Dithiafulvenylphosphine as P- and P,S-ligand towards metal carbonyl fragments

Article abstract of DOI:10.1016/j.jorganchem.2008.04.011

The ability of the dithiafulvenylphosphine (P-DTF) to react as a monodentate (P) or a bidentate (P,S) ligand with metal carbonyl complexes such as Mo(CO)₆ and MnBr(CO)₅ is presented. A series of metal carbonyl complexes are synthesis

Full text of DOI:10.1016/j.jorganchem.2008.04.011

Journal of Organometallic Chemistry 693 (2008) 2345–2350
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Dithiafulvenylphosphine as P- and P,S-ligand towards metal carbonyl fragments
*
Michel Guerro, Emmanuel Di Piazza, Xin Jiang, Thierry Roisnel, Dominique Lorcy
Sciences Chimiques de Rennes, UMR-CNRS 6226, Université de Rennes 1, Campus de Beaulieu, Bât 10A, 35042 Rennes cedex, France
a r t i c l e i n f o
a b s t r a c t
Article history:
The ability of the dithiafulvenylphosphine (P-DTF) to react as a monodentate (P) or a bidentate (P,S)
ligand with metal carbonyl complexes such as Mo(CO)6 and MnBr(CO)5 is presented. A series of metal
carbonyl complexes are synthesised and characterised by IR, 1H NMR and 31P NMR spectroscopy. X-ray
crystallographic analyses on the Mo(CO)5(P-DTF) and Mo(CO)4(P,S-DTF) complexes are reported together
with the structural investigations on the dithiafulvenes precursors. The electrochemical properties of the
various complexes investigated by cyclic voltammetry are discussed.
Received 21 March 2008
Received in revised form 9 April 2008
Accepted 9 April 2008
Available online 13 April 2008
Keywords:
Molybdenum
Manganese
Ó 2008 Elsevier B.V. All rights reserved.
Carbonyl complexes
P and P/S ligands
X-ray structure
1. Introduction
carbonyl complexes, we report that this redox active ligand be-
haves easily as a (P) ligand while its reactivity as a (P,S) ligand is
Redox active phosphines containing a tetrathiafulvalene (TTF)
core have received considerable attention in recent years particu-
larly as building blocks for the formation of hybrid multifunctional
materials or as ligands for catalytic applications [1–5]. Another
interesting electroactive moiety, related to TTF, is the dithiafulvene
(DTF) core. Besides being an excellent precursor of vinylogous TTF,
DTF substituted by a diphenylphosphino group has also proved to
be a good (P) ligand towards transition metal complexes such as
molybdenum or tungsten in [M(CO)4(P-DTF)2] [6]. Moreover, this
redox active vinyl phosphine (P-DTF) stands out by its ability to
form upon oxidation, when two of them are coordinated to a metal
carbonyl fragment M(CO)4 with M = Mo or W, a bidentate diphos-
phine complex with a redox active vinylogous tetrathiafulvalene
backbone [M(CO)4(P,P-TTFV)] (Chart 1).
When we first studied the coordinating ability of this redox ac-
tive ligand (P-DTF), we choose to prepare metal 0 complexes from
cis-M(CO)4(piperidino)2 with M = Mo and W, demonstrating that
(P-DTF) can behave either as a monodentate (P) ligand or as a
bidentate (P,S) ligand towards tungsten carbonyl fragment
W(CO)4 [6b]. In continuation of our studies on this vinyl phos-
phine, we wish now to report the reactivity of this ligand towards
Mo(CO)6. As compared with cis-[Mo(CO)4(piperidino)2], the CO li-
gands are less labile than the piperidino one. We also examined
the reactivity of this phosphine towards another metal carbonyl
fragment such as Mn1+ metal ion in BrMn(CO)5. Using these metal
subjected to the withdrawal facilities of one CO ligand. In addition,
the structural properties of the various dithiafulvene precursors as
well as the Mo complexes together with the electrochemical prop-
erties of the different complexes is presented.
