New studies on the chemical oxidation of (bisη5-cyclopentadienyl)dithiolatemolybdenum(IV) complexes. Crystal structures of [Mo(η5-C5H5)2S(C 6H4-o-SC6H5)][BF4] and [Mo(η5-C5H5)2(SC 6H5)2]

Article abstract of DOI:10.1016/S0022-328X(01)01038-5

A new pattern on the reactivity of bis(η⁵-cyclopentadienyl)dithiolatemolybdenum(IV) metalloligands was found upon study of several chemical reactions involving the redox behaviour of these compounds. Chemical oxidants, such as Ag⁺ and NO⁺, led to very different monochelate and binuclear final products. The molecular structure of the new compound which contains the metalloring cation [Mo(η⁵-C₅H₅)₂S(C ₆H₄-o-SC₆H₅)]⁺ was characterised by single-crystal X-ray diffraction, and for comparison, also the molecular structure of the parent compound [Mo(η⁵-C₅H₅)₂(SPh)₂] is also presented and discussed.

Full text of DOI:10.1016/S0022-328X(01)01038-5

Journal of Organometallic Chemistry 632 (2001) 107–112
www.elsevier.com/locate/jorganchem
New studies on the chemical oxidation of
bis(h5-cyclopentadienyl)dithiolatemolybdenum(IV) complexes.
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
Crystal structures of [Mo(h5-C5H5)2S(C6H4-o-SC6H5)][BF4] and
[Mo(h5-C5H5)2(SC6H5)2]
Alberto R. Dias a, M. Helena Garcia a,b,*, M. Fa´tima Minas da Piedade a,b,
M.A.A.F. de C.T. Carrondo c,*
a Centro de Qu´ımica Estrutural, Instituto Superior Te´cnico, A6. Ro6isco Pais, 1096 Lisbon codex, Portugal
b Faculdade de Cieˆncias da Uni6ersidade de Lisboa, C1, R. Ernesto de Vasconcelos, 1700 Lisbon, Portugal
c Instituto de Tecnologia Qu´ımica e Biolo´gica, R. da Quinta Grande 6, 2780 Oeiras, Portugal
Received 21 February 2001; accepted 30 April 2001
Dedicated to Professor A.R. Dias on the occasion of his 60th birthday
Abstract
A new pattern on the reactivity of bis(h5-cyclopentadienyl)dithiolatemolybdenum(IV) metalloligands was found upon study of
several chemical reactions involving the redox behaviour of these compounds. Chemical oxidants, such as Ag+ and NO+, led to
very different monochelate and binuclear final products. The molecular structure of the new compound which contains the
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
metalloring cation [Mo(h5-C5H5)2S(C6H4-o-SC6H5)]+ was characterised by single-crystal X-ray diffraction, and for comparison,
also the molecular structure of the parent compound [Mo(h5-C5H5)2(SPh)2] is also presented and discussed. © 2001 Elsevier
Science B.V. All rights reserved.
Keywords: Molybdenocenes; Thiolates; Oxidation reactions; Cyclic voltammetry; Crystal structures
1. Introduction
exploitation of their redox chemistry using a mild
chemical oxidant such as a ferrocenium salt led to the
synthesis of a new family of cationic monothiolate-re-
lated compounds with the general formula [M(IV)(h5-
C5H5)2 (SR)L][PF6], where L is a nucleophile such as
NCCH3, PPh3, NH3, CO, etc. [3]. Moreover, our fur-
ther studies in this field revealed that M(IV)(h5-C5H5)2
(SR)2 also could be involved in more complicated redox
reactions, and we were able to characterise by X-ray
diffraction a new bimetallic MoIII structure, containing
one fulvalene and one ꢀSC6H−5 group both acting as
bridging ligands, obtained upon the reaction of
[M(IV)(h5-C5H5)2(SC6H5)2] with [Re2(CO)10] [4]. Sur-
prisingly, the analogous reaction with [Mn2(CO)10], led
to an unusual manganese(I) cubane-type with an empty
corner structure, formed by Mn(I)(CO)3 metal frag-
ments bridged by ꢀSC6H−5 thiolate ligands, which was
also characterised by X-ray diffraction studies [5].
