Insertion of CS2 into a metal acetylide bond and conversion of the bonding mode of S2CC≡CPh from η2 to η3

Article abstract of DOI:10.1016/S0022-328X(03)00466-2

Photolysis of a benzene solution containing [(L)Mo(CO)₃(C≡CPh)](L=η⁵- C₅H₅ 1; η⁵-C₅ Me₅ 2 and CS₂ leads to the formation of dithiopropiolato containing complexes, [(L)Mo(CO)₂ (η²-S₂CC≡CPh)] (L=η⁵-C₅H₅ 4 L=η⁵-C₅Me₅ 5). In presence of air, [(η⁵-C₅H₅)Mo(CO)₃ (C≡CPh)] reacts with CS₂ to give 4 as the major and [(η⁵-C₅H₅)Mo(O) (η³-S₂CC≡CPh)] (6) as minor products. Similarly, [(η⁵-C₅Me₅) Mo(CO)₃(C≡CPh)] reacts with CS₂ under aerobic conditions to give compound 5 along with [(η⁵-C₅Me₅)Mo(O) (η³-S₂CC≡CPh)] (7) as minor product. When solutions of 4 or 5 are photolysed under a constant purge of air, 4 gives 6, and 5 gives 7 in high yields. Room temperature stirring of 5 with [W(CO)₅(THF)] forms [η⁵-C₅ Me₅)Mo(CO)₂CS₂{W(CO)₅} ₂C≡CPh] (9). All new compounds have been characterised by IR and ¹H-NMR spectroscopy and the structures of 4, 6, 7 and 9 have been established crystallographically.

Full text of DOI:10.1016/S0022-328X(03)00466-2

Journal of Organometallic Chemistry 678 (2003) 142ꢁ147
/
www.elsevier.com/locate/jorganchem
Insertion of CS2 into a metal acetylide bond and conversion of the
bonding mode of S2CCÅ
CPh from h2 to h3
/
Pradeep Mathur a,b,*, Abhijit K. Ghosh a, Sarbani Mukhopadhyay a,
Chimalakonda Srinivasu a, Shaikh M. Mobin b
a Chemistry Department, Indian Institute of Technology, Powai, Bombay 400076, India
b National Single Crystal X-Ray Diffraction Facility, Indian Institute of Technology, Powai, Bombay 400076, India
Received 10 December 2002; received in revised form 7 May 2003; accepted 16 May 2003
Abstract
Photolysis of a benzene solution containing [(L)Mo(CO)3(CÅ
of dithiopropiolato containing complexes, [(L)Mo(CO)2(h2-S2CCÅ
C5H5)Mo(CO)3(CÅ
CPh)] reacts with CS2 to give 4 as the major and [(h5-C5H5)Mo(O)(h3-S2CCÅ
Similarly, [(h5-C5Me5)Mo(CO)3(CÅCPh)] reacts with CS2 under aerobic conditions to give compound 5 along with [(h5-
C5Me5)Mo(O)(h3-S2CCÅ
CPh)] (7) as minor product. When solutions of 4 or 5 are photolysed under a constant purge of air, 4 gives
/
CPh)] (Lꢀ
/
h5-C5H5 1; h5-C5Me5 2) and CS2 leads to the formation
h5-C5H5 4; Lꢀh5-C5Me5 5). In presence of air, [(h5-
CPh)] (6) as minor products.
/
CPh)] (Lꢀ
/
/
/
/
/
/
6, and 5 gives 7 in high yields. Room temperature stirring of 5 with [W(CO)5(THF)] forms [h5-C5Me5)Mo(CO)2CS2{W(CO)5}2CÅ
/
1
CPh] (9). All new compounds have been characterised by IR and H-NMR spectroscopy and the structures of 4, 6, 7 and 9 have
been established crystallographically.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Acetylides; Mixed-metal; Chalcogen; Crystal structure
1. Introduction
of coupling reactions were observed and these were
found to be dependent on the nature of chalcogen
As an unsaturated electrophile and a potential source
of C1 chemistry carbon disulfide has attracted a plethora
of research activity, in particular on its reactivity
towards transition metal complexes [1]. A diverse array
of compounds are known where CS2 bonds in h1-end
bridges as well as the reaction conditions used [23ꢁ
Under oxidising conditions we were able to isolate some
novel oxo*containing mixed*metal clusters with
chalcogen and acetylide bridges [28,29]. Here we report
another facet to the reactions of metal acetylide com-
plexes, namely the photolytic reaction of molybdenum
acetylide complexes with CS2 under aerobic and anae-
robic reaction conditions. Two types of CS2 insertion
/
27].
