Antiferromagnetic complexes with metal-metal bonds. Part XXX. Synthesis and molecular structures of the antiferromagnetic adducts [Cp′Cr(μ-SPh)]2(μ3-Se).ML (Cp′=η5-CH3C5H4, ML=Fe3(μ3-S)2(CO)8

Article abstract of DOI:10.1016/S0022-328X(03)00048-2

The photochemical reactions of antiferromagnetic heterochalcogenic complex [Cp′Cr(μ-SPh)]₂(μ-Se) (1) (Cp′=η⁵-CH₃C₅H₄) with Fe₃(μ₃-Se)₂(CO)₉ or Mn₂(CO)₁₀ at room temperature gives new mixed-metal heterochalcogenic clusters [Cp′Cr(μ-SPh)]₂(μ₃-Se)Fe₃ (μ₃-Se)₂(CO)₈ (2), [Cp′Cr(μ-SPh)]₂(μ₃-Se)Mn₂ (CO)₉ (3) and [Cp′Cr(μ-SPh)]₂ (μ₄-Se)Mn₂(CO)₈ (4) which are antiferromagnetic (-2 J =256, 230 and 324 cm^-1, respectively) and characterized by X-ray diffraction analysis (2: Cr-Cr 2.763(1) A?; Fe-Fe 2.6184(9) and 2.706(1) A?; Cr-Se 2.447, 2.460 A?; 3: Cr-Cr 2.762 A?; Mn-Mn 2.920 A?; Cr-Se 2.447, 2.460 A?; 4: Cr-Cr 2.816 A?, Mn-Mn 2.835 A?, Cr-Se 2.464 A?). The photochemical reaction of 1 and Mn₂ (CO)₁₀ at higher temperature gives the paramagnetic complex Cp′Cr(μ-SPh)₃Mn(CO)₃ (5) with a weak Cr-Mn bond (3.0239 A?). The new heterochalcogenic complex [Cp′Cr(μ-SPh)]₂(μ-Te) (6) which obtained at the interaction of [Cp′Cr(CO)(μ-SPh)]₂ with Te and was studied by X-ray method (Cr-Cr 2.772 A?, Cr-S 2.359 A?, Cr-Te 2.601-2.607 A?, Cr-Te-Cr 64.3°), reacted with Co₂(CO)₈ with formation of the diamagnetic mixed-metal heterochalcogenic cluster [Cp′₂Cr₂(SPh)](μ₃-S) (μ₃-Te)Co(CO)₂ (7) (Cr-Cr 2. 646 A?, Cr-Co 2.627 A?-2.623 A?, Cr-μ₃-S 2.282-2.299 A?, Co-μ₃-S 2.199 A?, Cr-μ₃-Te 2.630-2.618 A?, Co-μ₃-Te 2.466 A?, Cr-μ-S_Ph 2.335 A?). The role of super-exchange spin-spin interaction through the chalcogen bridge atom is discussed.

Full text of DOI:10.1016/S0022-328X(03)00048-2

Journal of Organometallic Chemistry 671 (2003) 91ꢀ100
/
www.elsevier.com/locate/jorganchem
Antiferromagnetic complexes with metalꢀ
/
metal bonds.
Part XXX. Synthesis and molecular structures of the
antiferromagnetic adducts [Cp?Cr(m-SPh)]2(m3-Se).ML (Cp?ꢁ
CH3C5H4, MLꢁ
/
h5-
/
Fe3(m3-S)2(CO)8, Mn2(CO)9, Mn2(CO)8),
paramagnetic complexes Cp?Cr(m-SPh)3Mn(CO)3 and [Cp?Cr(m-
ꢀ
?