2. Results and discussion
2.1. Synthesis and molecular structures of the ligand
The vinyl phosphine 2 was prepared (Scheme 1) from the phos-
phine borane 1 by simply treating 1 with DABCO in order to realize
the decomplexation of the phosphine borane [6]. The dithiafulvene
2 is an air stable compound which can be stored for months with-
out being oxidized. We also prepared the thioxo derivative of 2 by
simply treating 2 with S8 in dichloromethane at room temperature.
Crystals of 1, 2 and 3 were isolated from recrystallization in
MeOH. The X-ray molecular structures of 1–3 are shown in Fig. 1
and selected bond lengths are listed in Table 1. X-ray crystal struc-
ture analysis demonstrates that in all the cases the dithiafulvene
cores are planar, while the diphenyl substituents on the phosphorus
atom are located differently due to the orientation of either BH3 or
the thioxo groups. Concerning compound 1 and the borane group
bound to the phosphorus atom, the P–B (1.922(2) Å) bond length
as well as the C–P–C and C–P–B angles are in agreement with those
of related phosphine borane derivatives with a slightly distorted
tetrahedral environment [7,8]. As can be seen in Table 1, there is
no significant influence of the electron withdrawing or releasing
character of the phosphino group on the bond lengths of the
* Corresponding author. Tel.: +33 2 23 23 62 73; fax: +33 2 23 23 67 38.
E-mail address: dominique.lorcy@univ-rennes1.fr (D. Lorcy).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.04.011

2346
M. Guerro et al. / Journal of Organometallic Chemistry 693 (2008) 2345–2350
Me
Me
S
Me
S
Me
Me
Me
Me
Me
Me
Me
S
S
S
P
S
S
S
S
S
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
P
P
P
M
M
H
PPh2
P-DTF
(CO)4
(CO)4
cis-M(CO)4(P-DTF)2
M(CO)4(P,P-TTFV)
M = Mo, W
Chart 1.
dithiole ring while the oxidation potential of the dithiole core is
more sensitive to this influence (vide infra).
The molecular structures of 4 and 5 are depicted in Fig. 2, and
selected bond lengths are listed in Table 1. As can be seen in
Fig. 2, the dithiole core of the vinylphosphine in 4 is planar while
in 5, due to the formation of the metallacycle, the dithiole ring is
folded along the Sꢀ ꢀ ꢀS axis with an angle of 26°. The strain brought
by the P,S coordination mode in 5 influences also the geometry of
the dithiole ring itself as the C–S bond within the metallacycle (S2–
C32 1.776(2) Å) is slightly longer than the other one (S3–C32
1.752(2) Å). Phosphorus–molybdenum bond lengths are in the
usual range, Mo–P1: 2.5531(7) Å for 4 and Mo–P11: 2.5141(4) Å
for 5 with a P11–Mo–S2 interligand angle of 76.367(15)° [9]. Com-
pared with the bis dithiafulvene derivative [Mo(CO)4(P-DTF)2] we
previously reported [6], it is interesting to note that the Mo–P bond
length in 4 is slightly longer than in [Mo(CO)4(P-DTF)2] (Mo1–P1
2.5084 (10) Å).
As the reaction of Mo(CO)6 at 150 °C in decahydronaphtalene
with a stoichiometric amount of 2 leads mainly to the monosubsti-
tuted metal carbonyl complex 4, we investigated another route for
the formation of the chelated complex 5. Assuming that the syn-
thesis of 5 could be realized from 4 through the loss of one CO li-
gand followed by an intramolecular coordination of the Mo atom
with one S atom of the dithiole ring, we studied three classical
pathways for eliminating one CO ligand. First, we investigated
the influence of the heat, under inert atmosphere, on a solution
2.2. Molybdenum complexes
In continuation of our work on the coordinating ability of this
vinyl phosphine 2 towards transition metal complexes, we investi-
gated its reactivity towards Mo(CO)6. In order to coordinate only
one vinyl phosphine ligand to the molybdenum atom, we heated
a solution of 2 in decahydronaphtalene with one equivalent of
Mo(CO)6 (Scheme 2). After 30 min, analysis of the medium by 31P
NMR reveals two singlets on the spectrum, at 24.1 ppm and
62.4 ppm, corresponding to the formation of two metal complexes.