/
/
on, h2-side on and bridging co-ordination modes [2ꢁ
/10].
It readily inserts into metal alkyl and metal hydride
bonds at room temperature or under mild thermolytic
conditions to form dithiocarboxylate or dithioformate
complexes where the S2C motif is bound to the metal in
into Moꢁacetylide bonds are observed with conversion
/
of one type into the other.
either h2 or h3 fashion [11ꢁ
CS2 into a MÃ
C (sp3) bond is the most common, there
exist some examples of CS2 additions yielding h3-S2CR
ligand systems [13ꢁ22]. In our previous studies we have
examined acetylide coupling reactions on chalcogen*
bridged mixed metal carbonyl clusters. Various modes
/
13]. Although insertion of
/
2. Results and discussion
/
On photolysis of
a
benzene solution of
h5-C5H5 1; h5-C5Me5 2)
/
[(L)Mo(CO)3(CÅ
/
CPh)] (Lꢀ
/
and CS2, formation of [(L)Mo(CO)2(h2-S2CCÅ
/
CPh)]
h5-C5H5 4; Lꢀh5-C5Me5 5) was observed (Eq. 1).
Compounds 4 and 5 were characterised by IR and H-
(Lꢀ
/
/
1
* Corresponding author. Tel./fax: ꢂ91-22-572-4089.
/
E-mail address: mathur@chem.iitb.ac.in (P. Mathur).
NMR spectroscopy and their compositions were
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00466-2

P. Mathur et al. / Journal of Organometallic Chemistry 678 (2003) 142ꢁ
/147
143
confirmed by elemental analysis. Both compounds dis-
play an identical carbonyl stretching pattern in their IR
spectra, and 1H-NMR show singlets to confirm the
presence of (h5-C5H5) and (h5-C5Me5) groups for 4 and
5, respectively, and a multiplet for a phenyl group in
each of these compounds. For an unambiguous struc-
ture elucidation, crystals of 4 were grown from
dichloromethaneꢁhexane solvent mixture at 4 8C, and
/
a single crystal X-ray diffraction study was undertaken.
Molecular structure of 4 (Fig. 1) shows a {(h5-
C5H5)Mo(CO)2} unit and a (S2CCÅ
/
CPh) ligand bonded
to the molybdenum atom in h2-bonding mode. The two
˚
S bond lengths in 4, (2.4639(11) and 2.4610(12) A)
MoÃ
/
are almost equal and marginally longer than the MoÃ
/
S
˚
2.455 A observed in other
bond distance range of 2.414ꢁ
/
˚
thio acid complexes [30ꢁ36]. A separation of 2.995 A
/
between molybdenum atom and the a-carbon of the
acetylide group is much longer than the Mo-C(acetylide)
˚
bond length of 1.196(9) A in 1 indicating absence of a
formal bond between Mo atom and the acetylide group.
Delocalisation of p-electron cloud over the S2C moiety
in 4 is indicated by shortening of C(6)Ã
/
C(7) single bond
to 1.415(6) A and lengthening of C(7)ÃC(8) to 1.206(6)
A from the normal values associated with CÃC single
and CÅ
C triple bonds, respectively as in [Ru3(m3-h2-
PhC2CÅ
˚
/
˚
/
/
CBut)(m-PPh2)2(CO)6]; CÃ
/
C, 1.439(5) A, CÅ
1.188(5) A [37]. The small bond angle of S(2)ÃMoÃ
S bond
/
C,
˚
/
˚
/
/
S(1), 68.34(4)8 is comparable to the SÃ
/
MoÃ
/
From the photolytic reaction between 1 and CS2, in
presence of air, 4 and [(h5-C5H5)Mo(O)(h3-S2CCÅ
angle of 72.4(1)8 of the h2-CS2 bonded moiety of
[MoO(S2CNPr2)2] [30], and is consistent with the ring
constraints imparted by the bidentate S2C ligand in
forming a four-membered ring.