SPh)]2Te, diamagnetic cluster Cp2Cr2(m-SPh)(m3-S)(m3-Te)Co(CO)2
A.A. Pasynskii a,*, I.V. Skabitski a, Yu.V. Torubaev a, N.I. Semenova a,
V.M. Novotortsev a, O.G. Ellert a, K.A. Lyssenko b
a N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, 31 Leninsky Prosp. Moscow GSP-1, 119991, Russia
b A.N. Nesmeyanov Institute of Organoelement Compounds RAS, 28 Vavilova str., Moscow V-334, 117813, Russia
Received 31 October 2002; received in revised form 9 January 2003; accepted 9 January 2003
Abstract
The photochemical reactions of antiferromagnetic heterochalcogenic complex [Cp?Cr(m-SPh)]2(m-Se) (1) (Cp?ꢁ
h5-CH3C5H4)
/
with Fe3(m3-Se)2(CO)9 or Mn2(CO)10 at room temperature gives new mixed-metal heterochalcogenic clusters [Cp?Cr(m-SPh)]2(m3-
Se)Fe3(m3-Se)2(CO)8 (2), [Cp?Cr(m-SPh)]2(m3-Se)Mn2(CO)9 (3) and [Cp?Cr(m-SPh)]2(m4-Se)Mn2(CO)8 (4) which are antiferromagnetic
˚
(ꢂ
/
2Jꢁ
/
256, 230 and 324 cmꢂ1, respectively) and characterized by X-ray diffraction analysis (2: Crꢀ
/
Cr 2.763(1) A; Feꢀ
/
Fe 2.6184(9)
Mn 2.835
Se 2.464 A). The photochemical reaction of 1 and Mn2(CO)10 at higher temperature gives the paramagnetic complex
˚
˚
˚
˚
˚
˚
and 2.706(1) A; Crꢀ
/
Se 2.447, 2.460 A; 3: Crꢀ
/
Cr 2.762 A; Mnꢀ
/
Mn 2.920 A; Crꢀ
/
Se 2.447, 2.460 A; 4: Crꢀ
/
Cr 2.816 A, Mnꢀ
/
˚
˚
A, Crꢀ
Cp?Cr(m-SPh)3Mn(CO)3 (5) with a weak Crꢀ
which obtained at the interaction of [Cp?Cr(CO)(m-SPh)]2 with Te and was studied by X-ray method (Crꢀ
/
˚
/
Mn bond (3.0239 A). The new heterochalcogenic complex [Cp?Cr(m-SPh)]2(m-Te) (6)
˚
˚
S 2.359 A,
/
Cr 2.772 A, Crꢀ
/
˚
Crꢀ
/
Te 2.601ꢀ
/
2.607 A, Crꢀ
/
Teꢀ
/
Cr 64.38), reacted with Co2(CO)8 with formation of the diamagnetic mixed-metal heterochalcogenic
˚
˚
˚
˚
?
cluster [Cp2Cr2(SPh)](m3-S)(m3-Te)Co(CO)2 (7) (Crꢀ
/
Cr 2. 646 A, Crꢀ
/
Co 2.627 Aꢀ
/
2.623 A, Crꢀ
/
m3-S 2.282ꢀ
/
2.299 A, Coꢀm3-S 2.199
spin interaction through the
/
˚
˚
˚
˚
A, Crꢀ
/
m3-Te 2.630ꢀ
/
2.618 A, Coꢀ
/
m3-Te 2.466 A, Crꢀ
/
m-SPh 2.335 A). The role of super-exchange spinꢀ
/
chalcogen bridge atom is discussed.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Chromium; Manganese; Cobalt; Iron; Chalcogenide; Cyclopentadienyl complexes; Metal carbonyls; Mixed-metal clusters; Magnetic
properties; X-ray analyses
1. Introduction
In our preceding researches of antiferromagnetic
homo- and heterochalcogenic complexes [h5-
(RC5H4)2Cr2(m-SR?)2](m-X) where Rꢁ
/
CH3, R?ꢁPh,
/
ꢀ For Part XXIX see Ref. [1].
* Corresponding author. Tel.: ꢃ
1279.
E-mail address: aapas@rambler.ru (A.A. Pasynskii).
XꢁSe [1] or RꢁH, R?ꢁCMe3, XꢁS [2] and their
/
/
/
/
/
7-095-954-3841; fax: ꢃ7-095-954-
/
mixed-metal derivatives [1,3,4] we observed the signifi-
cant effect of the chalcogen bridge atom nature on the
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00048-2

92
A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ100
/
magnetic properties of clusters. In the investigated
clusters the contribution of super-exchange interactions
via chalcogenide bridge is comparable to the contribu-
tions of direct interactions through CrꢀCr bond [5].
/
Moreover the substitution of sulphur atom by a bigger
selenium atom results in the significant increasing of
exchange parameter ꢂ
SCMe3)]2(m-S) [2] to 578 cmꢂ1 for [Cp?Cr(m-SPh)]2(m-
Se) (1) notwithstanding with the elongation of CrꢀCr
bond from 2.689 to 2.730A [1]. It was known too that
the biggest elongation of the CrꢀCr bond took place at
the substitution of sulphur by tellurium atoms: from
/
2J from 430 cmꢂ1 for [CpCr(m-
/
˚
/
˚
˚
2.676 A in [CpCr(m-SPh)]2(m-S) [6] up to 2.935 A in
[CpCr(m-TePh)]2(m-Te) [7] (the magnetic properties of
the last complex were not learned-only a suggestion was
done about its paramagnetic activity because of the
signal broadening in H- and 13C-NMR spectra [7]).