The chemistry of bent metallocene derivatives of the
general formula [M(h5-C5H5)2(SR)2] (M=Mo(IV),
W(IV), Ti(IV); R=alkyl or aryl) was for many years
related exclusively with their use as chelating ligands in
the synthesis of different polynuclear complexes
through thiolate bridges [1].
Our studies on the electrochemistry of these metal-
loligands by means of cyclic voltammetry showed that
they could be easly oxidised, with formation of new
stabilised species [2]. These studies suggested to us a
new approach on the reactivity of these bisthiolates,
besides their use as bidentate ligands. In fact, the
* Corresponding authors. Tel.: +351-21-8419317; fax: +351-21-
8464455/7.
E-mail address: lena.garcia@ist.utl.pt (M. Helena Garcia).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01038-5

108
A.R. Dias et al. / Journal of Organometallic Chemistry 632 (2001) 107–112
2.1.4. Spectroscopic characterisation of
These unexpected results led us to pursue the study
[Mo(IV)Cp2(v-(SC6H5)2Mo(III)Cp(NO)][BF4]2
of new redox reactions in order to get a better under-
standing on the reactivity of these bisthiolate metalloli-
gands; and we present in this paper, reactions involving
oxidants stronger than ferrocenium cations, namely
Ag+ and NO+. In the cases studied, new unexpected
structures were found.
The NO (three-electron donor) ligand was identified
as a linear end-group on the basis of the IR spectrum,
which showed w(NO)=1660 cm−1, in good agreement
with the studies of Lewis and Wilkinson [6,7]. The
1H-NMR spectrum at room temperature, in a CD3CN
solution, displayed three typical sharp Cp singlets, with
chemical shifts of 6.397, 6.194 and 5.284 ppm, and two
additional multiplets centered at 7.610 and 7.690 ppm,
corresponding to phenyl proton rings, with the relative
intensities of 5:5:5:3:2, respectively. The existence of
two different Cp signals attributed to the fragment
MoCp2(IV)(m-SC6H5)2 suggests a cis-structure for this
bimetallic complex. Variable temperature 1H-NMR
studies showed some broadening on the phenyl multi-
plets at −30 °C, that can be explained by a cis–trans
isomerisation equilibrium, involving pyramidal inver-
sion at the sulfur centres, which was also found for
other sulfur derivatives [8]. The stability observed for
this new compound might be explained by a metal–
metal interaction, providing the 18-electron configura-
tion, to both metals. Our electrochemical studies by
means of cyclic voltammetry, in 10−3 M CH3CN solu-
tions, showed a quasi-reversible wave at Ep1/2=0.99 V
(DE=90 mV), which was assigned to MoIV“MoV
oxidation on the Mo(IV)Cp2(m-SC6H5)2 moiety, accord-
ing to our knowledge of this family of compounds [1,2].
Moreover, a second quasi-reversible redox process at
Ep1/2=0.05 V (DE=90 mV), was found compatible
with the MoIII“MoIV oxidation occurring at the
Mo(III)Cp(NO) moiety.
2. Results and discussion
2.1. Chemical studies
2.1.1. Chemical oxidation of
[Mo(IV)(p5-C5H5)2(SC6H5)2] with AgBF4
The reaction was carried out in a non-coordinative
solvent (CH2Cl2), by addition of the molar equivalent
of AgBF4 to a stirred suspension of [Mo(IV)(h5-
C5H5)2(SR)2], at room temperature. A deep orange–
brown solution was formed almost instantaneously
producing, after work up, a very stable orange crys-
talline compound. Slow diffusion of diethyl ether on
this filtered solution, afforded red single crystals suit-
able for X-ray diffraction studies.
2.1.2. Spectroscopic characterisation of
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
[Mo(h5-C5H5)2S(C6H4-o-SC6H5)][BF4]
1
The H-NMR spectrum of the studied compound in
CD3CN solutions displayed multiplet signals in the
aromatic region, characteristic of ortho-disubstituted
phenyl rings at 7.01, 7.19, 7.34 and 7.65 ppm (relative
integrals, 1:1:1:1), together with two multiplets at-
tributed to the thiolate ligand at 7.42 and 7.54 ppm
(relative integrals, 2 and 3, respectively). To this new
Unfortunately, the slow decomposition in acetonitrile
solutions (the only solvent found to dissolve the com-
pound) did not allow to grow adequate crystals for
X-ray diffraction studies to confirm this structure.
compound
was
attributed
the
formulation
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
[Mo(h5-C5H5)2S(C6H4-o-SC6H5][BF4], which was also
in good agreement with the 1:1 electrolyte behaviour of
a 10−3 M solution of the pure compound in ni-
tromethane (molar conductivity=76 V−1 cm2 mol−1).