/
CPh)] (6) were obtained in yields of 34 and 13%,
respectively (Eq. 2). Under similar conditions, reaction
between 2 and CS2 led to the formation of 5 (38%) and
[(h5-C5Me5)Mo(O)(h3-S2CCÅ
/
CPh)] (7) (13%) (Eq. 3).
Compound 6 and the analogous [(h5-C5Me5)Mo(O)(h3-
S2CCÅCPh)] (7) were obtained in reasonable yields
/
when a benzene solution of 4 or 5 was photolysed in
presence of air (Eq. 4 and Eq. 5). Absence of bands in
the carbonyl region, and a band at 975 cmꢃ1 (6) or 973
cmꢃ1 (7) assignable to a MoÄ
/
O group are the notable
features in their IR spectra [28,29]. Presence of (h5-
C5H5), (h5-C5Me5) and phenyl groups were confirmed
by H-NMR spectra. Single crystals of 6 and 7 were
1
grown from dichloromethaneꢁhexane mixture solvent
/
at 0 8C and single crystal X-ray diffraction analyses were
carried out. Molecular structures of 6 (Fig. 2) and 7
(Fig. 3) are similar and consists of a {(h5-C5H5)Mo(Ä
/
O)} or {(h5-C5Me5)Mo(Ä
(h3-S2CCÅ
CPh) ligand attached to the Mo atom. The
unusual h3-bonding mode of this ligand is confirmed on
the basis of the following observations: the MoÃC(6)
separations of 2.228(4) A in 6 and 2.216(5) A in 7 are
/
O)} moiety, respectively and a
/
Fig. 1. ORTEP diagram of 4 with 30% probability ellipsoids. Selected
˚
bond distance (A) and bond angles (8): MoÃ
/
S(1)ꢀ
1.6770(4), S(2)ÃC(6)ꢀ
1.206(6), C(8)ÃC(9)ꢀ1.435(6), S(2)Ã
C(6)ÃC(7)ꢀ125.2(3), S(2)ÃC(6)ÃC(7)ꢀ
C(8)ꢀ176.8(4), C(7)ÃC(8)ÃC(9)ꢀ176.5(4),
68.34(4)
/
2.4610(12), MoÃ
/
/
S(2)ꢀ
C(7)ꢀ
C(6)ÃS(1)ꢀ
124.0(3), C(6)Ã
S(2)ÃMoÃS(1)ꢀ
/
2.4639(11), S(1)Ã
1.415(6), C(7)ÃC(8)ꢀ
110.6(2), S(1)Ã
C(7)Ã
/
C(6)ꢀ
/
/
/
1.688(4), C(6)Ã
/
˚
˚
/
/
/
/
/
/
˚
much shorter than the usual
observed for the more common h2-S2CÃ
systems [38]; additionally the planarity of the S1Ã
:
/
3.0 A separation
R bonded
S2Ã
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

144
P. Mathur et al. / Journal of Organometallic Chemistry 678 (2003) 142ꢁ147
/
Fig. 2. ORTEP diagram of 6 with 30% probability ellipsoids. Selected
˚
bond distances (A) and bond angles (8): MoÃ
S(1)ꢀ2.3366(10), MoÃC(6)ꢀ2.228(4), MoÃ
S(2)ꢀ1.744(4), C(6)ÃS(1)ꢀ1.732(3), C(6)ÃC(7)ꢀ
C(8)ꢀ1.204(5), C(8)ÃC(9)ꢀ1.432(5), S(2)ÃC(6)Ã
S(2)ÃC(6)ÃMoꢀ70.99(14), S(1)ÃC(6)Moꢀ71.06(13), MoÃ
C(7)ꢀ127(3), C(6)ÃC(7)ÃC(8)ꢀ174.3(4), C(7)ÃC(8)ÃC(9)ꢀ
177.6(4), S(1)ÃMoÃS(2)ꢀ80.17(4).