Chromatographic separation of the reaction mixture on silica gel
affords two crystalline metal complexes 4 and 5 in 45% and 5%
yield, respectively. Assignment of the structures [Mo(CO)5-
(P-DTF)] (4) and [Mo(CO)4(P,S-DTF)] (5), was realized thanks to
X-ray crystal structure analysis (Fig. 2). The monosubstituted
molybdenum complex [Mo(CO)5(P-DTF)] (4), exhibits the signal
at 24.1 ppm on the 31P NMR spectrum. It is worth mentioning that
4 and the bis substituted molybdenum derivative, [Mo(CO)4
(P-DTF)2] [6], exhibit a singlet at the same chemical shift on the
31P NMR spectra (24.1 ppm) (Table 2). Contrariwise, the phospho-
rus atom in 5 resonates at lower field than in 4 and a deshielding of
38 ppm is observed consistent with the strain brought by the P,S
coordination mode of P-DTF to the metal in 5. Actually, close
deshielding (36 ppm) was already noticed when going from
[Mo(CO)4(P-DTF)2] to the five-membered metallacycle [Mo
(CO)4(P,P-TTFV)] (see Chart 1).
Table 1
Selected bond distances (Å) for compounds 1–5
Me
d'
Me
d
1
2
3
4
5
e
S
S
c'
c
b
Me Me
Me Me
Me Me
a
P
H
DABCO
S8
S
H
S
S
H
S
S
H
S
a
1.787(2)
1.357(3)
1.741(2)
1.755(2)
1.760(2)
1.760(2)
1.329(3)
1.796(3)
1.347(4)
1.753(2)
1.747(2)
1.759(3)
1.753(3)
1.318(4)
1.7789(15)
1.352(2)
1.796(3)
1.346(4)
1.748(3)
1.751(3)
1.761(3)
1.760(3)
1.320(5)
1.8120(18)
1.325(3)
1.7517(17)
1.7762(18)
1.767(2)
b
c
c0
d
d0
e
S
1.7509(15)
1.7467(15)
1.7527(16)
1.7587(16)
1.337(2)
PPh2(BH3)
PPh2
P
Ph2
2
3
1
1.7764(18)
1.328(3)
Scheme 1.
A
B
C
S2
S3
P1
C34
S1
S2
C31
C32
C35
C4
C3
S2
S1
P1
S1
P1
C5
C6
C25
C23
B1
C21
C22
Fig. 1. Molecular structures of 1 (left A), 2 (middle B) and 3 (right C) (Hydrogen atoms omitted for clarity). Ellipsoids are drawn at 50% probability.

M. Guerro et al. / Journal of Organometallic Chemistry 693 (2008) 2345–2350
2347
Table 2
Me
Me
Me
Me
Me
Me
31P parameters and oxidation peak potentials for the Molybdenum metal carbonyl
complexes
S
S
S
S
Mo(CO)6
S
S
+
Compound
dP (ppm)
Epa (V) vs. SCE
Mo(CO)4
Mo(CO)5
1
14.3
ꢁ13.2
32.1
1.07
0.73
1.01
H
P
H
P
H
PPh2
P-DTF, 2
3
Ph2
Ph2
2
4
5
[Mo(CO)5(P-DTF)] (4)
[Mo(CO)4(P,S-DTF)] (5)
[Mo(CO)4(P-DTF)2]
24.1
62.4
24.1
0.88
0.92
0.60, 1.35
Scheme 2.
of 5 in various solvents and the reaction was monitored by
31P NMR (Scheme 3). After 3 h of reflux in dichloromethane, it
was possible to detect the formation of a small amount of complex
5 in the medium through the appearance of the signal at 62.4 ppm.