2.1.5. Spectroscopic characterisation of
[Mo(IV)Cp2(v-(StBu)2Mo(III)Cp(NO)][BF4]2
The stretching vibration band attributed to the NO
group was found at 1585 cm−1, a value in the frontier
between the linear NO and NO bent structures. The
bent structure could be explained, in this case, by the
existence of Mo“NO p backdonation as was found
for MoCp(NO)(Me2CHCHMe2) [9] and MoCp(NO)-
(CH2C6H2-2,4,6-Me3)2 [10], due to the better donor
2.1.3. Chemical oxidation of [Mo(IV)(p5-C5H5)2(SR)2]
(R=C6H5 and Bu) with NOBF4
t
To a suspension of NOBF4 in dichloromethane, was
added one equivalent of the corresponding bisthiolate.
The reaction was found to occur almost instanta-
neously with the formation of an orange precipitate, in
the case of [Mo(IV)(h5-C5H5)2(SC6H5)2], and a deep-red
solution in the case of [Mo(IV)(h5-C5H5)2(StBu)2]. To
both new compounds, was attributed the binuclear
[Mo(IV)Cp2(m-(SR)2Mo(III)Cp(NO)][BF4]2 structure,
on the basis of the IR and 1H-NMR spectroscopic data,
molar conductivities (ꢀ165 V−1 cm2 mol−1, as ex-
pected for 2:1 electrolytes) and elemental analysis.
t
properties of Bu, compared with the phenyl group.
However, our experimental data supports the existence
of NO as a three-electron donor ligand, slightly bent as
a result of the bulky StBu bridging ligands, lowering the
NO stretching vibration energy. The influence of the
bulky StBu ligands on the structure of the new bimetal-
lic species is also present in the 1H-NMR data spectrum
obtained at room temperature in a CD2Cl2 solution,
which presented only one sharp singlet at 6.197 ppm
attributed to the MoCp2(m-StBu)2 moiety and the ex-

A.R. Dias et al. / Journal of Organometallic Chemistry 632 (2001) 107–112
109
pected singlet for Mo(III)Cp(NO) fragment at 6.092
ppm (relative intensities 2:1). Therefore, the existence of
two equivalent Cp rings in MoCp2(m-StBu)2 can be
explained by the adopted trans-structure, converse to
the analogous SPh-bridged compound.
Fig. 3. ORTEP drawings of the two independent molecules in the
asymmetric unit in the crystal structure of [Mo(h5-C5H5)2S(C6H5)2]
with the labelling scheme used (ellipsoids with 40% probability level).
The hydrogens are omitted for clarity.
2.2. Crystallographic studies
¸¹¹¹¹¹¹¹¹¹¹¹º
Fig. 1. An ORTEP view of cation [Mo(h5-C5H5)2S(C6H4)SC6H5][BF4],
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
with the labelling scheme used. The ellipsoids were drawn with 40%
probability level. The hydrogens are omitted for clarity.
2.2.1. Structures of [Mo(h5-C5H5)2S(C6H4-o-SC6H5)]-
[BF4] and [Mo(h5-C5H5)2(SC6H5)2]
X-ray diffraction studies, carried out on a single
crystal obtained by slow diffusion of diethyl ether in a
dilute dichloromethane solution of the pure compound,
confirm the structure suggested by our spectroscopic
data, and the presence of a dithioaryl fragment un-
evenly chelated to the metal centre, forming a five-
member metalloring, as shown in Fig. 1. This
five-member metalloring is clearly on the same plane as
the disubstituted phenyl group (showing a dihedral
angle between the plane S–Mo–S and the phenyl group
of 2.2(3)°). The structural study confirmed the presence
of a BF−4 anion. The values of selected bond lengths
and bond angles for the complex are given in Table 1.