/
S(2)ꢀ
O(1)ꢀ
1.428(5), C(7)Ã
S(1)ꢀ120.0(2),
C(6)Ã
/
2.3399(12), MoÃ
/
/
/
/
/
/
1.689(3), C(6)Ã
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Fig. 4. ORTEP diagram of 9 with 30% probability ellipsoids. Selected
˚
bond distances (A) and bond angles (8): MoÃ
S(2)ꢀ2.513(3), MoÃC(11)ꢀ2.220(11), C(11)Ã
C(12)ÃC(13)ꢀ1.197(18), W(2)ÃS(2)ꢀ2.536(3),
2.549(3), C(13)ÃC(14)ꢀ1.394(18), S(2)ÃC(11)ꢀ
C(11)ꢀ1.763(11), MoÃS(1)ÃC(11)ꢀ59.2(4), MoÃ
59.6(4), S(1)ÃC(11)ÃC(12)ꢀ123.1(8), S(2)ÃC(11)ÃC(12)ꢀ
MoÃC(11)ÃS(1)ꢀ77.7(4), MoÃC(11)ÃS(2)ꢀ77.5(4), C(12)Ã
C(14)ꢀ177.8(15), MoÃS(2)ÃW(2)ꢀ128.94(12), MoÃS(1)ÃW(1)ꢀ
C(12)ÃC(13)ꢀ176.4(13), S(1)ÃC(11)ÃS(2)ꢀ
/
S(1)ꢀ
C(12)ꢀ
W(1)Ã
1.755(11), S(1)Ã
S(2)ÃC(11)ꢀ
124.3(8),
C(13)Ã
/
2.525(3), MoÃ
1.447(16),
S(1)ꢀ
/
C6Ã
/
C7 (C2S2) found in 4, is lost in 6 and 7. The SÃ
/
MoÃ
/
/
/
/
/
/
S bond angles, 80.17(4)8 in 6 and 79.44(7)8 in 7 are
significantly larger than that observed in 4 and is
indicative of release of some strain on conversion of
the four membered MoS2C ring in 4 to an open, allyl-
type bonding between the Mo atom and the S2C unit.
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
This is also reflected in the SÃ
4 opening to 120(2)8 in 6 and 119.6(3)8 in 7. The (CÅ
/
CÃS angle of 110.6(2)8 in
/
132.5(11),
108.6(6).
C(11)Ã
/
/
/
/
/
/
/
CPh) substituent and the oxo on the molybdenum atom
are mutually endo in both 6 and 7; without observation
of any exo-isomer in our reaction mixtures.
due to the CÃ
/
S and CÅ
C groups. Presence of both (h5-
/
C5Me5) and phenyl groups were confirmed by 1H-NMR
spectra. Crystallographic analysis of 9 was undertaken
We observed that h2ꢁ
/
h3 conversion of the S2CÃ
/
CÅ
/
CPh ligand can also be brought about by the addition of
‘W(CO)5’ groups to the S atoms of 5. Thus, when a THF
solution of 5 was treated with [W(CO)5(THF)] and the
solution stirred at room temperature in vacuum, the
after obtaining its crystals from dichloromethaneꢁ
hexane solvent mixtures at ꢃ4 8C. Its molecular struc-
ture (Fig. 4), shows an endo-[h5-C5Me5)Mo(CO)2(h3-
S2CCÅCPh)] unit with a ‘W(CO)5’ group attached to
each S atom. The reduced p electron delocalization over
the S2C moiety is reflected in C(11)ÃC(12) bond length,
1.447(16) A which is comparable to a CÃC single bond,
CSiMe3)CCÄCPh2}
C(13) bond distance,
/
/
/
adduct, [h5-C5Me5)Mo(CO)2CS2{W(CO)5}2CÅ
/CPh] (9)
was isolated in 30% yield (Eq. 6). IR spectrum of 9
shows bands due to terminal carbonyls as well as bands
/
˚
/
˚
1.443(5) A in [Ru3{m3-Me3SiCC(CÅ
/
/
(m-OH)(CO)9] [39]. The C(12)Å
/
˚
1.197(18) A in 9 is similar to the acetylide triple bond
5
˚
distance, 1.196(9) A in [(h -C5H5)Mo (CO)3(CÅ
/
CPh)]
5
˚
and 1. 197(5) A in [{h -C5H5)Mo(CO)2}2{m-1, 2-PhCÃ
/
C(CO)CÅCPh}] [24,40].