Actually, by increasing the reaction time for 5 days, we were able
to transform 25% of the starting complex 4 into the (P,S) chelate
complex 5 (Scheme 3). Then, we realized similar experiment with
a solution of 4 in toluene, expecting that the elevation of the reflux
temperature will favour the departure of the CO ligand. Actually,
by increasing the temperature, we induced the decoordination of
the phosphine one instead of the CO, as the signature of dithiaful-
vene 2 was observed on the 31P NMR spectrum. Therefore, we
choose another approach involving the reaction of 4 at room tem-
perature during 3 h in the presence of one equivalent of
Me3NO ꢀ 2H2O [10] in dichloromethane. Actually, in these condi-
tions, the use of this reactant with 4 did not allow the release of
one coordination site as complex 4 is entirely recovered. This is
surprising as it is known that similar reaction realized with
Mo(CO)5(PPh3) in the presence of Me3NO and PPh3 yielded the
trans bisubstituted complex, trans-Mo(CO)4(PPh3)2 [10]. One
explanation for the inertia of 4 with Me3NO ꢀ 2H2O could be that
the vinyl phosphine ligand behaves as a good electron donor
inducing a diminution of the electrophilic character of the carbon
in the C+„O ligand towards the reagent. In agreement with this
observation, the length of the bond between the metal and the
trans-carbonyl carbon atom is shorter than the metal-cis-carbonyl
bonds indicating a back donation to the trans carbonyl ligand due
to the donating ability of the phosphine 2.
Me
Me
Me
Me
Δ
S
S
S
S
Mo(CO)4
or hν
Mo(CO)5
Ph2
H
P
H
P
Ph2
4
5
Scheme 3.
and 1H NMR. Photolysis of 4 for 1 h at 300 nm showed the forma-
tion of the chelate ring in [Mo(CO)4(P,S-DTF)] complex and after
5 h of photolysis only 30% of 4 was converted into 5.
2.3. Manganese complexes
We studied also the group 7 carbonyl complexes using bromo-
pentacarbonylmanganese, [MnBr(CO)5] as precursor as substitu-
tion of two CO ligands can easily been performed [11]. First, we
investigated the reaction of 2 with half equivalent of Mn(CO)5Br
in refluxing dichloromethane for 7 h with the aim of preparing
the bisubstituted manganese complex [MnBr(CO)3(P-DTF)2]. After
purification by chromatography on silica gel column, the desired
complex [MnBr(CO)3(P-DTF)2] (6), was obtained in 40% yield as a
yellow precipitate. 31P NMR investigation of this precipitate shows
two signals at 41.6 and 21.3 ppm of different intensities indicating
likely the presence of two isomers. It is worthnoting that three iso-
meric forms can be envisioned for [MnBr(CO)3(P-DTF)2]: fac, mer-
cis and mer-trans [12]. 31P NMR investigation is a very convenient
tool for structural determination by comparison of the chemical
shift values with close derivatives [13]. Accordingly, we attributed
to the signal observed at 41.6 ppm the mer-trans-P–Mn–P isomer
and to the 21.3 ppm the fac-cis-P–Mn–P isomer (Scheme 5) [14].
The cis and trans configurations are also evident from the
1H NMR spectrum for the vinylogous proton which appears as a
doublet and resonates at 5.58 ppm (2JPH = 21 Hz) for the fac, cis
and 6.56 ppm (2JPH = 21 Hz) for the mer, trans. From the 1H NMR,
In order to check this point we also tried the formation of com-
plex 5 directly from Mo(CO)6 by using one equivalent of vinyl
phosphine 2 in the presence of two equivalents of Me3NO ꢀ 2H2O
in dichloromethane. Under these reaction conditions, after 3 h,
we were able to form 5 in 40% yield besides the formation of 4
in 20% yield and the formation of the bisubstituted complex cis-
[Mo(CO)4(P-DTF)2] in 30% yield (Scheme 4).
Photoreaction of metal carbonyl complexes is also a useful
route for inducing the loss of CO ligands. Therefore, UV irradiation
of 4 in a CDCl3 solution was realized and monitored by 31P NMR
Mo1
Mo1
P11
S2
S1
P1
C35
C33
C31
C34
C33
C32
S2
C31
C32
S3
Fig. 2. Molecular structures of 4 and 5. H atoms omitted for clarity. Ellipsoids are drawn at 50% probability.

