Triosmium clusters with bridging terpenic thioureato-like ligands

Article abstract of DOI:10.1016/j.jorganchem.2004.04.040

The reaction of acetone-4-(2-methoxy-phenyl)thiosemicarbazone with triosmium cluster Os₃(CO)₁₁(NCMe) results in the formation of the cluster with the μ₂ chelate-bridging ligand coordinated by S and N¹ atoms, whi

Full text of DOI:10.1016/j.jorganchem.2004.04.040

Journal of Organometallic Chemistry 689 (2004) 2535–2542
www.elsevier.com/locate/jorganchem
Triosmium clusters with bridging terpenic thioureato-like ligands
a,
a
a
Vladimir P. Kirin *, Vladimir A. Maksakov , Alexandr V. Virovets ,
b
Sergey A. Popov , Alexey V. Tkachev
b
a
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS, Acad Lavrentyev Avenue 3, Novosibirsk 630090, Russia
b
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of RAS, Acad Lavrentyev Avenue 9, Novosibirsk 630090, Russia
Received 22 January 2004; accepted 14 April 2004
Abstract
The reaction of acetone-4-(2-methoxy-phenyl)thiosemicarbazone with triosmium cluster Os3(CO)11(NCMe) results in the forma-
tion of the cluster with the l2 chelate-bridging ligand coordinated by S and N1 atoms, which was studied by X-ray diffraction
analysis. Reaction of (3aR, 3bR, 4aR, 5aS)-5a-hydroxy-3,4,4-trimethyl-3a,3b,4,4a,5,5a-hexahydrocyclopropa[3, 4]cyclopenta[1,2-
c]pyrazole-1-carbothioic acid amide with Os3(CO)11(NCMe) gives rise to the complex with the bridging ligand coordinated by
sulphur atom. Further transformation of the complex in hot benzene results in tautomeric rearrangement of the organic ligand
and the cleavage of the pyrazolinol cycle to form an open chain tautomer. Unusual silica gel induced oxidative cleavage of the
cyclopropane ring in the open chain derivative and epoxidation of cycloalcane C–C bond are observed on the air.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Triosmium clusters; Terpenoids; Ligand activation; X-ray structure; 1H and 13C NMR spectroscopy
1. Introduction
caused by (a) involving of lone electronic N2 atom pair in-
to the aromatic-system of pyrazolic cycle; (b) the pres-
ence of the bulky substituent at the nitrogen atom N3
and decreasing of electronic density on this atom owing
to electronegativity of the pyrazolic cycle; (c) steric re-
strictions arising at coordination of bulky tricyclic ligand
on cluster core. To examine these assumptions we have
investigated the reactions of cluster Os3(CO)11(NCMe)
(2) with acetone-4-(2-methoxy-phenyl)thiosemicarba-
zone (3) and (3aR, 3bR, 4aR, 5aS)-5a-hydroxy-3,4,
4-trimethyl-3a,3b,4,4a,5,5a-hexahydro-cyclopropa[3,4]
cyclopenta[1,2-c]pyrazole-1-carbothioic acid amide (4)
(Scheme 1).
We have reported earlier the reactions of the triosmi-
um clusters with a number of the carane derivatives.
These reactions proceeded quite different as compared
with those of the simplest analogues. We have found
CH [1] or CN [2] activation at very mild conditions and
changes of the ligand coordination mode as a result of
the ligands steric demands [2,3]. For example, (3bS,
4aR)-3,4,4-trimethyl-3b,4,4a,5-tetrahydro-cyclopropa[3,4]
cyclopenta[1,2-c]pyrazole-1-carbothioic acid (2-meth-
oxy-phenyl)-amide (amide 1), which contains thiourea-
like fragment N–C(‚S)–N, coordinates in triosmium
cluster in the tautomeric N–C(‚NR)–S form [3] with
the ligand coordinated only on two osmium atoms by sul-
phur and N1 atoms in contrast to simple analogues bridg-
ing three metal atoms [4,5]. This difference could be
2. Results and discussion
Thiosemicarbazone 3 reacts with 2 similarly to amide
1. On heating in benzene the complex 5 is formed in a
good yield (74%), in which thiosemicarbazone substi-
tutes NCMe and two CO groups and is coordinated
*
Corresponding author. Tel.: +7-383-2-343052; fax: +7-383-2-
344489.