In the case of Cp2Cr2(m-SCMe3)2(m-S).ML the super-
exchange interactions depend strongly upon the type of
1
ML coordination [4,8ꢀ11] (see Table 1)
/
The greatest exchange parameter values were ob-
?
served in the triangular metal clusters Cp2Cr2(SR)(m3-
S)(m3-X)Co(CO)2 (Xꢁ
/
S, Rꢁ
/
CMe3
ꢂ
/
2Jꢁ
/
578 cmꢂ1
[12]; XꢁSe, RꢁPh, ꢂ
/
/
/
2Jꢁ
/
692 cmꢂ1 [1]).
So we prepared some ML- containing derivatives of 1
on one hand and tellurium-containing complexes
?
[Cp?Cr(m-SPh)]2(m-Te)
and
Cp2Cr2(SPh)(m3-S)(m3-
Fig. 1. Molecular structure of complex 2.
Te)Co(CO)2 on the other hand to study the influence
of ML and chalcogen atom nature on the structures and
magnetic properties of clusters.
temperature gives the adduct [Cp?Cr(m-SPh)]2(m3-
Se).Fe3(m3-Se)2(CO)8 (2) which was structurally charac-
terized by means of single-crystal X-ray diffraction
analysis (Fig. 1, Tables 2 and 3):
2. Results and discussion
?
The photochemical interaction between [Cp2Cr2(m-
SPh)2](m-Se) (1) and Fe3(m3-Se)2(CO)9 at the room
Table 1
Types of complexes and ꢂ2J values
/

A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ
/100
93
Table 2
Crystal data and structure refinement for 2ꢀ
/
4
2
3
4
Empirical formula
Formula weight
Diffractometer
C
32H24Cr2Fe3O8S2Se3
1109.06
C33H24Cr2Mn2O9S2Se1/2(C4H10O)
958.54
C32H24Cr2Mn2O8S2Se
893.47
Smart 1000 CCD
110(2)
Smart 1000 CCD
293(2)
Siemens P3
293(2)
Temperature (K)
˚
Radiation, l(Moꢀ
Crystal system
Space group
/
Ka) (A)
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
Cc
Unit cell dimensions
˚
a (A)
˚
10.532(3)
25.344(1)
11.0719(7)
15.712(1)
16.032(3)
13.766(3)
16.377(3)
104.72(1)
3496(1)
4
b (A)
˚
c (A)
13.581(5)
94.72(2)
3613(2)
21.601(1)
96.943(1)
3730.2(4)
b (8)
3
˚
V (A )
Z
4
2.039
49.45
4
1.707
23.70
rcalc (g cmꢂ3
)
1.698
25.19
Linear absorption, m (cmꢂ1
Absorption correction
F(000)
)
Semiempirical from equivalents
2160
0.752/0.443
Semiempirical from equivalents
1916
0.838/0.753
c-curve
1776
Tmax/Tmin
Scan type
0.852/0.673
u/2u
v-scan 0.38/10 s exposure per frame
v-scan 0.38/10 s exposure per frame
u Range (8)
Measured
1.61ꢀ
42203
/
30.05
1.61ꢀ
23121
/
28.95
1.98ꢀ
3167
/25.05
Unique
10445 [Rint
6686
ꢁ/0.0524]
9027 (Rint
5871
ꢁ/
0.0323)
3167 (Rint
2442
ꢁ/0.0215)
With [I ꢀ2s(I)]
/
Parameters
Final R(Fhkl ): R1
wR2
453
571
427
0.0358
0.0675
0.972
0.0406
0.1007
0.810
0.0647
0.1517
0.974
GOF
˚
rmax/rmin (e A
ꢂ3
)
0.881/ꢂ
/0.632
1.505/ꢂ
/
0.415
1.623/ꢂ1.437
/
Table 3
˚
Selected bond lengths (A) and bond angles (8) for 2ꢀ4
/
2
3
4
Bond lengths
Cr(1)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Fe(1)ꢀ
Fe(1)ꢀ
Fe(1)ꢀ
Fe(2)ꢀ
Fe(2)ꢀ
Fe(3)ꢀ
Fe(3)ꢀ
Fe(2)ꢀ
Fe(1)ꢀ
/
Cr(2)
Se(1)
Se(1)
Se(2)
Se(3)
Se(1)
Se(2)
Se(3)
Se(2)
Se(3)
Fe(3)
Fe(3)
2.763(1)
2.4483(9)
2.4560(8)
2.320(1)
2.3493(8)
2.4648(9)
2.3595(8)
2.374(1)
2.366(1)
2.3758(8)
2.6184(9)
2.706(1)
Cr(1)ꢀ
Se(1)ꢀ
Se(1)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
Se(1)ꢀ
Mn(1)ꢀ
/
Cr(2)