2348
M. Guerro et al. / Journal of Organometallic Chemistry 693 (2008) 2345–2350
Me
Me
Me
Me
Me
Me
Mo(CO)6
S
S
S
S
S
S
cis-Mo(CO)4(P-DTF)2
Mo(CO)4
+
Scheme 4.
S
+
Me3NO.2H2O
Mo(CO)5
Ph2
H
PPh2
H
P
30%
H
P
Ph2
2
5 (40%)
4
(20%)
Me
Me
Me
Me
Ph
P
S
S
Ph
Ph
Ph
Me
Ph Ph
CO
Mn
Me
Br
P
Br
Mn
P
S
P
S
S
S
Me
Me
0.5 equiv Mn(CO)5Br
+
OC
OC
CO
OC
S
Ph
OC
Ph
6 mer,trans
Me
Me
6 fac,cis
S
S
Me
Me
Me
Ph
Me
H
PPh2
S
S
2
S
S
1 equiv Mn(CO)5Br
MnBr(CO)3
+
P
Ph
Ph
Ph
P
Mn(CO)4Br
8
7
Scheme 5.
we can determine a ratio 4:1 for those two isomers, the main iso-
mer being the mer, trans derivative. We were able to isolate 6 mer,
trans isomer by fractional crystallisation as this isomer is less sol-
uble in MeOH. IR investigation confirms also the structural assign-
ment, as it exhibited on the spectra three carbonyl bands, two
intense bands at 1943 and 1893 cmꢁ1 and a weaker and sharper
band at 2032 cmꢁ1 supportive with the mer, trans derivative. For
the fac, cis isomer three carbonyl bands of equal intensity were ob-
quired to oxidize the metal in those complexes, Mo(0) to Mo(+1)
and Mn(+1) to Mn(+2), are out of the limit of the working range
of dichloromethane. This might be attributed to the electron-with-
drawing effect of the oxidized phosphine coordinated to the metal-
lic center. Comparison of the oxidation peak potentials of the
various complexes with the one of the vinyl phosphine 2 shows
the influence of the nature of the metal and also of the mode of
coordination. For instance, for the Mo (Table 2) as well as for the
Mn (Table 3) series, the oxidation of the dithiafulvene core occurs
at a higher potential when it acts as a P,S-bidentate ligand than as a
monodentate P ligand. Similarly when two vinyl phosphines are
coordinated to the metallic center the electron-withdrawing effect
of the metal center is decreased. Moreover for the M(P-DTF)2, M(P-
DTF) and M(P,S-DTF) complexes it can be observed that the nature
and the oxidation state of the metal has also a significant effect on
the oxidation potential of the DTF moiety, as the Mn1+ complexes
exhibit higher oxidation potentials than the Mo complexes. Upon
recurrent scans, the cyclic voltammograms obtained for the vari-
ous complexes maintained the same shape, demonstrating the ab-
sence of any C–C coupling reactions.
served on the spectra at 2015, 1948 and 1899 cmꢁ1
.
Reaction of [MnBr(CO)5] with one equivalent of 2 in refluxing
CH2Cl2 for 3 h leads mainly to the monosubstituted complex 7,
[MnBr(CO)4(P-DTF)] in 56% yield after column chromatography.
Actually, investigation of the reaction medium by 31P NMR shows
two signals one at 27 ppm, assigned to complex 7, and another one
at lower field, 78.7 ppm attributed to complex 8 where 2 behaves
as a bidentate ligand towards Mn and form a chelate ring [15,16].
As previously observed for the molybdenum derivative described
above, the signal of the phosphorus atom in this five-membered
metallacycles is shifted of about 50 ppm downfield. In order to sep-
arate complex 8 from complex 7 we attempted chromatography on
silica gel, but we did not isolate 8 [MnBr(CO)3(P,S-DTF)] probably
due to the cleavage of the weaker link of the chelate ring, the
Mn–S bond.
Table 3
31P parameters and oxidation peak potentials for the manganese metal carbonyl
complexes
2.4. Electrochemistry
Compound
dP (ppm)
Epa (V) vs. SCE
P-DTF (2)
[Mn Br(CO)3(P,S-DTF)2] (6)
ꢁ13.2
0.73
0.80, 1.25
–
The redox behavior of the dithiafulvenes 1–3 as well as the dif-
ferent complexes was investigated by cyclic voltammetry in
dichloromethane. For all these derivatives, except for 6, only one
irreversible oxidation wave was observed on the voltammogram.