/
3. Conclusion
In this paper we have reported the photolytic inser-
tion of CS2 into Moꢁacetylide bond to give two types of
co-ordinated S2CÃCÅ
CPh ligands; one is the h2-bond-
ing mode and the second, the rather rare h3-bonding
mode [13ꢁ CÅCPh)
22]. We observe that the (h2-S2CÃ
can be transformed to (h3-S2CÃ
CÅCPh) ligand by two
/
Fig. 3. ORTEP diagram of 7 with 30% probability ellipsoids. Selected
/
/
˚
bond distances (A) and bond angles (8): MoÃ
/
S(1)ꢀ
O(1)ꢀ
1.189(7), C(13)ÃC(14)ꢀ
C(11)ꢀ1.733(5), S(1)ÃMoÃ
119.6(3), MoÃS(1)ÃC(11)ꢀ63.85(18),
63.89(18), S(1)ÃC(11)ÃC(12)ꢀ120.5(4), S(2)Ã
124.3(8), MoÃC(11)ÃS(1)ꢀ71.66(19), MoÃC(11)Ã
71.52(19), C(12)ÃC(13)ꢀ177.7(6), C(12)ÃC(13)Ã
C(11)Ã
C(14)ꢀ177.9(6).
/
2.3431(17), MoÃ
1.689(4), C(11)Ã
1.451(8),
S(2)ꢀ
/
S(2)ꢀ
C(12)ꢀ
S(1)ÃC(11)ꢀ
79.44(7), S(2)Ã
MoÃS(2)ÃC(11)ꢀ
C(11)ÃC(12)ꢀ
S(2)ꢀ
/
2.3404(16), MoÃ
1.429(7), C(12)Ã
1.730(6),
S(2)Ã
C(11)ÃS(1)ꢀ
/
C(11)ꢀ
/
2.216(5), MoÃ
/
/
/
/
/
C(13)ꢀ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
different pathways: by oxidation at the metal atom or by
/
/
/
/
/
/
/
addition of electron-withdrawing metal carbonyl groups
to the S atoms of the (h2-S2CÃ
/
/
/
/
/
/
/
/
CÅ
/
CPh) group. Thus,
under aerobic photolytic conditions [(L)Mo(CO)2(h2-
/
/
/
/
/
/
/

P. Mathur et al. / Journal of Organometallic Chemistry 678 (2003) 142ꢁ
/147
145
S2CÃ
CÅ
CPh)] (6 and 7). Room temperature reaction of [(h5-
C5Me5)Mo(CO)2(h2-S2CÃ
CÅCPh)] (5) with
[W(CO)5(THF)] forms the adduct [(h5-C5Me5)M-
/
CÅ
/
CPh)] (4 and 5) convert to [(L)Mo(O)(h3-S2CÃ
/
Compound 5 was prepared similarly using [(h5-
C5Me5)Mo(CO)3(CÅCPh)] (100 mg, 0.24 mmol) and
carbon disulfide (0.02 ml, 0.3 mmol). Yield: 49 mg
/
/
/
/
(46%). M.p. 170ꢁ171 8C. Anal. Found: C, 54.0; H, 4.53.
/
o(CO)2{SW(CO)5}2CÃ
/
CÅ/CPh] (9) in which the S2C
C21H20MoO2S2 Calc.: C, 54.08; H, 4.33%. IR (cmꢃ1):
1979 (s), 1922 (vs) n(CO); 2183 (w) n(CC); 1064 (m), 887
unit is h3 bonded to the Mo atom.
1
(s), 760 (sh), 722 (vs) n(CS). H-NMR (d 1.88 (s, 15H,
C5Me5), 7.32ꢁ7.56 (m, 5H, C6H5).