2.7620(7)
2.4593(6)
2.4469(6)
2.360(1)
Cr(1)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Se(1)ꢀ
Se(1)ꢀ
/
Cr(2)
Se(1)
Se(1)
S(1)
2.816(3)
/
/Cr(1)
/
2.463(2)
2.464(3)
2.375(4)
2.379(5)
2.343(4)
2.344(4)
2.413(2)
2.425(3)
2.835(3)
/
/Cr(2)
/
/
/S(1)
/
/
/S(2)
2.359(1)
/S(1)
/
/Mn(1)
2.5506(6)
2.9502(7)
/S(2)
/
/
Mn(2)
/S(2)
/
/Mn(2)
/
/Mn(1)
/
Mn(1)ꢀMn(2)
/
/
/
Bond angles
Cr(1)ꢀSe(1)ꢀ
Cr(1)ꢀSe(1)ꢀ
Cr(2)ꢀSe(1)ꢀ
Fe(1)ꢀSe(2)ꢀ
Fe(1)ꢀSe(2)ꢀ
Fe(2)ꢀSe(2)ꢀ
Fe(1)ꢀSe(3)ꢀ
Fe(1)ꢀSe(3)ꢀ
Fe(2)ꢀSe(3)ꢀ
/
/
Cr(2)
Fe(1)
Fe(1)
Fe(2)
Fe(3)
Fe(3)
Fe(2)
Fe(3)
Fe(3)
68.58(3)
114.56(3)
112.53(3)
97.84(3)
70.53(2)
67.29(3)
96.66(3)
69.88(3)
66.92(2)
Cr(2)ꢀ
Cr(2)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
/
Se(1)ꢀ
/
Cr(1)
68.52(2)
71.82(3)
71.54(3)
71.54(3)
Mn(2)ꢀ
Mn(2)ꢀ
Mn(1)ꢀ
Mn(2)ꢀ
Mn(1)ꢀ
Cr(1)ꢀSe(1)ꢀ
Cr(1)ꢀS(2)ꢀCr(2)
/
Se(1)ꢀ
Se(1)ꢀ
Se(1)ꢀ
Se(1)ꢀ
Se(1)ꢀ
/
Mn(1)
Cr(1)
Cr(1)
Cr(2)
Cr(2)
71.75(9)
136.05(9)
126.72(1)
139.5(1)
122.61(8)
69.71(7)
73.9(1)
/
/
/
S(1)ꢀ
S(2)ꢀ
S(2)ꢀ
/
Cr(1)
Cr(2)
Cr(2)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/Cr(2)
/
/
/
/
/
/
/
/

94
A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ100
/
The geometry of Fe3(m3-Se)2(CO)8 fragment does not
undergoes significant changes in comparison with the
initial Fe3(m3-Se)2(CO)9 [13]. The length of Cr(1)ꢀCr(2)
Se(1)ꢀ
Cr(2) (68.58(3)8) are close to those for complex 1 but
/
˚
bond (2.763(1) A) and the value of angle Cr(1)ꢀ
/
/
˚
Se bonds (2.4483(9) and 2.4560(8) A) are elongated
Crꢀ
in comparison with 1 (Crꢀ
this elongation could be the reason of the decreasing of
the exchange parameter of 2 (ꢂ2Jꢁ
256 cmꢂ1): meff
reduced from 1.8mB (287 K) to 0.42mB (79 K) with
respect to 578 cmꢂ1 for 1.
/
˚
/
Se 2.401 and 2.396 A) and
/
/
Selenium atom is coordinated to only one of manga-
˚
nese atoms (Mnꢀ
/
Se 2.5506(6) A). The Mnꢀ
/
Mn and Crꢀ
/
˚
Cr bond lengths (2.920 and 2.762 A, respectively)
remain almost unchanged in comparison with initial
The photochemical interaction between
1 and
Mn2(CO)10 at the room temperature gives black crystals
of [Cp?Cr(m-SPh)]2(m3-Se)Mn2(CO)9 (3) studied by X-
ray analysis (Fig. 2, Tables 2 and 3).
compounds, while significant elongation of Crꢀ
/
Se
bonds up to 2.447 and 2.460 A takes place. The similar
elongation of CrꢀSe bonds was observed in 2 and in the
known cluster Cp2Cr2(SePh)2SeCr(CO)5 [14]. This Crꢀ
Se bond elongation in 3 is accompanied by decreasing of
its ꢂ
2J value to 230 cmꢂ1 (meff reduced from 1.68 down
to 0.56mB in the 295ꢀ80 K temperature range) with
respect to 578 cmꢂ1 for 1. It is noteworthy that ꢂ
2J
values for all adducts Cp2Cr2(m-SCMe3)2(m-S).ML (Ta-
440 cmꢂ1 [3], e.g. very close to 430
˚
/
/
/
/
/
ble 1) are near 400ꢀ
/
cmꢂ1 for the initial Cp2Cr2(m-SCMe3)2(m-S) [2]. It
means that antiferromagnetic exchange interactions in
selenide-bridged complexes are more sensitive to the
nature of chalcogen atom than in the case of sulfide-
bridged complexes.