This oxidation wave is attributed to the oxidation of the dithiaful-
vene core into the cation radical. Presumably, the potentials re-
mer, trans 41.6
fac, cis 21.3
27.0
[Mn(CO)4Br(P-DTF)] (7)
[Mn(CO)3Br(P,S-DTF)] (8)
1.09
78.7
1.21a
a
Determined from a mixture of complexes 7 and 8 based on the data obtained
for 7.

M. Guerro et al. / Journal of Organometallic Chemistry 693 (2008) 2345–2350
2349
Table 4
Crystal data and structure refinement parameters for 1, 2, 3, 4 and 5
Structure parameter
1
2
3
4
5
Empirical formula
Molecular weight
C
18H20BPS2
C18H17PS2
328.41
C18H17PS3
360.47
C23H17MoPO5S2
564.4
C22H17MoPO4S2
536.39
342.24
Crystal system
Space group
a (Å)
b (Å)
c (Å)
a (°)
b (°)
orthorhombic
Pbca
12.9378(2)
16.3803(2)
16.5194(2)
90
monoclinic
C2/c
21.3825(6)
9.5756(2)
17.0144(4)
90
101.597(2)
90
3412.59(14)
293(2)
monoclinic
Pn
9.7597(4)
9.2355(4)
10.0459(4)
90
108.422(2)
90
859.09(6)
100(2)
triclinic
P1
monoclinic
P21/c
11.3306(2)
10.8819(2)
18.8649(3)
90
100.1857(7)
90
2289.35(7)
293(2)
ꢀ
8.4587(2)
11.7987(3)
12.9315(3)
71.8085(14)
86.6956(15)
81.6192(10)
1212.86(5)
293(2)
90
90
c (°)
V (Å3)
T (K)
3500.87(8)
120(2)
Z
8
8
2
2
4
Dcalc (g/cm3)
1.299
0.388
1.278
0.397
1.393
0.518
1.545
0.812
1.556
0.850
l (mmꢁ1
)
Total reflections
48360
7356
12370
18961
48124
Unique data (Rint
Observed reflections (I > 2r(I))
R1, wR2
R1, wR2 (all data)
Goodness-of-fit
)
4004 (0.0743)
3120
0.0365, 0.0813
0.0594, 0.0923
1.092
3874 (0.0289)
3051
0.0525, 0.1465
0.0660, 0.1573
1.050
3308 (0.0236)
3283
0.0194, 0.0515
0.0192, 0.0515
1.081
5277 (0.0455)
3734
0.0312, 0.0619
0.0621, 0.0745
1.069
5186 (0.0296)
4591
0.0222, 0.0573
0.0275, 0.0607
1.047
2
CH3), 1.94 (s, 3H, CH3), 5.90 (d, H, CH, JPH = 14 Hz), 7.3–7.9 (m,
3. Conclusions
10H, Ar); 13C RMN (75 MHz, CDCl3) d = 12.7, 13.5, 93.9 (d, JPC
=
2
97.4 Hz), 121.5, 124.9, 128.4, 128.6, 131.0, 131.1, 131.2, 131.3,
To summarize, we have investigated the coordinating ability of
the electroactive dithiafulvenyl phosphine towards Mo(CO)6 and
MnBr(CO)5 complexes. In both cases we have formed a new series
of mononuclear complexes with this hemilabile ligand and have
shown that, no matter the nature of the metallic center, it readily
reacts as a monodentate (P) ligand and also forms P,S-chelate com-
plexes if a coordination site is available for the ring closure. Com-
parison of the Mn complexes formed with the Mo complexes
shows that in general they are less stable even if their oxidation
potentials occur at higher potentials.
2
133.5, 134.7, 159.7 (d, JPC = 16.5 Hz); 31P NMR (121 MHz,CDCl3)
d = 32.1; HRMS calcd for C18H17PS3: 360.0230. Found: 360.0228.
