CpFe(dppe)}2(
l
,
g
1:1-P4)](PF6)2ꢁ0.6CH2Cl2ꢁ0.6C7H8 (4)
C
32H32F3FeO6P3S (7): C, 51.22; H, 4.30. Found: C, 51.10; H, 4.40%.
[CpFe(dppe)(
g
1-P4)]PF6 2 (390 mg, 0.50 mmol) was dissolved in
1H NMR [d, (CD3)2CO, 20 °C]: 7.90–7.20 (20H, m, Ph), 4.67 (5H, s,
Cp), 2.92 (4H, m, CH2). 31P{1H} NMR [d, (CD3)2CO, 20 °C], spin sys-
tem of the anion A2F: 165.6 (1P, t, 2J(PF–PA) = 95.0, PF), 100.1 (2P, d,
PA). Anal. Calc. for C32H32F3FeO3P3S (8): C, 54.72; H, 4.60. Found: C,
54.40; H, 4.55%. 1H NMR [d, (CD3)2CO, 20 °C]: 7.90–7.20 (20H, m,
Ph), 4.75 (5H, s, Cp), 4.60 (3H, dt, 3J(H–PA) = 6, HP), 2.78 (4H, m,
CH2). 31P{1H} NMR [d, (CD3)2CO, 20 °C], spin system of the
anion A2F: 96.5 (2P, d, 2J(PA–PF) = 59.5, PA), ꢀ81.9 (1P, t,
1J(PA–H) = 347.5, PF).
CH2Cl2 (40 cm3) and the solution stratified under toluene (40 cm3).
Red crystals of 4, suitable for X-ray analysis, were obtained over-
night. The solid was filtered, washed with n-hexane and dried.
Yield: 120 mg (30%). Anal. Calc. for C67.3H64.6Cl1.3F12Fe2P10: C,
51.52; H, 4.15; P, 19.75. Found: C, 51.10; H, 4.22; P, 19.13%. 1H
NMR [d, (CD3)2CO, 20 °C]: 7.90–7.10 (43H, m, Ph), 5.61 (0.6H, s,
CH2Cl2), 4.75 (10H, s, Cp), 2.75 (8H, mbr, CH2), 2.30 (0.6H, s,
CH3C6H5). 31P{1H} NMR [d, (CD3)2CO, 20 °C], spin system of the
A2A0 FF0M2:
89.3
(4P,
J(PA–PF) = J(PA –PF ) = 50.5,
2
2
0
0
anion
2
3
3
3
3
0
0
0
J(PA–PF ) = J(PA –PF) = ꢀ2.0, J(PA–PM) = J(PA –PM) = 3.0, PA and
3.3. X-ray crystallography of (4)
PA ), ꢀ147.3 (2P, sept, 1J(P–F) = 711.5, PF6), ꢀ265.5 (2P,
0
1
1
1
0
0
0
J(PF–PF ) = 210.0,
ꢀ488.2 (2P, PM).
J(PF –PM) = J(PF–PM) = 153.5, PF and PF ),
X-ray diffraction data for 4, as dichloromethane and toluene sol-
vate, were collected on an Oxford Diffraction Xcalibur PX Ultra CCD
diffractometer equipped with Enhance Ultra optics, using Cu K
a
3.2.4. [{CpFe(dppe)}2(l,g
1:1-Papical-Pbasal-P4S3)](OTf)2 (5)
radiation (k = 1.5418 Å). Crystal data and the main data collection
and structure refinement parameters are given in Table 2. Lattice
constants were obtained from the setting angles of 22 649 reflec-
tions in the h range 4.11–72.13°. Intensity data were corrected for
absorption by a multi-scan procedure [26]. The structures were
solved by direct methods, with SIR-97 [27], and were refined by
full-matrix least-squares on F2 values [28]. All non-hydrogen atoms
were refined anisotropically. All hydrogens bound to carbons were
placed in idealized positions, each riding on the respective carrier
atom, with its temperature factor linked to the isotropic equivalent
U of the latter. Acceptable temperature factors for atoms of the sol-
vate molecules were only attained if the molecules were assigned
fractional occupancy factors; the values of these were refined. The
highlydisordered dichloromethane molecule was modelled as being
distributed over two positions; restraints on geometry and thermal
parameters of both solvate molecules were imposed. Too close ap-
proaches between a fraction of CH2Cl2 and the toluene molecule
could be excluded in view of the fractional occupancy factors. Pro-
grams used in the crystallographic calculations included WINGX
[29] and ORTEP [30] for graphics.