Keeping of the ether solution of 3 at ꢂ
/
10 8C for 48 h
Fig. 2. Molecular structure of complex 3.
favours the further decarbonylation with the formation

A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ
/100
95
place the significant decreasing of ꢂ
/
2J values in
comparison with m3-S-containing clusters, particularly
containing Mn2(CO)9 group (Table 1). Probably some
role could play the presence of Mnꢀ
whereas known m4-S-containing clusters had two ML
groups linked by two iodine bridges only without Mꢀ
bond between them (Table 1).
/
Mn bond in 4
/
M
The conservation of the structure of 1 during the
photochemical inter-reaction with Fe3(m3-Se)2(CO)9 or
Mn2(CO)10 and formation of the adducts 2ꢀ
contrast to the known photochemical transformations
of Cp2Cr2(m-SCMe3)2(m-S) into pentanuclear metalꢀ
spirane cluster
Cp2Cr2(m-SCMe3)(m3-S)2Fe(m3-
S)2Fe2(CO)9 [15] and triangular cluster Cp2Cr2(m-
SCMe3)(m3-S)2Mn(CO)3 [16], respectively. Probably
this difference results from the longer distance between
ML group and chromium atoms in the presence of
bulky selenide bridge in comparison with sulfide bridge,
/
4 is in
/
Fig. 3. Molecular structure of complex 4.
of a new cluster [Cp?Cr(m-SPh)]2(m4-Se)Mn2(CO)8 (4)
which was characterized by X-ray analyses (Fig. 3,
Tables 2 and 3) and has a spirane-like metalꢀchalco-
/
on one hand, and on the other hand *
/
the stronger Sꢀ
/
genide core where m4-Se atom is coordinated with two
˚
˚
Se av. 2.464 A) and
Ph bond in respect to SꢀCMe3 bond, does not favour
/
chromium (Crꢀ
two manganese atoms (Mnꢀ
/
Cr 2.816(3) A, Crꢀ
/
˚
the elimination of CMe3 accompanying the transforma-
tion of SPh into m3-S bridging ligand.
/
Mn 2.835(3) A, Mnꢀ
/
Se av.
˚
2.419 A).
Due to an elongation of Crꢀ
The photochemical reaction of 1 and Mn2(CO)10 at
higher temperature (in refluxing benzene) unexpectedly
leads to Cp?Cr(m-SPh)3Mn(CO)3 (5) instead of triangu-
/
Cr bond in 4 with respect
to 2.76 A in 3 one could expect decreasing of ꢂ2J value
but its unexpected increasing up to 324 cmꢂ1 (meff
reduced from 1.51mB down to 0.53mB in the 292ꢀ79 K
˚
/
?
lar Cp2Cr2(m-SPh)(m3-Se)(m3-S)Mn(CO)3 supposed by
/
analogy with known Cp2Cr2(m-SCMe3)(m3-S)2Mn(CO)3
[16,17].
temperature range) was observed. The reason is still not
clear. We could only suppose that it is a result of some
electronic features of m4-Se atom which has no lone pair
According to the X-ray data (Fig. 4, Tables 4 and 5)
˚
(particularly, in 4 the significant shortening of the Mnꢀ
/
the Cr(1)ꢀMn(1) bond (3.0239(7) A) has probably an
/
˚
Se bond lengths (av. 2.418(3) A) takes place in compar-
order 0.5 in accordance with the observed paramagnetic
properties of 5 * three unpaired electrons (mof (3.67mB)
does not depend on the temperature).
˚
Se distance (2.5506(6) A in 3). But in the
ison with Mnꢀ
/
/
case of two known clusters with m4-S-bridge atom took

96
A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ100
/
Single-crystal X-ray diffraction analysis of 7 (Fig. 6,
Tables 4 and 5) demonstrated the similarity of its core to
?
those found earlier for Cp2Cr2(SR)(m3-S)(m3-X)Co(CO)2
(Xꢁ
/
S; Rꢁ
/
CMe3 (8) [8] or Xꢁ
/
Se; RꢁPh (9) [1]). In 7
/
m3-telluride and m3-sulfide bridging atoms are situated
˚
over and under Cr2Co triangle (Crꢀ
/
S 2.299(1) A, CoꢀS
/
˚
˚
˚
2.199(1) A, Crꢀ
/
Te 2.6303(9) A, CoꢀTe 2.466(1) A).