4.2.2. Mo(CO)5(P-DTF) (4) and cis-Mo(CO)4(P,S-DTF) (5)
To a solution of phosphine 2 (1 g, 3 mmol) in 15 mL of dry and
degassed decahydronaphtalene added (790 mg, 3 mmol) of
Mo(CO)6 and the reaction mixture was heated to 150 °C for
30 min under nitrogen. The heterogeneous medium becomes rap-
idly an homogeneous solution. The solvent was removed under re-
duced pressure and the residue was chromatographied over silica
gel using CH2Cl2/pentane (1/5) as eluent. Mo(CO)5(P-DTF) (4) was
obtained in 44% yield as white crystals and cis-Mo(CO)4(P,S-DTF)
(5) was obtained in 5% yield as white crystals.
4. Experimental
4.1. General
1H NMR, 31P NMR and 13C NMR spectra were recorded on Bruker
AC 300P spectrometers. Chemical shifts are reported in ppm refer-
enced to TMS for 1H NMR and 13C NMR and to H3PO4 for 31P NMR.
Melting points were measured using a Kofler hot stage apparatus.
Elemental analyses results and Mass spectra were performed by
the Centre Régional de Mesures Physiques de l’Ouest, Rennes.
Methanol was distilled from calcium and dichloromethane from
P2O5. Chromatography were performed using silica gel Merck 60
(70–260 mesh). The vinyl phosphine borane 1 and the vinyl phos-
phine 2 were prepared according to previously published proce-
4.2.3. Mo(CO)5(P-DTF) (4)
m.p. 164 °C; 1H NMR (300 MHz; CDCl3) d = 1.86 (s, 3H, CH3),
2
1.96 (s, 3H, CH3), 6.17 (d, 1H, CH, JPH = 14 Hz), 7.30–7.60 (m,
10H, Ar); 13C NMR (75 MHz, CDCl3) d = 12.9, 13.5, 99.9 (JPC
=
160 Hz), 122.9, 123.8, 128.6, 128.7, 129.9, 132.0, 132.1, 134.6,
135.1, 152.0, 205.8, 210.5; 31P NMR (121 MHz; CDCl3) d = 24.1; IR
(cmꢁ1
C
)
m(CO)
23H17MoO5PS2: C, 48.94; H, 3.04; S, 11.36. Found: C, 48.85; H,
3.01; S, 11.50%.
: 1904, 1924, 1987, 2027, 2067; Anal. Calc. for
dures [6]. Cyclic voltammetry were carried out on a 10ꢁ3
M
4.2.4. cis-Mo(CO)4(P,S-DTF) (5)
m.p. 166 °C; 1H NMR (300 MHz; CDCl3) d = 2.07 (s, 3H, CH3),
solution of the derivatives in dichloromethane, containing a 0.1 M
nBu4NPF6 as the supporting electrolyte. Voltammograms were re-
corded at 0.1 V sꢁ1 at a platinum disk electrode (A = 1 mm2). The
potentials were measured vs. Saturated Calomel Electrode.
2
2.09 (s, 3H, CH3), 6.54 (d, 1H, CH, JPH = 0.9 Hz), 7.40–7.60 (m,
10H, Ar); 31P NMR (121 MHz; CDCl3) d = 62.4; IR (cmꢁ1) m(CO)
:
1876, 1897(br), 2022; HRMS (FAB): Calc. for C22H17MoO4PS2
537.9360. Found: 537.9373.
4.2. Synthesis and characterization
4.2.5. [MnBr(CO)3(P-DTF)2] (6)
To a solution of vinyl phosphine 2 (0.16 g, 0.5 mmol) in 3 mL of
dry and degassed CH2Cl2 was added (70 mg, 0.25 mmol) of
BrMn(CO)5. The reaction mixture was heated to reflux for 7 h. After
evaporation of the solvent the residue was chromatographied on
silica gel column using CH2Cl2:pentane (1:1) as eluent. The com-
plex 6, MnBr(CO)3(P-DTF)2 was obtained as a mixture of two iso-
mers in 40% yield. The mer, trans isomer was isolated by
fractional crystallisation as this isomer is less soluble in MeOH.