The complex was prepared through the same procedure to ob-
tain 3 by adding to the slurry of [CpFe(dppe)Cl] 1 (280 mg,
0.50 mmol) and AgOTf (128 mg, 0.50 mmol) half equivalent of
P4S3 dissolved in toluene. Yield: 290 mg (75%). Anal. Calc. for
C64H58F6Fe2O6P8S5: C, 49.37; H, 3.76; P, 15.91. Found: C, 49.02;
H, 3.60; P, 15.20%. 1H NMR (d, CD2Cl2, 20 °C): 7.90–7.20 (40H, m,
Ph), 4.69 (5H, s, Cp), 4.33 (5H, s, Cp), 2.52 (8H, m, CH2). 31P{1H}
NMR (d, CD2Cl2, 20 °C), spin system of the anion A2B2FM2Q:
178.5 (1P, dtt, 2J(PF–PQ) = 24.0, 2J(PF–PM) = 38.0, 2J(PF–PB) = 40.0,
PF), 89.8 (2P, d, 2J(PA–PQ) = 42.0, PA), 88.7 (2P, d, PB), 40.5 (1P, dtt,
1J(PQ–PM) = 206.0, PQ), ꢀ129.6 (dd, 2P, PM).
3.2.5. [CpFe(dppe){RP(OH)2}]OTf [R = H (6), OH (7)] and
[CpFe(dppe)(PH3)]OTf (8)
The complexes were prepared through the same procedure to
obtain 2 by adding to the slurry of [CpFe(dppe)Cl] 1 (280 mg,
0.50 mmol) and TlOTf (175 mg, 0.50 mmol) the stoichiometric
amount of the acid (H3PO2 or H3PO3) or by bubbling PH3 through
the suspension. Pure complexes were obtained after recrystalliza-
tion from CHCl3 and n-hexane with a ca. 40% yield. Anal. Calc. for
C32H32F3FeO5P3S (6): C, 52.33; H, 4.39. Found: C, 52.10; H, 4.50%.
1H NMR [d, (CD3)2CO, 20 °C]: 8.20 (1H, dt, 3J(H–PA) = 5, HP), 7.90–
7.20 (20H, m, Ph), 4.62 (5H, s, Cp), 2.88 (4H, m, CH2). 31P{1H}
NMR [d, (CD3)2CO, 20 °C], spin system of the anion A2F: 171.5
(1P, t, 2J(PF–PA) = 85.0, PF), 100.7 (2P, d, PA). Anal. Calc. for
4. Supplementary material
CCDC 755705 contains the supplementary crystallographic data
for 4. These data can be obtained free of charge from The Cam-

820
M. Di Vaira et al. / Journal of Organometallic Chemistry 695 (2010) 816–820
[11] P. Dapporto, L. Sacconi, P. Stoppioni, F. Zanobini, Inorg. Chem. 20 (1981) 3834–
3839.
[12] M. Di Vaira, M.P. Ehses, M. Peruzzini, P. Stoppioni, Eur. J. Inorg. Chem. (2000)
2193–2198.
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/da-
ta_request/cif.
[13] T. Gröer, G. Baum, M. Scheer, Organometallics 17 (1998) 5916–5919.
[14] A.W. Cordes, R.D. Joiner, E.D. Shores, Inorg. Chem. 13 (1974) 132–134.
[15] R. Jefferson, H.F. Klein, J.F. Nixon, J. Chem. Soc., Chem. Commun. (1969) 536–
537.
[16] M. Di Vaira, M. Peruzzini, P. Stoppioni, Inorg. Chem. 22 (1983) 2196–2198.