E-mail address: kirin@che.nsk.su (V.P. Kirin).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.04.040

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V.P. Kirin et al. / Journal of Organometallic Chemistry 689 (2004) 2535–2542
10
10
7
9
8
9
8
7
1
6
2
1
6
5
3
2
4
5
3
<1>
N
4
<2>
NH
<1>
N
<2>
N
<1>
N
O
<2>
N
11
<3>
N
O
H
11
H
<3>
H
N
O
S
3
S
S
<3>
H2N
4
1
Scheme 1.
by a ‘‘chelate-bridging’’ mode by of sulphur and N1 at-
oms: (See Scheme 2).
˚
bridged Os–Os edge (2.8653 and 2.8470 A) and Os–N
˚
(2.181 and 2.14 A) bonds are lengthened, and N–N
The cluster 5 has been characterized by 1H, 13C
NMR, and IR spectroscopy and elemental analysis, all
the data are in agreement with the structure proposed
(Table 1).
For this compound the single crystal has been ob-
tained and its X-ray crystal analysis has been performed
(see Fig. 1).
There is an unique fragment Os3(l-H)(l,g2-SCNN)
presented in the molecule 5. No similar structures were
found in the Cambridge Structural Database except for
recently discovered cluster with a similar fragment
Os3(CO)9(l-H)(l,g2-SC{‚NC6H4OMe}N2C10H13) (9)
having the group N–N incorporated into pyrazole cycle
[2]. The comparison of the bond lengths in chelated frag-
ments has shown, that in 5 in comparison with 9 the
(1.405 and 1.47 A), S–C (1.798 and 1.84 A) and C(1)–
˚
˚
˚
N(2) (1.298 and 1.39 A for 5 and 9 respectively) bonds
are shortened noticeably. The bonds Os–S have close val-
ues in 5 and 9. Presence of the pyrazolic cycle influences
first on the bond lengths in the five-membered OsSCNN
ring though the Os2S fragment is also concerned. The
crystal packing of compound 5 is typically molecular,
without appreciably shortened intermolecular contacts.
Unlike the above reaction, the interaction of the clus-
ter 2 with amide 4 cleanly proceeds already at ambient
temperature. According to TLC in 10 min after dissolv-
ing the reagents, there is only complex 6 as the reaction
product. Unfortunately this compound is not stable on a
silica gel plate in air enough to be isolated by chroma-
tography. So complex 6 has been characterized only
CO
CO
CO
CO
CO
Os
CO
CO
CO
CO
CO
Os
C O
Os
CO
CO
H
CO
Os
Os
3
CO
Os
CO
CO
CO
CO
benzene, 80˚C
CO
S
N
N
2
N
HN
O
5
Scheme 2.