For comparison, Fig. 2 represents the molecular dia-
gram of the bisthiolate starting material Mo(h5-
C5H5)2(SC6H5)2 along the plane defined by SꢀMoꢀS,
showing also one of the phenyl groups in the equatorial
plane almost bisecting the angle defined by the Mo(h5-
C5H5)2 fragment. The molecular structure of
MoCp2(SC6H5)2 is shown in Fig. 3 which has two
independent molecules per asymmetric unit. The struc-
tural parameters of each individual MoCp2(SPh)2
molecule are essentially the same (Table 2). The crystal
packing diagram of this compound indicates a rela-
Table 1
,
Selected bond lengths (A) and bond angles (°) for
¸¹¹¹¹¹¹¹¹¹¹¹¹º
[Mo(h5-C5H5)2S(C6H4-o-SC6H5][BF4]
Bond lengths
Mo(1)ꢀS(11)
Mo(1)ꢀS(12)
Mo(1)ꢀCp(11)
Mo(1)ꢀCp(2)
S(11)ꢀC(112)
S(12)ꢀC(111)
S(12)ꢀC(121)
2.447(2)
2.496(2)
1.984(8)
1.944(5)
1.757(7)
1.788(6)
1.793(6)
Bond angles
S(11)ꢀMo(1)ꢀS(12)
C(112)ꢀS(11)ꢀMo(1)
C(111)ꢀS(12)ꢀC(121)
C(111)ꢀS(12)ꢀMo(1)
C(121)ꢀS(12)ꢀMo(1)
C(112)ꢀC(111)ꢀS(12)
C(111)ꢀC(112)ꢀS(11)
C(113)ꢀC(112)ꢀS(11)
Cp(1)ꢀMo(1)ꢀCp(2)
82.93(7)
106.0(2)
102.1(3)
106.7(2)
116.1(2)
118.7(5)
125.5(5)
117.0(6)
135.4(6)
,
tively close interaction (within 2.80(1) A) of a hydrogen
on a Cp ring with a sulfur of an adjacent molecule,
similar to that found in the structure of the
NbCp2(SPh)2 [11].
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
In both complexes, [Mo(h5-C5H5)2S(C6H4-o-SC6H5]-
[BF4] and [Mo(h5-C5H5)2(SC6H5)2], the metal is coordi-
Fig. 2. Molecular diagram of [Mo(h5-C5H5)2S(C6H5)2] along the
plane defined by S–Mo–S atoms.

110
A.R. Dias et al. / Journal of Organometallic Chemistry 632 (2001) 107–112
Table 2
5
,
Bond lengths (A), bond angles (°) and torsion angles (°) for [Mo(h -
C5H5)2SC6H5)2][BF4]
Molecule 1
Molecule 2
Bond lengths
Mo(1)ꢀS(11)
Mo(1)ꢀS(12)
2.470(2) Mo(2)ꢀS(21)
2.505(2) Mo(2)ꢀS(22)
2.494(2)
2.463(2)
Mo(1)ꢀCp(C11–C15)) 1.988(6) Mo(2)ꢀCp(C21–C25) 1.984(6)
Mo(1)ꢀCp(C16–C20) 1.989(6) Mo(2)ꢀCp(C26–C30) 2.002(8)
S(11)ꢀC(111)
S(12)ꢀC(121)
1.769(8) S(21)ꢀC(211)
1.760(9) S(22)ꢀC(221)
1.786(8)
1.776(8)
Fig.
4.
Numbering
scheme
for
1H-NMR
of
cation
¸¹¹¹¹¹¹¹¹¹¹¹º
Bond angles
S(11)ꢀMo(1)ꢀS(12)
CpꢀMo(1)ꢀCp
C(111)ꢀS(11)ꢀMo(1) 115.9(3) C(211)ꢀS(21)ꢀMo(2)
C(121)ꢀS(12)ꢀMo(1) 108.9(3) C(221)ꢀS(22)ꢀMo(2)
[Mo(h5-C5H5)2S(C6H4)SC6H5]+
.
73.17(7) S(22)ꢀMo(2)ꢀS(21)
132.3(4) CpꢀMo(2)ꢀCp
73.56(7)
134.6(4)
110.2(2)
113.8(3)
180°, (see Table 2) confirming the exo configuration
expected by electronic factors at the molybdenum atom
and predicted by theoretical calculations [13].