/
Diamagnetic properties of 7 are unexpected because the
˚
metalꢀ
/
metal bonds (Crꢀ
/
Cr 2.646(1) A, Crꢀ
/
Co 2.628(1)
˚
˚
Cr 2. 590 A,
A) in 7 are elongated in respect to 8 (Crꢀ
/
˚
˚
Crꢀ
/
Co 2.530 and 2.569 A) and 9 (Crꢀ
/
Cr 2. 624 A, Crꢀ
/
˚
Co av. 2. 612 A) which appeared antiferromagnetic
properties. Apparently in 7 the super-exchange interac-
tions via tellurium atom are more important than direct
spinꢀ
/
spin interactions via MꢀM bonds.
/
Fig. 4. Molecular structure of complex 5.
The Te-bridged binuclear chromium complex
3. Experimental
[CpCr(m-SPh)]2(m-Te) (6) was prepared by the reaction
of elemental tellurium with [Cp?Cr(CO)(m-SPh)]2 which
was obtained while the decarbonylation of
[Cp?Cr(CO)2(m-SPh)]2:
All manipulations were carried out in pure argon
atmosphere with using of absolute solvents. Commercial
Mn2(CO)10
was
recrystallized
from
hexane.
The structure of the black crystals of 6 was studied by
single-crystal X-ray diffraction analyses (Fig. 5, Tables 4
[Cp?Cr(CO)3]2 was prepared in accord with [18].
Fe3(CO)9(Se)2 was prepared as in Ref. [19]. IR-spectra
were recorded at ‘Specord-75 IR’ in KBr pellets.
Differential scanning calorimetry (DSC) was studied
with thermoanalyser ‘Mettler’ TA-3000 in dry argon.
The temperature dependence of the magnetic suscept-
ibilities (xm) of the investigated compounds was deter-
mined by the Faraday technique between 77 and 296 K
using original device [20]. The effective magnetic mo-
ments of compounds were calculated by formula (1)
and 5). It contains two Cp?Cr groups linked by direct
˚
Crꢀ
(Crꢀ
Te 2.601(2)ꢀ
/
Cr bond (2.772(3) A), two thiolate bridge groups
˚
/
S av. 2.359 A) and one telluride bridge atom (Crꢀ
/
˚
/
2.607(2) A, Crꢀ
/
TeꢀCr 64.30(7)8). Complex
/
6 is unstable and it was impossible to get the clear data
on its magnetic properties.
The reaction of 6 with Co2(CO)8 gives mixed-metal
?
heterochalcogenic cluster [Cp2Cr2(m-SPh)](m3-S)(m3-
Te)Co(CO)2 (7) as diamagnetic brown crystals which
are stable under argon.
meff ꢁ797:7(BmT)1=2
(1)

A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ
/100
97
Table 4
Crystal data and structure refinement for 5ꢀ
/7
5
6
7
Empirical formula
Formula weight
Diffractometer
C
597.57
27H22CrMnO3S3
C24H24Cr2S2Te
608.15
C20H19CoCr2O2S2Te
646.00
Smart 1000 CCD
190(2)
Siemens P3
298(2)
Smart 1000 CD
110(2)
Temperature (K)
˚
Radiation, l(Moꢀ
Crystal system
Space group
/
Ka) (A)
0.71073
Orthorhombic
Pbca
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/c
Unit cell dimensions
˚
a (A)
˚
14.5207(9)
18.623(1)
12.447(6)
13.827(7)
13.719(7)
92.24(4)
2359.4(19)
4
10.220(3)
16.187(5)
b (A)
˚
c (A)
19.380(1)
90
5240.5(5)
13.373(4)
101.07(3)
1636.3(9)
b (8)
3
˚
V (A )
Z
8
1.515
4
1.681
rcalc (g cmꢂ3
)
1.712
23.18
Linear absorption, m (cmꢂ1
Absorption correction
F(000)
)
11.63
Semiempirical from equivalents
32.61
Empirical from equivalents
c-curve
1200
2440
0.967/0.77
1256
0.801/0.543
Tmax/Tmin
Scan type
0.756/0.643
u/2u
v-scan 0.38/10 s exposure per frame
v-scan with 0.38/10 s exposure per frame
u Range (8)
Measured
2.07ꢀ
38037
/
29.06
2.62ꢀ
2099
/20.04
2.61ꢀ
20742
/
27.52
Unique
6973 (Rint
3757
ꢁ/0.0543)
1974 (Rint
1577
ꢁ/0.0434)