Table 1
Spectroscopic data for compounds 4–8
À1
IR, m(CM
)
1H NMR, d(J Hz)
13C NMR, d(J Hz)
4
5
a3516, 3384, 1572, 1484, 1381, 1335, 1286, 1182,
1128, 1075, 1022, 955, 902, 854
b0.93 d (J=7 Hz, H-7), 0.97 s (3H-10), 1.09 s (3H-
9), 1.16 dd (J=7 and 7 Hz, H-6), 1.95 d (J=15 Hz,
H-5a), 1.98 s (3H-1), 2.91 dd (J=15 and 7 Hz, H-
5b), 2.97 br.s, 5.1 br.s. (OH), 5.69 br.s (NH2)
b14.56 (C-1), 62.33 (C-3), 107.45 (C-4), 40.36 (C-5), 30.75
(C-6), 32.14 (C-7), 20.52 (C-8), 26.66 (C-9), 14.20 (C-10),
154.45 and 155.59 (C-2 and NCSNH2)
c2092 m, 2056 s, 2016 s, 2011 vs, 1997 s, 1982 m,
f7,94 – 6,88 (m, 4H, C6H4); 7,52 (br.s, 1H, NH);
3.97 (s, 3H, OMe); 2.81 and 2.46 (s, 6H,‚CMe2);
À16.14 (s, 1H, l-H)
f188.43 (d, JCH 2.4), 182.07 (d, JCH 1.4), 179.81 (d, JCH 1.9),
176.74 (d, JCH 2.9), 174.28 (d, JCH 9.6), 173.44(s), 172.42
(s), 172.28 (d, 14.4), 169.85 (d, JCH 1.0), 169.41 (d, JCH 3.8)
(‘‘Os3(CO)9’’ + C–S); 176.02 (sept, JCH 6.2,‚CMe2);
148.00 (s), 128.86 (s); 123.54 (ddd, JCH 162.7, 8.9, 1.7),
120.49 (dd, JCH 162.7, 8.2), 119.54 (dddd, JCH 164.1, 8.2,
5.3, 2.9), 109.93 (dd, JCH 159.8, 8.9) (C6H4); 55.82 (q, JCH
144.9, OMe); 32.37 (qq, JCH 128.6, 3.1, (‚CMe2), 25.05
(qq, JCH 129.8, 3.3)‚CMe2)
1972 sh, 1930 m; d3408 w (mN –H
)
g6
c2110 w, 2071 s, 2063 m, 2028 s, 2019 sh, 2008 m,
f6.0 and 5.7 (br.s, 1H, NH); 3.37 (m, 1H, H5a);
2.73 (m, 1H, H3); 2.18 (m, 1H, H5b); 2.03 and 1.96
(s, 3H, H1); 1.48 (m, 1H, H6); 1.15 (m, 1H, H7);
1.22 and 1.08 (s, 3H, H10); 1.14 and 1.09 (s, 3H,
H9); À17.19 and –17.48 (s, 1H, l-H)
f182.97, 181.55, 180.63, 177.11, 177.05, 174.42, 173.42,
170.88, 170.73, 170.56, 169.65, 169.51, 165.55, 162.18,
162.07, 159.07 (‘‘Os3(CO)10’’ + C11); 123.42 (C2), 86.27 and
84.14 (C4), 64.78 and 63.56 (C3), 43.01 and 42.42 (C5),
33.21 and 33.01 (C6), 31.69 and 31.41 (C7), 23.49 and 20.81
(C10), 21.16 and 20.58 (C8), 14.83 and 14.45 (C1/C9), 14.33
and 14.25 (C9/C1)
e
1994 sh, 1989 m, 1958 w; 3616b br.w (mOH),
3513br.w(mNH), 3386 br.w (mNHassoc
)
7
8
c2111 w, 2071 s, 2063 m, 2026 s, 2016 m, 2012 sh,
h5.31 (br., 2H, >NH +=NH); 3.36 (m, 1H, H3);
3.29 (dd, 1H, 15.6, 7.0, H5a); 2.74 (dd, 1H, 15.6, 8,
H5b); 2.11 (s, 3H, H1); 1.98 (m, 1H, H6); 1.69 (m,
1H, H7); 1.05 (s, 3H, H10); 0.75 (s, 3H, H9); –17.3
(s, 1H, l-H)
h202.37 (C4); 181.43, 180.26, 180.15, 176.71, 174.13,
174.03, 170.69, 170.55, 169.46, 155.91, 152.49
(‘‘Os3(CO)10’’ +C11); 96.53 (C2); 63.31 (C3); 37.93 (C5);
32.88 (C6); 30.69 (C7); 26.89 (C10); 21.54 (C8); 15.65 (C9);
14.62 (C1)
e
1989 w, 1733 w; 3470 w, 3377 w (mNH
)
c2112 w, 2071 s, 2062 m, 2026 s, 2016 m, 2008 m,
1988 w, 1717 w; d3615 v.w, 3593 v.w, 3500 w, 3363
f5.75 (br. s, 2H, NH); 4.07 (d, 1H, 1.1, H7); 2.47
(dd, 1H, 17.6, 8.2, H5a); 2.39 (dd, 1H, 8.2, 1.1, H6);
2.22 (dd, 1H, 17.6, 8.2, H5b); 1.97 (s, 3H, H1); 1.37
+ 1.26 (s, 3H + 3H, H9 + H10); –17.19 (s, 1H, l-H)
h203.80 (s, C4); 181.71, 180.28, 176.74, 176.72, 173.97,
173.93, 170.61, 170.51, 169.36, 169.30, 162.89
(‘‘Os3(CO)10’’ + C11), 156.18 (t, JCH 6.5, C2),
96.52 (s, C8), 71.44 (s, C3), 64.43 (dd, JCH 191.2, 4.1, C7),
44.89 (d, JCH 127.4, C6), 34.29 (dd, JCH 136.5, 126.4, C5),
28.78 (q, JCH 124.3, C9/C10), 27.53 (q, JCH 125.2, C10/C9),
14.78 (q, JCH 129.6, C1)
i
w (mOH and mNH); 1743(mCO); 1622, 1592, 1558
(mCN and dNH); 1461, 1453 (dCH); 1373, 1363, 1280
a
b
c
d
e
f
In CDCl3.