Torsion angles
S(12)ꢀMo(1)ꢀS(11)ꢀ 174.4(3) S(22)ꢀMo(2)ꢀS(21)ꢀ −170.9(3)
C(111) C(211)
S(11)ꢀMo(1)ꢀS(12)ꢀ 168.1(3) S(21)ꢀMo(2)ꢀS(22)ꢀ −173.1 (4)
C(121) C(221)
It might be suggested, by comparison of both crystal
structures shown in Figs. 1 and 2, that the exo structure
adopted by the bisthiolate starting material might con-
tribute to the stabilisation of any possible reactional
intermediate species leading to the formation of the
second co-planar sulfur metalloring.
nated to two h5-cyclopentadienyl rings and two sulfur
atoms of the thiolate ligands, showing the typical struc-
tures of metallocene complexes in a tetrahedral dis-
torted geometry. The structural parameters are similar
to molybdenocenes with thiolate ligands found in the
Cambridge Structural Database [12], as can be seen in
Table 3.
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
The formation of the new [Mo(h5-C5H5)2(SC6H4-o-S-
C6H5]+ cationic species by oxidation of the parent
bisthiolate shows a new pattern for the reactivity of
these compounds involving the coordinate thiolate
groups, where the sulfur atom plays an active role
towards the final product. In fact, this is the very first
case, in all our studies concerning redox reactions on
[M(IV)(h5-C5H5)2(SR)2] compounds, where the reaction
Each one of the independent molecules of MoCp2-
(SPh)2 displays a torsion angle RꢀSꢀMoꢀS close to
Table 3
Structural data for molybdenocenes with bisthiolates ligands
MoꢀS
SꢀMoꢀL
CpꢀMo
CpꢀMoꢀCp
SꢀMoꢀSꢀC
173.3/173.5
ref. code
MoCp2(StBu)2
2.501
71.06
2.014/1.999
130.4
BIGPAI10
2.491
MoCp2(SPh)(NH3)]PF6]·CH3COCH3
MoCp2(SPh)(p-NC(C6H4)NMe2)][PF6]
MoCp2(SPh)(s-CH(CN)CH3)
MoCp2(S2C6H3CH3)]
2.467
2.473
2.500
2.435/2.430
2.450
76.7
79.8
77.4
82.4
88.2
1.988/1.989
1.986/1.989
1.982/1.987
1.992/1.999
2.002
134.8
137.0
132.9
132.5
134.2
−178.7
−171.4
−156.1
–
JAFNIN
JILHAN
DIGKIN
CPDTMO10
CPMOTS
MoCp2(S4)
–
2.456
1.997
MoCp2(S2C2(2-quinoxalina)(C(O)Me)]
[MoCp2(S(CH2)2NH2)[I]
[MoCp2(2,3-S,S-C4H3CONEt2)]
[MoCp2(o-S,S-C4S2H2)]
2.436
2.438
2.439
81.94
78.4
1.998
1.990
1.977
2.001
1.997
1.998
1.970
2.018
1.988(6)
1.989(6)
1.984(6)
2.002(8)
1.984(8)
1.944(5)
135.1
130.9
132.6
131.9
–
–
–
–
KOLRAE
CPMOAE
LEHQUK
ZOLLAN
This work
2.431
2.424
2.436/2.440
81.98
81.91
MoCp2(SPh)2
2.470(2)
2.505(2)
2.494(2)
2.463(2)
2.447(2)
2.496(2)
73.17(7)
73.56(7)
132.3(4)
134.6(4)
174.4(3)
168.1(3)
−170.9(3)
−173.1(4)
–
¸¹¹¹¹¹¹¹¹º
[MoCp2S(C6H4-o-SC6H5][BF4]
73.17(7)
135.4(6)
This work

A.R. Dias et al. / Journal of Organometallic Chemistry 632 (2001) 107–112
111
proceeds without de-coordination of the thiolate lig-
ands, being the final product apparently formed
through an intramolecular reaction.