4966 (Rint
3353
ꢁ/0.0477)
With [I ꢀ2s(I)]
/
Parameters
Final R(Fhkl ): R1
wR2
404
262
329
0.0472
0.1000
0.977
0.0447
0.1136
1.027
0.0367
0.0833
0.980
GOF
˚
rmax/rmin (e A
ꢂ3
)
1.008/ꢂ
/
0.315
0.579/ꢂ
/
0.464
1.110/ꢂ1.076
/
The best-fit of the values was obtained with the
HeisenbergꢀDirakꢀVan Vlek (HDVV) theoretical
model for two exchange-coupled paramagnetic ions in
the absence of orbital degeneracy of the complex ground
/
/
Table 5
Selected bond lengths (A) and bond angles (8) for 5ꢀ
˚
/
7
5
6
7
Bond lengths
Cr(1)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
Mn(1)ꢀ
Mn(1)ꢀ
Mn(1)ꢀ
/
S(2)
2.3429(8)
2.3591(9)
2.3711(9)
3.0239(7)
2.3985(8)
2.3997(9)
2.4210(8)
Cr(2)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Cr(2)ꢀ
/
Te(1)
Te(1)
S(1)
2.609(2)
2.602(2)
2.359(3)
2.357(3)
2.358(3)
2.364(3)
Cr(2)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Cr(2)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Co(1)ꢀ
Te(1)ꢀCo(1)
/
Te(1)
Te(1)
S(1)
2.618(1)
2.630(1)
2.282(2)
2.335(1)
2.290(1)
2.333(1)
2.628(1)
2.623(1)
2.199(1)
2.466(1)
/S(1)
/
/
/S(3)
/
/
/Mn(1)
/
S(2)
/
S(2)
/
S(2)
S(1)
S(3)
/
S(1)
S(2)
/
S(1)
/
/
/
S(2)
/
/
Co(1)
Co(1)
/
/S(1)
/
Bond angles
Cr(1)ꢀS(1)ꢀ
Cr(1)ꢀS(2)ꢀ
Cr(1)ꢀS(3)ꢀ
/
/
Mn(1)
Mn(1)
Mn(1)
78.90(3)
79.24(3)
78.24(3)
Cr(2)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
/
Te(1)ꢀ
/
Cr(1)
64.28(6)
71.97(10)
71.90(10)
Cr(2)ꢀ
Cr(1)ꢀ
Cr(2)ꢀ
Co(1)ꢀ
Co(1)ꢀ
Co(1)ꢀ
Co(1)ꢀ
/
Te(1)ꢀ
/
Cr(1)
60.56(3)
70.55(5)
69.05(4)
62.03(3)
61.97(3)
71.77(4)
71.28(4)
/
/
/
S(1)ꢀ
/
Cr(2)
Cr(1)
/
S(1)ꢀ
/
Cr(2)
Cr(1)
/
/
/
S(2)ꢀ
/
/
S(2)ꢀ
/
/Te(1)ꢀ
/Cr(2)
/Te(1)ꢀ
/Cr(1)
/S(1)ꢀ/Cr(1)
/S(1)ꢀ/Cr(2)

98
A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ100
/
where J is the isotropic exchange parameter, g is the
isotropic g factor and S are the spins of the exchange
coupled ions. The calculation of the theoretical meff
values and the least-squares treatment were carried as
reported [21].
Crystal structures were solved by direct method and
refined in full-matrix anisotropicꢀisotropic (H-atoms)
/
approximation. All calculations were carried out with
the complex of programs SHELXTL PLUS 5 [22]. The
important crystallographic data and refinement para-
meters for 2ꢀ
important bond lengths and angles of the complexes 2ꢀ
are presented in the Tables 3 and 5.
/
7 are given in Tables 2 and 4. The most
/7
?
3.1. Preparation of Cp2Cr2(SPh)2SeFe3Se2(CO)8 (2)
The solution of 0.15 g (0.26 mmol) of 1 and 0.15 g
(0.26 mmol) Fe3Se2(CO)9 in benzene (20 ml) was
irradiated by UV-light for 9 h while stirring and cooling
by running water. Resulting dark brown reaction
mixture was evaporated to dryness and the residue was
extracted with 25 ml of hexane and then with 30 ml of
ether. To the ether solution 15 ml of hexane was added
and both extracts were concentrated in vacuo to 1/4 of
initial volume and kept at ꢂ
brown crystals were separated, washed by hexane and
recrystallized from Et2Oꢃhexane (1:2) mixture. Yield
0.17g (57%).
IR-spectra (cmꢂ1): 584 w, 608 w, 688 w, 744 w, 816 w,
800 m, 1952 m, 1976 s, 1990 s, 2016 s, 2048 s. Anal.
Found: C, 34.58; H, 2.16; S, 6.27; (DSC) CO, 20.2. C6H5
13.9; Cp? 14.3. Residue after pyrolyses: Cr2Fe3S2Se3.