In CDCl3–CCl41:1 v/v.
In hexane.
In CCl4.
In CH2Cl2.
In CDCl3.
g
h
i
Mixture of two rotamers.
In C6D6.
In KBr.

2538
V.P. Kirin et al. / Journal of Organometallic Chemistry 689 (2004) 2535–2542
by NMR and IR spectroscopy. IR spectrum of this clus-
ter in the CO stretching region is characteristic for trios-
mium clusters with bridging thiolate ligand [6]. The OH
vibration band is clearly visible at 3613 cmÀ1. The bridg-
ing coordination of the ligand by sulphur atom is con-
1
firmed by NMR data. In H NMR spectrum there are
two very close singlet signals of l-H ligands (ꢀ1:2) in
the area characteristic for (l-H)Os3(CO)10(l-SR) clus-
ters [2]. Other part of the spectrum does not much differ
from the spectrum of uncoordinated 4 except for dou-
bling of the singlets of the methyl groups signals in the
ratio similar to that of hydrides mentioned above. The
intensity of NH signal is reduced by half in comparison
with corresponding signal of free 4. Carbon-13 NMR
spectrum of the complex demonstrates two sets of sig-
nals (ꢀ2:1) whose chemical shifts and multiplicity are
similar to those of free ligand 4. The signal of C11 atom
in complex 6 is located in the area of carbonyl carbons
of the moiety Os3(CO)10 and so the signal was not
identified.
Presence of 2 sets of signals in the NMR spectra
of the complex could be explained in terms of steric
hindrance: intramolecular rotation around S–C bond
in the bridging ligand is inhibited by unfavourable inter-
action of the ligand with the carbonyl environment and
results in high rotational barrier. Even in the case of the
Fig. 1. Molecule 5 as 35% probability ellipsoids according to X-ray
˚
crystallography. Main bond distances (A): Os(1)–Os(2) 2.8653(5),
Os(1)–Os(3) 2.8234(5), Os(1)–S(1) 2.3731(19), Os(1)–N(1) 2.181(6),
Os(2)–S(1) 2.444(2), Os(2)–Os(3) 2.8510(6), S(1)–C(1) 1.798(7), C(1)–
N(2) 1.298(8), C(1)–N(3) 1.346(9), N(2)–N(1) 1.405(8), N(1)–C(2)
1.293(9), C(2)–C(3) 1.486(11), C(2)–C(4) 1.478(11), N(3)–C(111)
1.401(10).
CO
CO
CO
CO
Os
CO
CO
Os
CO
CO
CO
CO
CO
CO
H
Os
Os
CO
4
Os
CO
Os
CO
CO
CO
CO
CO
CO
benzene, 25˚C
CO
N
S
N
N
HN
HO
CO
CO
CO
Os
Os
benzene, 80˚C
CO
CO
6
CO
H
Os
CO
CO
CO
CO
CO
CO
CO
Os
CO
S
Os
N
O2, SiO2
CO
CO
NH
H
HN
Os
CO
CO
CO
O
CO
S
N
NH
HN
7
O
O
8
OH
Scheme 3.