In addition to the well-known oxidation of
MCp2(SR)2 with the mild ferrocinium oxidant, this
work shows two different patterns of reactivity with
strong oxidising reagents.
was filtered, washed with Et2O, and dried in vacuo. The
compound was insoluble in acetone, CH2Cl2, Et2O,
EtOH, THF, hexane, pentane and toluene, but it was
moderately soluble in MeCN. Yield, 45%. Anal.
Found: C, 40.47; H, 3.31; N, 1.87; Mo, 24.56. Calc. for
C27H25NOS2B2F8Mo2: C, 40.08; H, 3.31; N, 1.73; Mo,
23.71%. IR (KBr, cm−1): w(C5H5) 3100; w(C6H5) 3040;
Indeed, the stronger oxidant Ag+ gave a mononu-
clear biscyclopentadienyl structure, where a dithioaryl
chelate ligand was formed, while the stronger and coor-
dinative oxidant, NO+, gave dimolybdenum thiolate-
bridged compounds, where a Cp ring in one of the
fragments MoCp2 is substituted by NO.
1
w(NO) 1660; w(BF4) 1100. H-NMR (MeCN-d3): l 5.24
(s, 5H, h5-C5H5), 6.19 (s, 5H, h5-C5H5), 6.39 (s, 5H,
h5-C5H5), 7.61 (m, 6H, 2×SC6H5-meta, para), 7.69 (m,
4H, 2×SC6H5-ortho).
3.4. Synthesis of
[MoCp2(IV)(v(StBu)2Mo(III)Cp(NO)][BF4]2
3. Experimental
To a solution of [MoCp2(StBu)] (0.3 g, 0.74 mmol) in
CH2Cl2, was added NOBF4 (0.098 g, 0.84 mmol). A
change of colour from red to grenat was observed
immediately. The mixture was stirred at r.t. for 2 h.
After filtration, Et2O was added yielding a precipitate
which was filtered, washed with ether and dried in
vacuo. Yield, 45%. Anal. Found: C, 40.50; H, 4.51; N,
1.63; S, 9.47. Calc. for C23H33NOS2BF4Mo2: C, 40.49;
H, 4.87; N, 2.05; S, 9.40%. IR (KBr, cm−1): w(C5H5)
3110; w(CH3) 2950–2880; w(NO) 1585; w(BF4) 1100.
1H-NMR (CH2Cl2-d2): l 1.47 (s, 18H, S(CH3)3), 6.09 (s,
5H, h5-C5H5), 6.19 (s, 10H, h5- C5H5).
3.1. General procedures
All experiments were carried out under nitrogen by
the use of standard Schlenk-tube techniques. Solvents
were purified according to the usual methods [14].
Solid-state IR spectra were measured on a Perkin–
Elmer 457 spectrophotometer, with KBr pellets; only
significant bands are cited in the text.
1H-NMR spectra were recorded on a Bruker CXP
300 spectrometer, at probe temperature. Microanalyses
were performed, in our laboratories, using a Fisons
Instruments EA1108 system. Data acquisitions, integra-
tion and handling were performed using a PC with the
software package Eager-200 (Carlo Erba Instruments).
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
3.5. X-ray analysis of [Mo(p5-C5H5)2S(C6H4-o-S-
1
C6H5][BF4] and [Mo(p5-C5H5)2(SC6H5)2]
The H-NMR (MeCN-d3 and CHCl3-d) chemical shifts
are reported in parts per million downfield from inter-
nal Me4Si.
Diffraction data for both the complexes,
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
[Mo(h5-C5H5)2S(C6H4-o-SC6H5][BF4] and [Mo(h5-
C5H5)2(SC6H5)2], were obtained at 298 K on an Enraf–
Nonius TURBOCAD4 diffractometer with graphite
monochromatised Mo–Ka radiation using a ꢀ–2q scan
technique. Unit cell dimensions and the orientation
matrix were obtained by least-squares refinement of 25
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
3.2. Synthesis of [Mo(p5-C5H5)2S(C6H4-o-SC6H5][BF4]
To a solution of [Mo(h5-C5H5)2S(C6H5)2] (0.4 g, 0.9
mmol), in CH2Cl2, was added AgBF4 (0.175 g, 0.9
mmol). The solution became immediately dark-red. Af-
ter a 30 min period stirring, the light-brown solution
was filtered, leaving a precipitate and a thin glass
mirror in the Schlenk tube. Slow diffusion of Et2O in
this solution produces orange-reddish crystals suitable
centred
reflections
with
8.1BqB15.4°
for
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
[Mo(h5-C5H5)2S(C6H4-o-SC6H5][BF4] and with 14.0B
qB16.8° for [Mo(h5-C5H5)2(SC6H5)2]. Using the
MOLEN software [15], data were corrected for Lorentz
and polarization effects and for absorption using exper-
imental „-scans.