/
4. Experimental
4.3. Synthesis of [(h5-C5H5)Mo(O)(h3-S2CCÅ
/
CPh)]
(6) and [(h5-C5Me5)Mo(O)(h3-S2CCÅ
CPh)] (7)
/
4.1. General procedures
A
benzene
solution
(50
ml)
of
[(h5-
CPh)] (80 mg, 0.232 mmol) and
Reactions and manipulations for the preparation of
C5H5)Mo(CO)3(CÅ
/
4ꢁ7 and 9 were carried out using standard Schlenk line
/
CS2 (0.02 ml, 0.3 mmol) was subjected to photolysis
for 1 h at 0 8C in a photochemical reaction vessel under
a continuous flow of air. After removal of the solvent in
vacuum, the residue was subjected to chromatographic
techniques under an atmosphere of argon unless other-
wise stated. Solvents were purified, dried and distilled
under an argon or nitrogen atmosphere prior to use.
Infrared spectra were recorded on a Nicolet Impact 400
FT IR spectrophotometer, as hexane solutions in 0.1
mm path length cells and NMR spectra were recorded
work up on silica gel column by using hexaneꢁdichlor-
/
omethane mixture (60:40 v/v) as an eluant. A major
band of a violet compound 4 (31 mg, 34%) eluted first
followed by an orange band of compound 6 (11 mg,
13%). Compound 6 was obtained in better yield by
carrying out photolysis of a benzene solution (50 ml) of
[(h5-C5H5)Mo(CO)2(h2-S2CCÅ
mmol) at 0 8C under a constant purge of air for 45 min.
Using hexaneꢁdichloromethane mixture (60:40 v/v) as
an eluant, trace amounts of 4 were obtained, followed
by the major orange band of compound 6 (12 mg, 39%).
M.p. 160ꢁ
2187 (w) n(CC); 975 (w) n(MoÄ
d 6.28 (s, 5H, C5H5), 7.26ꢁ
Found: C, 47.07; H, 2.95. C14H10MoOS2 Calc. C, 47.20;
H, 2.83%.
Compound 7 was similarly obtained by photolysing a
benzene solution (50 ml) of [(h5-(C5Me5)Mo(CO)3(CÅ
CPh)] (80 mg, 0.19 mmol) and CS2 (0.02 ml, 0.3 mmol)
at 0 8C in air for 1 h. Chromatographic work up on a
silica gel column using hexaneꢁdichloromethane mix-
on a Varian VXR*
Elemental analyses were performed using a Carloꢁ
Erba automatic analyser. The compounds
[(L)Mo(CO)3ÃCÅCPh] (Lꢀ
h5-C5H5, h5-C5Me5) [41]
/300S spectrometer in CDCl3.
/
/
/
/
/
CPh)] (4) (34 mg, 0.87
and [W(CO)5(THF)] [42] were prepared by established
procedures. Photochemical reactions were carried out in
a water cooled double-walled quartz vessel having a 125-
W immersion type mercury lamp manufactured by
Applied Photophysics Ltd.
Tungsten hexacarbonyl, molybdenum hexacarbonyl
and pentamethyl cyclopentadiene were purchased from
Strem Chemical Co., phenyl acetylene was purchased
from Aldrich Chemical Co. and these were used without
further purification.
/
/
161 8C. IR (cmꢃ1): 1060 (sh), 745 (vs) n(CS);
1
O). H-NMR (d, ppm):
7.40 (m, 5H, C6H5). Anal.
/
/
/
4.2. Synthesis of [(h5-C5H5)Mo(CO)2(h2-S2CCÅ
CPh)] (4) and [(h5-C5Me5)Mo(CO)2(h2-S2CCÅ
CPh)] (5)
/
/
/
ture (60:40 v/v) as an eluant afforded compound 5 (34
mg, 38%) followed by 7 (10 mg, 13%). Alternatively, it
was obtained in higher yield from direct photolysis of a
benzene solution (50 ml) of [h5-C5Me5)Mo(Co)2(h2-
A
benzene solution (50 ml) containing [(h5-
C5H5)Mo(CO)3(CÅCPh)] (100 mg, 0.29 mmol) and
/
carbon disulfide (0.02 ml, 0.3 mmol) was photolysed
for 15 min at 0 8C under continuous bubbling of argon.
The solvent was removed in vacuo and the residue was
dissolved in minimum amount of dichloromethane. The
dichloromethane solution was filtered through Celite to
remove insoluble material and the solution was sub-
jected to chromatographic work-up on a silica gel
column. Elution with hexaneꢁ
(60:40, v/v) yielded a violet coloured compound 4. Yield:
58 mg (52%). M.p. 155ꢁ157 8C. Anal. Found: C, 48.09;
S2CCÅ
/
CPh)] (5) (50 mg, 0.11 mmol) at 0 8C for 30 min
under constant purge of air. Yield: 19 mg (41%). M.p.