V.P. Kirin et al. / Journal of Organometallic Chemistry 689 (2004) 2535–2542
2539
less bulkier derivative (l-H)Os3(CO)10(l-NHCHMe-
COOEt) estimation of the intramolecular rotation barri-
er resulted in the value of about 55 kJ/mol [7].
À17.19 ppm) of the new complex 8 prove the presence of
the moiety (l-H)Os3(CO)10(l-S-) in the molecule. How-
ever proton and carbon NMR spectra of the organic
unit differ strongly from the spectra of the ligand in
clusters 6 and 7 and demonstrate disappearance of
gem-dimethylcyclopropane unit and formation of the
group –CMe2X (X‚O or N) instead. Careful analysis
of 2D C–H correlation NMR spectra of the new com-
plex (See Figs. 2 and 3) allowed us to suppose the com-
pound to be hydroxyl epoxide 8. Formation of the small
heterocycle (oxyrane) is confirmed by the value of the
C7-H coupling constant in the carbon-13 NMR spec-
trum (1JH–C =191 Hz), which is characteristic for epox-
ides [9], and by chemical shifts of the C3 and C7
signals (77.44 and 64.43 ppm respectively) [9]. IR spec-
trum of the compound 8 proves the formation of
hydroxyl (mO–H =3615 cmÀ1) and oxirane (mC–O =1280
cmÀ1) [10].
Conversion 7fi8 is induced by a silica gel support.
Thus, when compound 7 has been formed, passing of
the air through the reaction mixture for two days result-
ed only in some decomposition of the complex. The stir-
ring the reaction mixture with Silicagel under argon
atmosphere for two days has no results, whereas pres-
ence both Silicagel and air results in rapid decomposi-
tion of 7. Exposition of isolated by TLC 7 solution to
In boiling benzene complex 6 is completely converted
for 5 h to a number of products, cluster 7 being the main
component. IR and NMR spectroscopy prove the new
compound is the Os3(CO)10(l-SR) type cluster. IR spec-
trum of the new cluster indicates no O–H group but
demonstrates the presence of a ketonic group, whereas
13C NMR spectrum shows the signal of organic carbon-
yl (202.37 ppm). Other parts of NMR spectra are similar
to those of cluster 6, so we assume the new cluster 7 is a
tautomeric form of cluster 6 (Scheme 3).
Similar tautomerism for the non-coordinated com-
pounds is known for the series of 5-hydroxy-4,5-dihyd-
ropyrazoles [8], however linear isomers can be detected
only in polar solvents (like DMSO) or in case of strong
electron withdrawing substituents in the hydropyrazole
moiety. As the tautomeric rearrangement 6fi7 is irre-
versible, the driving force of the transformation seems
to arise from the decrease of steric hindrance due to for-
mation of longer and flexible linker between C10 terpe-
noid unit and bulky Os3(CO)10(l-S-) cluster fragment.
When complex 7 is exposed to the air, a slow trans-
formation 7fi8 takes place. IR spectrum (CO stretching
region) and 1H NMR spectrum (signal of the l-H ligand
Fig. 2. D NMR spectrum of 8: heteronuclear 13C–1H correlation at the direct spin–spin coupling constants (J=135 Hz).

2540
V.P. Kirin et al. / Journal of Organometallic Chemistry 689 (2004) 2535–2542
Fig. 3. D NMR spectrum of 8: heteronuclear 13C–1H correlation at the long-range spin–spin coupling constants (J=10 Hz).
air results in slow conversion 7fi8. The transformation
is completed in five days.
treatment of 1-isothiocyanato-2-methoxybenzene with
an excess of hydrazine hydrate. The starting reagents
– Os3(CO)11(NCMe) (2) [12], and (1R,5R)-6,6-dimeth-
yl-2-(1-hydroxyethylidene)-bicyclo[3.1.0]hexan-3-one
(‘‘diketone’’) [13] were obtained by published procedures.
Analytical and preparative thin layer chromatography
(TLC) were performed on ready-made Silufolꢁ plates.