4.2.1. [(4,5-dimethyl-1,3-dithiol-2-ylidene)methyl](diphenyl)phosphine
sulphide (3)
To a solution of 2 (0.32 g, 1 mmol) in 15 ml of dry and degassed
dichloromethane sulfur S8 (0.07 g, 2 mmol) was added under nitro-
gen. The reaction mixture was stirred at room temperature for 16 h
and the solvent was removed in vacuo. Recrystallisation of the pre-
cipitate in ethylacetate: diethylether leads to 3 as white crystals in
88% yield. m.p. = 181 °C; 1H NMR (300 MHz, CDCl3) d 1.90 (s, 3H,

2350
M. Guerro et al. / Journal of Organometallic Chemistry 693 (2008) 2345–2350
m.p. = 165 °C; 1H NMR (300 MHz, CDCl3) d = 1.69 (s, CH3, 6H), 1.87
ated with this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2008.04.011.
2
(s, CH3, 6H), 6.56 (d, 2H, JPH = 21 Hz), 7.30–7.90 (m, Ar, 20H); 31P
NMR (121 MHz, CDCl3) d = 41,6; IR (KBr) mCO = 2032 (w), 1943(s),
1893(s) cmꢁ1; The fac, cis isomer 1H NMR (300 MHz, CDCl3) d =
2
References
1.68 (s, CH3, 6H), 1.89 (s, CH3, 6H), 5.58 (d, 2H, CH, JPH = 21 Hz),
7.30–7.90 (m, Ar, 20H); 31P NMR (121 MHz, CDCl3) d = 23.4 ppm;
IR (KBr) mCO = 2015 (s), 1948(s), 1899(s) cmꢁ1; HRMS calcd for
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C
39H34BrMnO3P2S4: [MꢁBr]+: 795.0246. Found: 795.0213.
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4.2.6. [MnBr(CO)4(P-DTF)] (7)
To a solution of vinyl phosphine 2 (0.20 g, 0.6 mmol) in 5 mL of
dry and degassed CH2Cl2 was added (165 mg, 0.6 mmol) of
BrMn(CO)5. The reaction mixture was heated to reflux for 2 h.
Investigation of the medium by 1H NMR and 31P NMR allowed us
to determine the spectroscopic characteristics of 8 [MnBr(CO)3-
(P,S-DTF)] 1H NMR (300 MHz, CDCl3) d = 1.72 (s, CH3, 3H), 1.90 (s,
CH3, 3H), 6,65 (d, JPH = 0.3 Hz), 7.20–7.60 (m, 10H, Ar); 31P NMR
(121 MHz, CDCl3) d = 78 ppm; After evaporation of the solvent
the residue was chromatographied on silica gel column using
CH2Cl2:pentane (1:2) as eluent. The complex 7, [MnBr(CO)4(P-
DTF)] was obtained as an orange powder in 56% yield. m.p. =
144 °C; 1H NMR (300 MHz, CDCl3) d = 1.79 (s, CH3, 3H); 1.96 (s,
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1
CH3, 3H); 6.42 (d, 1H, JPH = 21 Hz), 7.40–7.90 (m, 10H, Ar); 31P
NMR (121 MHz, CDCl3) d = 27; IR (KBr) mCO = 1956, 1999 cmꢁ1
;
HRMS calcd for C22H17O4BrPS2Mn: 573.8869. Found: 573.8862.
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4.3. Crystallography
Single-crystal diffraction data were collected on Nonius Kap-
paCCD diffractometer for compounds 1, 2 and 4 and on APEX II
Bruker AXS diffractometer for compounds 3 and 5 (Centre de Dif-
fractométrie X, Université de Rennes, France). Details of the crys-
tallographic are given in Table 4.
Appendix A. Supplementary material
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55.
CCDC 682242, 682243, 682244, 682245 and 682246 contain the
supplementary crystallographic data for 1, 2, 3, 4 [Mo(CO)5(P-DTF)]
and 5 [Mo(CO)4(P,S-DTF)]. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-