1
for X-ray diffraction studies. H-NMR (MeCN-d3): l
5.44 (s, 10H, h5-C5H5), 7.01 (m, 1H, H3%), 7.19 (m, 1H,
H2%), 7.34 (dd, 1H, H4%, JHH=7.9, 1.2 Hz), 7.42 (m,
2H, H1, H5), 7.54 (m, 3H, H2, H3, H4), 7.65 (dd, 1H,
H1%, JHH=7.9, 1.2 Hz) Fig. 4.
The structures were solved by a combination of
direct methods and Fourier synthesis and then refined
by full-matrix least-squares on F2.
Non-hydrogen atoms were anisotropically refined
and all hydrogen atoms were inserted in calculated
positions and refined isotropically with a thermal
parameter equal to 1.2 times that of the carbon atoms
to which they are bonded. In both the structures, the
thermal parameters of the carbon atoms of one of the
3.3. Synthesis of
[MoCp2(IV)(v(SC6H5)2Mo(III)Cp(NO)][BF4]2
To a solution of NOBF4 (0.105 g, 0.9 mmol) in 20 ml
of CH2Cl2, was added [Mo(h5-C5H5)2S(C6H5)2] (0.4 g,
0.9 mmol), at room temperature (r.t.). The suspension
was stirred for 2 h, and the orange solid precipitated

112
A.R. Dias et al. / Journal of Organometallic Chemistry 632 (2001) 107–112
Table 4
Crystal
Data Centre, CCDC nos. 157905 and 157906, for the
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
data
and
structure
refinement
parameters
for
compounds [Mo(h5-C5H5)2S(C6H4-o-SC6H5][BF4] and
¸¹¹¹¹¹¹¹¹¹¹¹¹º
[Mo(h5-C5H5)2S(C6H4-o-SC6H5][BF4] and [Mo(h5-C5H5)2(SC6H5)2]
[Mo(h5-C5H5)2(SPh)2], respectively. Copies of this in-
formation may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ
UK (Fax: +44-1223-336033; e-mail: deposit@ccdc.
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
¸¹¹¹¹¹¹¹¹¹¹¹¹º
[Mo(h5-C5H5)2S(C6H4-o-S- [Mo(h5-C5H5)2-
C6H5][BF4]
(SC6H5)2]
Empirical formula
Formula weight
C22H19BF4MoS2
530.24
C44H40Mo2S4
888.88
,
Wavelength (A)
0.71069
Monoclinic
P21/c
0.71069
Orthorhombic
Pbca
Crystal system
Space group
Acknowledgements
Unit cell dimensions
,
a (A)
10.977(2)
8.603(5)
22.094(5)
91.24(2)
2086.0(14)
4
13.828(2)
21.766(2)
24.830(2)
–
7473.3(14)
8
,
b (A)
This research was financially supported by Junta
Nacional de Investigac¸a˜o Cient´ıfica e Tecnolo´gica.
,
c (A)
i (°)
V (A )
3
,
Z
Dcalc (g m−3
Absorption
)
1.688
0.871
1.580
0.927
References
coefficient (mm−1
)
[1] (a) A.R. Dias, M.L.H. Green, J. Chem. Soc. A (1971) 1951;
(b) A.R. Dias, M.L.H. Green, J. Chem. Soc. A (1971) 2807;
(c) M.A.A.F. de C.T. Carrondo, A.R. Dias, M.H. Garcia, P.
Matias, M.F.M. Piedade, M.J. Villa de Brito, J. Organomet.
Chem. 466 (1994) 159.
[2] J.C. Kotz, W. Vining, W. Cocco, R. Rosen, A.R. Dias, M.H.
Garcia, Organometallics 2 (1983) 68.
[3] M.J. Calhorda, M.A.A.F. de C.T. Carrondo, A.R. Dias, A.M.T.