IR spectra were obtained using Specord IR-75 spectrom-
eter. NMR spectra were recorded at ambient temperature
on Bruker AM-400 (1H 400.13 MHz, 13C 100.61 MHz)
and Bruker DRX-500 (1H 500.13 MHz, 13C 125.75
MHz) spectrometers, using the solvent signals as internal
standard. Signals were assigned using the 13C NMR spec-
tra recorded in the J-modulation mode (noise proton de-
coupling, opposite phase for signals from atoms with
even and odd numbers of added protons with adjusting
to the constant J=135 Hz) and from data of the two-di-
mensional spectra (see Fig. 2): (1) J1H–1H homonuclear
correlation, (2) 13C–1H heteronuclear correlation on di-
rect spin–spin coupling constants (J=135 Hz), and (3)
13C–1H heteronuclear correlation on long-range spin–
spin coupling constants (J=10 Hz) (see Fig. 3). The num-
bering of the C-atoms shown in Scheme 1 does not
coincide with the numbering of the system according to
IUPAC. This numbering scheme is usual for this type
of derivatives and given for NMR interpretation only.
It should be stressed that opening of cyclopropanes
is rather usual, although the oxidative cleavage of
gem-dimethylcyclopropane moiety in complex 7 seems
to be exceptional. Radical oxidation of the medium
ring cycloalkanes with O(3P) results in epoxides in
small yields and shows the possibility of oxidative
transformation of non-functionalised cycloalkanes un-
der quite drastic conditions [11]. Reaction 7fi8 dem-
onstrates the unique example of activation of an
organic ligand on a cluster core as a very complex ox-
idative process which takes place under mild reaction
conditions.
3. Experimental
3.1. General
All reactions were carried out in freshly distilled
solvents and under argon atmosphere. The solvents were
removed from reaction mixtures at the reduced
pressure. Commercially available thiosemicarbazide
and Os3(CO)12 were used without additional purification.
4-(2-Methoxyphenyl)thiosemicarbazide was prepared by

V.P. Kirin et al. / Journal of Organometallic Chemistry 689 (2004) 2535–2542
2541
The mass spectra were measured on Aligent 1100 HPLS-
MS using electrospray ionisation technique and Finnigan
MAT 8200 (EI, 70 eV) spectrometers. The optical rota-
tion was measured on Polamat A polarimeter at the
wavelength of 578 nm.
(b) A mixture of Os3(CO)11(NCMe) (97 mg, 0.105
mmol) and 4 (39 mg, 0.163 mmol) in 50 ml of ben-
zene was stirred at room temperature for long as all
starting cluster was consumed (ꢁ10 min). Then the
reaction mixture was heated under reflux for 5 h,
evaporated to dryness and the residue was chroma-
tographed on Siluphol plates using petroleum
ether:benzene:acetone=5:3:0.5 mixture as eluent.
A bright yellow fraction with Rf ꢁ0.2 was extracted
by acetone to give 7 (60 mg, 52.2%).
3.2. (3aR, 3bR, 4aR, 5aS)-5a-Hydroxy-3,4,4-trimethyl-
3a,3b,4,4a,5,5a-hexahydrocyclopropa[3,4]–cyclopenta-
[1,2-c]pyrazole-1-carbothioic acid amide
Thiosemicarbazide (0.88 g, 4.5 mmol) was added to a
stirred solution of the diketone (0.66 g, 4 mmol) in a
mixture of methanol (25 ml) and glacial AcOH
(1 ml). The reaction mixture was heated and allowed
to stay under reflux for 3–4 h. The solvent was distilled
off at reduced pressure; the residue was treated with
water (40 ml) and extracted with CH2Cl2 (2·30 ml).
The combined extracts were dried (Na2SO4) and
concentrated to give the crude product that was then
purified by column chromatography (Al2O3, benzene)
followed by crystallization from MeCN–CHCl3 to give
an analytical sample of the title compound (yield 78%)
as pale-yellow crystals with m.p. 162–165 ꢂC (dec.,
(c) Solution of 7 (120 mg, 0.11 mmol) in flask filled
with air was standing at room temperature for six
days. Then solution was evaporated to dryness
and the residue was chromatographed on Silufol
plates,
eluent petroleum
ether:benzene:ace-
tone=5:3:0.5. A pale-yellow fraction was extracted
with acetone to give 8 (84 mg, 68%). Anal. Calc. for
C21H17N3O13Os3S: C, 22.48; H, 1.53; Os, 50.86.