175ꢁ177 8C. Anal. Found: C, 53.21; H, 4.85.
/
C19H20MoOS2. Calc. C, 53.52; H, 4.73%. IR (cmꢃ1):
1060 (sh), 745 (vs) n(CS); 2187 (w) n(CC); 973 (w)
n(MoÄ
/
O). 1H-NMR (d, PPM); d 2.12 (s, 15H, C5Me5),
/dichloromethane mixture
7.20ꢁ7.50 (m, 5H, C6H5).
/
/
4.4. Synthesis of [h5-
C5Me5)Mo(CO)2CS2{W(CO)5}2CÅ
H, 2.60. C16H10MoO2S2 Calc.: C, 48.49; H, 2.55%. IR
(cmꢃ1): 1980 (s), 1922 (vs) n(CO); 2187 (w) n(CC); 1066
(m), 891 (s), 764 (sh), 729 (vs) n(CS). 1H-NMR (d,
/
CPh} (9)
To a solution of [(h5-C5Me5)Mo(CO)3(CÅ
mg, 0.054 mmol) in dry THF (70 ml) was added
/
CPh)] (25
ppm): d 5.53 (s, 5H, C5H5), 7.31ꢁ7.56 (m, 5H, C6H5).
/

146
P. Mathur et al. / Journal of Organometallic Chemistry 678 (2003) 142ꢁ147
/
[W(CO)5(THF)]. The reaction mixture was stirred under
vacuum for 30 min, during which, the colour of the
solution changed from green to brown. The solvent was
removed in vacuo. The residue was dissolved in a
minimum amount CH2Cl2 and was chromatographed
mixtures and X-ray diffraction studies were undertaken.
Relevant crystallographic data and details of measure-
ments are given in Table 1. Data were collected from
single crystals of 4 (0.3ꢄ
0.25ꢄ
0.15 mm3), 7 (0.25ꢄ
(0.35ꢄ0.10ꢄ
0.15 mm3). Unit cell dimensions were
obtained using 25 centered reflections in u range
5.6900ꢁ12.6800 mounted on a Nonius MACH 3 dif-
fractometer equipped with graphite monochromated
/
0.15ꢄ
/
0.15 mm3), 6 (0.4ꢄ
/
/
/
0.125ꢄ
/
0.1 mm3) and 9
using silica gel coated TLC plates. Use of hexaneꢁ
/
/
/
dichloromethane mixture (60:40 v/v) as an eluant
afforded a violet band 9. Yield: 18 mg (30%). M.p.
/
240ꢁ241 8C (decomposition). Anal. Found: C, 33.11; H,
/
1.97. C31H20MoW2O12S2 Calc. C, 33.40; H, 1.81%. IR
(cmꢃ1): 1942 (vs), 1895 (s) n(CO); 2187 (w) n(CC); 1060
(sh), 899 (m), 745 (vs) n(CS). 1H-NMR (d, ppm): d 2.04
˚
Moꢁ
collected by v ꢁ
/
Ka radiation (0.7093 A). Intensity data were
2u scan mode, and corrected by Lorentz
/
polarization and absorption effects using Psi-Scan (c-
scan). Three standard reflections monitored after every
200 reflections and 3 Intensity controlled reflections
monitored every hour showed no significant changes
(s, 15H, C5Me5), 7.39ꢁ7.60 (m, 5H, C6H5).