Domingos, M.T.L.S. Duarte, M.H. Garcia, C.C. Roma˜o, J.
Organomet.Chem. 320 (1987) 63.
F(000)
1064
3616
2.04–27.96
Theta range for data 1.84–25.49
collection (°)
Index ranges
−135h513, 05k510,
05l526
05h518,
05k528,
05l532
8983
Reflections collected 3386
Reflections observed 2660
[I\2|(I)]
5571
Independent
3386
8983
[4] M.J. Calhorda, M.A.A.F. de C.T. Carrondo, A.R. Dias, V.
Fe´lix, A.M. Galva˜o, M.H. Garcia, P.M. Matias, M.J. Villa de
Brito, J. Organomet. Chem. 453 (1993) 231.
[5] M.J. Villa de Brito, PhD thesis, Faculdade de Cieˆncias da
Universidade de Lisboa, 1995.
[6] J. Lewis, R.J. Irving, G. Wilkinson, J. Inorg. Nucl. Chem. 7
(1958) 32.
[7] W.P. Griffith, J. Lewis, G. Wilkinson, J. Inorg. Nucl. Chem. 7
(1958) 38.
[8] J.R. Ascenso, M.D. Carvalho, A.R. Dias, C.C. Roma˜o, M.J.
Calhorda, L.F. Veiros, J. Organomet. Chem. 478 (1994) 147.
[9] A.D. Hunter, P. Legzdins, C.R. Nurse, F.W.B. Einstein, A.C.
Willis, J. Am. Chem. Soc. 107 (1985) 1791.
reflections
Refinement method Full-matrix least-squares
Full-matrix least-
squares on F2
8983/30/452
on F2
3386/54/271
R1=0.0589
Data/restraints/
parameters
Final R indices
[I\2|(I)]
R indices (all data) R1=0.0824
Goodness-of-fit on 1.170
F2
R1=0.0588
R1=0.1187
1.083
Largest difference
1.581 and −0.904
1.465 and
−1.088
peak and hole
−3
,
(e A
)
[10] P. Legzdins, R.H. Jones, E.C. Phillips, V.C. Yee, J. Trotter,
F.W.B. Einstein, Organometallics 10 (1991) 986.
[11] M.Y. Darensbourg, R. Silva, J. Reibenspies, C.K. Prout,
Organometallics 8 (1989) 1315.
[12] F.H. Allen, O. Kennard, R. Taylor, Acc. Chem. Res. 16 (1983)
146.
Cp ligands were restrained (E.S.D. of 0.005). The ther-
mal parameters of the fluorine atoms of the anion in
¸¹¹¹¹¹¹¹¹¹¹¹¹¹º
the complex [Mo(h5-C5H5)2S(C6H4-o-SC6H5][BF4] were
also refined with ISOR (E.S.D. of 0.01). All calcula-
tions to solve and refine the structures were carried out
[13] M.J. Calhorda, A.M. Galva˜o, Bonding and conformations in
biscyclopentadienyl-thiolate derivatives of early transition
metals, in: M. Gielen (Ed.), Topics in Physical Organometallic
Chemistry, Freud Publishing House, Tel-Aviv, 1991, pp. 93–138.
[14] D.D. Perrin, W.L.F. Amarego, D.R. Perrin, Purification of
Laboratory Chemicals, 2nd ed., Pergamon, New York, 1980.
[15] Enraf–Nonius, CAD-4 Software, Version 5.0, Enraf–Nonius,
Delft, The Netherlands, 1989.
[16] G.M. Sheldrick, Acta Crystallogr. Sect. A 46 (1990) 467.
[17] G.M. Sheldrick, SHELXL-97: A Program for Refining Crystal
Structures, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
[18] P. McArdle, J. Appl. Crystallogr. 28 (1995) 65 (PC Windows
Version).
with SHELXS-86 [16] and SHELX-93 [17] from OSCAIL
8
package [18]. The illustrations were drawn with the
program ORTEP-III [19], also included in the same
package. Other details of data collection and refinement
are given in Table 4.
4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
[19] C.K. Johnson, M.N. Burnett, ORTEP-III, Report ORNL-6895,
Oak Ridge National Laboratory, TN, USA, 1996.