Found: C, 22.71; H, 1.47; Os, 52.60. MS, m/z:
1126 (C21H17N3O13Os3S, 192Os, M+).
3.5. X-ray analysis of 5
20
MeCN–CHCl3) and [a]578 À224 (c 0.95, CHCl3).
MS, m/z: 239.11036 (M+, C11H17N3OS, requires
239.10923). UV (EtOH) kmax/nm 335 (e 530), 236
(e 10500), 272 (e 21400).
The structure of 5 was solved by X-ray structural
analysis. Crystal data: C20H15N3O10Os3S, F.W.
1060.01, monoclinic, space group P21/c, a=9.1943(12),
˚
b=22.653(3), c=12.8709(19) A, b=102.200(10), V=
3
2620.2(6) A , Z=4, dc =2.687 gcmÀ3, l=14.649 cmÀ1
.
Data were measured at room temperature on four-cycle
˚
3.3. Interaction of Os3(CO)11(NCMe) with acetone-4-
(2-methoxy-phenyl)thiosemicarbazone
Nonius CAD4 diffractometer using Mo Ka radiation
˚
A mixture of Os3(CO)11(NCMe) (1) (212 mg, 0.23
mmol) and acetone-4-(2-methoxy-phenyl)thiosemicar-
bazone (82 mg, 0.35 mmol) in 40 ml of benzene was
heated at reflux for 8 h. Then the reaction mixture was
evaporated to dryness and the residue was chromato-
graphed on Siluphol plates, using petroleum ether:ben-
zene:acetone=7:3:0.3 mixture as eluent. Complex 5
was obtained as a yellow amorphous solid (Rf ꢁ0.7,
185.2 mg, 74%). Anal. Calc. for C20H15N3O10Os3S: C,
22.60; H, 1.14; Os, 53.82. Found: C, 21.72; H, 0.96;
Os, 54.44. MS, m/z: 1064 (Os3C20N3O10Os3S, 192Os,
M+). The single-crystals of 5 were obtained by crystalli-
zation from benzene.
(k=0.7107 A) from orange plate crystal of 0.40.36·
0.04 mm size. Total 4888 reflections was measured up
to 2hmax =50ꢂ, of which 4588 are unique, Rint =0.0281.
Absorption corrections were applied by integration
from crystal shape, T=0.0370–0.5189. Structure was
solved by direct methods and refined by full-matrix
least-squares method in anisotropic for all non-hydro-
gen atoms approximation using SHELX 97 program
set. Final residuals are: R1 =0.0217 for 3374 Fhkl
4r(F), wR2 =0.0508, GoF=0.897 for all unique
reflections.
P
4. Supplementary material
3.4. Interaction of Os3(CO)11(NCMe) with (3aR,3-
bR,4aR,5aS)-5a-hydroxy-3,4,4-trimethyl-3a,3b,4,4a,5,5a
hexahydro-cyclopropa[3,4]cyclopenta[1,2-c]pyrazole-1-
carbothioic acid amide
Atomic coordinates, details of diffraction experiment
and full tables of bond distances and angles for 5 are de-
posited in Cambridge Crystallographic Data Centre,
CCDC No. 193254 for compound.
(a) A mixture of Os3(CO)11(NCMe) (85.5 mg, 0.0929
mmol) and 4 (16.7 mg, 0.0697 mmol) in 2 ml
CD2Cl2 was stirred at ambient temperature. On
the TLC data after dissolution of all reagents in
the solution there is the only complex 6, except of
starting cluster remains.
Acknowledgement
This work was supported by Russian Foundation for
Basic Research (Grant 01-03-33041).

2542
V.P. Kirin et al. / Journal of Organometallic Chemistry 689 (2004) 2535–2542
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