/
4.5. Crystal structure determination of 4, 6, 7 and 9
(B
SHELXS 97) and refined by full-matrix least squares
against F2 using SHELXL-97 software [43]. Non-hydro-
/
3%). The structure was solved by direct methods
(
Suitable X-ray quality crystals of 4, 6, 7 and 9 were
grown by slow evaporation of CH2Cl2-n-hexane solvent
Table 1
Crystal data and structure refinement details for 4, 6, 7 and 9
4
6
7
9
Empirical formula
Formula weight
Temperature (K)
Wavelength
C16H10MoO2S2
394.30
293(2)
C14H10MoOS2
354.28
293(2)
C19H20MoOS2
424.41
293(2)
C31H20MoO12S2W2
1112.23
221(2)
0.70930
Monoclinic
P21/a
0.70930
Monoclinic
P21/a
0.70930
Monoclinic
C2/c
0.70930
Monoclinic
P21/c
Crystal system
Space group
Unit cell dimensions
˚
a
b
c
(A)
13.2560(10)
9.7660(12)
13.3740(12)
90.000(8)
115.003(6)
90.000(8)
1569.1(3)
4, 1.669
10.469(2)
11.6280(13)
11.544(2)
90.000(12)
102.635(16)
90.000(13)
1371.3(4)
4, 1.716
21.6530(12)
11.2990(11)
16.5520(15)
90.000(9)
109.305(6)
90.000(6)
3821.9(6)
8, 1.475
12.7070(10)
19.1550(14)
14.7290(13)
90.000(6)
100.929(7)
90.000(6)
3520.1(5)
4, 2.099
˚
(A)
˚
(A)
a
b
g
(8)
(8)
(8)
3
˚
V (A )
Z, calculated density (Mg mꢃ3
Adsorption coefficient (mmꢃ1
F(0 0 0)
)
)
1.101
784
1.244
704
0.906
1728
7.048
2096
Crystal size (mm)
u range of data collection
Index ranges
0.3ꢄ
1.68ꢁ
05h 5
155l 5
2487/2487
/
0.15ꢄ
24.91
15, 05
14
/
0.15
0.4ꢄ
1.80ꢁ
05h 5
135l 5
2368/2368
/
0.25ꢄ
24.93
12, 05
13
/
0.15
0.25ꢄ
1.99ꢁ24.92
05h 525, 05
195l 518
2604/2604
/
0.125ꢄ
/
0.1
0.35ꢄ
1.63ꢁ24.92
05h 515, 05
175l 517
5509/5509
/
0.10ꢄ0.15
/
/
/
/
/
/
/
/
k 5
/11,
/
/
/k 5
/13,
/
/
/k 5
/
13,
/
/
/
k 522,
/
ꢃ/
/
/
ꢃ/
/
/
ꢃ/
/
/
ꢃ/
/
/
Reflections collected/unique
[R(int)ꢀ0.0000]
/
Completeness to 2u
2uꢀ
/
24.91, 85.0%
2uꢀ/27.93, 92.6%
2uꢀ/24.92, 36.7%
2uꢀ24.92, 86.2%
/
Absorption correction
Max. and min. transmission
Refinement methods
c-scan
1.000 and 0.957
c-scan
1.000 and 0.871
c-scan
1.000 and 0.990
c-scan
1.000 and 0.911
Full-matrix least-squares Full-matrix least-squares Full-matrix least-squares Full-matrix least-squares on
on F2
on F2
on F2
F2
Data/restraints/parameters
Goodness-of-fit on F2
2487/0/230
1.110
2368/0/196
1.125
2604/0/288
1.050
5509/0/433
1.094
Final R indices [I ꢀ
R indices (all data)
/
2s(I)]
R1ꢀ
R1ꢀ
0.531 and ꢃ
/
0.321, wR2ꢀ
0.0403, wR2ꢀ
0.587
/
0.0777 R1ꢀ
0.0872 R1ꢀ
0.855 and ꢃ
/
0.0452, wR2ꢀ
0.0473, wR2ꢀ
0.874
/
0.1101 R1ꢀ
0.1124 R1ꢀ
0.335 and ꢃ
/
0.0380, wR2ꢀ
0.0650, wR2ꢀ
0.290
/
0.0675 R1ꢀ
0.0783 R1ꢀ
3.099 and ꢃ
/
0.0754, wR2ꢀ
0.0820, wR2ꢀ
6.995
/
0.1845
0.1954
/
/
/
/
/
/
/
/
Largest diff. peak and hole
ꢃ3
/
/
/
/
˚
(e A
)

P. Mathur et al. / Journal of Organometallic Chemistry 678 (2003) 142ꢁ
/147
147
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
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of this information may be obtained free of charge from
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P.M. is grateful to the Department of Science and
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