[17] M. Di Vaira, M. Peruzzini, P. Stoppioni, J. Organomet. Chem. 258 (1983) 373–
381.
Acknowledgements
Financial support by the Italian Ministero dell’Istruzione,
dell’Università e della Ricerca is gratefully acknowledged. This
work has been carried out within the frame of COST ACTION
CM0802 of the European Community.
[18] P. Barbaro, M. Di Vaira, M. Peruzzini, S. Seniori Costantini, P. Stoppioni, Angew.
Chem., Int. Ed. Engl. 47 (2008) 4425–4427.
[19] P. Barbaro, M. Di Vaira, M. Peruzzini, S. Seniori Costantini, P. Stoppioni, Inorg.
Chem. 48 (2009) 1091–1096.
References
[20] M. Baudler, K. Glinka, Chem. Rev. 94 (1994) 1273–1297.
[21] B. Cordero, V. Gómez, A.E. Platero-pratz, M. Revés, J. Echeverría, E. Cremades, F.
Barragán, S. Alvarez, Dalton Trans. (2008) 2832–2838.
[22] D.N. Akbaieva, M. Di Vaira, M. Peruzzini, S. Seniori Costantini, P. Stoppioni,
Dalton Trans. (2006) 389–395.
[23] D.D. Perrin, W.L.F. Armarego, Purification of Laboratory Chemicals, third ed.,
Pergamon, New York, 1988.
[24] P.H.M. Budzelaar, GNMR V4.0, Cherwell Scientific Publishing, Copyright 1995–
1997 Iviry soft.
[25] M.J. Mays, P.L. Sears, J. Chem. Soc., Dalton Trans. (1973) 1873–1876.
[26] Oxford Diffraction, CRYSALIS RED (Version 171.32.29), Oxford Diffraction Ltd.,
Abingdon, Oxfordshire, England, 2006.
[27] M.C. Burla, R. Caliandro, M. Camalli, B. Carrozzini, G.L. Cascarano, L. De Caro, C.
Giacovazzo, G. Polidori, R. Spagna, J. Appl. Crystallogr. 38 (2005) 381–388.
[28] G.M. Sheldrick, Acta Crystallogr., Sect. A 64 (2008) 112–122.
[29] L.J. Farrugia, J. Appl. Crystallogr. 32 (1999) 837–838.
[30] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.
[1] I. de los Rios, J.-R. Hamon, P. Hamon, C. Lapinte, L. Toupet, A. Romerosa, M.
Peruzzini, Angew. Chem., Int. Ed. 40 (2001) 3910–3912.
[2] M. Di Vaira, P. Frediani, S. Seniori Costantini, M. Peruzzini, P. Stoppioni, Dalton
Trans. (2005) 2234–2236.
[3] M. Di Vaira, M. Peruzzini, S. Seniori Costantini, P. Stoppioni, J. Organomet.
Chem. 691 (2006) 3931–3937.
[4] P. Barbaro, M. Di Vaira, M. Peruzzini, S. Seniori Costantini, P. Stoppioni, Chem.
Eur. J. 13 (2007) 6682–6690.
[5] M. Caporali, M. Di Vaira, M. Peruzzini, S. Seniori Costantini, P. Stoppioni, F.
Zanobini, Eur. J. Inorg. Chem. (2010) 152–158.
[6] B.M. Cossairt, C.C. Cummins, J. Am. Chem. Soc. 131 (2009) 15501–15511.
[7] E. Guidoboni, I. de los Rios, A. Ienco, L. Marvelli, C. Mealli, A. Romerosa, R. Rossi,
M. Peruzzini, Inorg. Chem. 41 (2002) 659–668.
[8] I. de los Rios, F. Mani, M. Peruzzini, P. Stoppioni, J. Organomet. Chem. 689
(2004) 164–169.
[9] M. Di Vaira, I. de los Rios, F. Mani, M. Peruzzini, P. Stoppioni, Eur. J. Inorg. Chem.
(2004) 293–300.
[10] P. Dapporto, S. Midollini, L. Sacconi, Angew. Chem., Int. Ed. 18 (1979) 469.