C32H24S2Se3Cr2Fe3O8. Calc.: C, 34.66; H, 2.18; S, 5.78;
CO, 20.0; C6H5, 13.6; Cp?, 14.4%.
/
18 8C for 48 h. Blackꢀ
/
Fig. 5. Molecular structure of complex 6.
/
states. The spin Hamiltonian has the form (2)
H ꢁꢂ2JS1S2 ꢃgbH(S1z ꢃS2z)
(2)
The single crystals of 2 were used for X-ray analysis.
?
3.2. Preparation of Cp2Cr2(m-SPh)2(m3-Se)Mn2(CO)9
(3)
The solution of 0.5 g (0.89 mmol) of 1 and 0.4 g (0.96
mmol) of Mn2(CO)10 in benzene (30 ml) was irradiated
by UV-light for 1.5 h while stirring and cooling by
running water. Reaction mixture was evaporated to
dryness and the residue was extracted with 30 ml of
Et2O. Hexane (10 ml) was added to extract, the mixture
was concentrated until the beginning of crystallization
and kept at ꢂ10 8C for 12 h. Black needle-like crystals
/
were dried in vacuo. Yield 0.45 g (54%).
IR (cmꢂ1): 2960 w, 2920 w, 2360 w, 2072 s, 2000 s,
1975 s, 1936 s, 1905 s, 1665 w, 1576 m, 1470 w, 1065 w,
1025 w, 1000 w, 825 s, 745 s, 688 m, 650 s, 615 m, 480 m,
410 m. Anal. Found: C, 43.12; H, 3.87; S, 7.09. Calc. for
C33H24S2SeCr2Mn2O9: C, 43.01; H, 2.63; S, 6.96.%.
The single crystals of 3 were used for X-ray analysis.
Fig. 6. Molecular structure of complex 7.

A.A. Pasynskii et al. / Journal of Organometallic Chemistry 671 (2003) 91ꢀ
/100
99
?
3.3. Preparation of Cp2Cr2(m-SPh)2(m-Se)Mn2(CO)8
(4)
?
3.6. Preparation of Cp2Cr2(m-PhS)(m-S)(m-
Te)Co(CO)2 (7)
A mother solution left after precipitation of 3 was
evaporated to dryness, extracted with 20 ml of Et2O,
concentrated to 20 ml after addition of 10 ml of hexane
A violet solution of 0.1 g (0. 16 mmol) of 6 in 10 ml
CH2Cl2 was added to the yellowꢀbrown solution of 0.1
/
g (0.32 mmol) Co2(CO)8 in 20 ml of CH2Cl2. The
mixture was evaporated in vacuum, the residue was
washed by 10 ml of hexane and extracted by 20 ml of
Et2O. This extract after addition of 10 ml of hexane was
concentrated until the small quantity of brown precipi-
tate forms. The solution was filtered and after addition
of 5 ml of hexane was again concentrated to 3 ml and
and then kept at ꢂ
/
10 8C for 48 h. Blackꢀgreen crystals
/
were separated, washed with hexane and dried in vacuo.
Yield 0.08 g (10%). IR (cmꢂ1): 2045 m, 1970 s, 1925 s,
1900 s, 825 m, 740 s, 700 w, 655 m, 620 s.
The single crystals of 4 recrystallized from CH2Cl2ꢃ
/
hexane were used for X-ray analysis.
then kept at ꢂ10 8C for 12 h. Needle-like crystals of 6
/
3.4. Preparation of Cp?Cr(m-SPh)3Mn(CO)3 (5)
were washed by cold hexane and dried in vacuo. Yield
0.02g (19%).
The solution of 0.3 g (0.53 mmol) of 1 and 0.2 g (0.51
mmol) of Mn2(CO)10 in boiling benzene (20 ml) was
irradiated by UV-light for 2 h. Reaction mixture was
evaporated to dryness, washed with 10 ml of hexane and
the residue was extracted with 40 ml of ether. To this
extract 10 ml of hexane was added and the solution was
IR spectrum (cmꢂ1): 1975 s, 1935 s, 830 m, 735 w, 535
w. Anal. Found: C, 36.82; H, 3.41; S, 9.66. Calc. for
C20H19S2SeCr2CoO2: C, 37.21; H, 2.94; S, 9.92%.
The single crystal of 7 was used for X-ray analysis.
concentrated in vacuo to 20 ml and kept at ꢂ10 8C for
/
4. Supplementary material
12 h to give black prisms washed with hexane and dried
in vacuo. Yield 0.05 g (23%). IR (KBr, cmꢂ1): 2010 s,
1930 s, 1905 s, 1020 w, 820 m, 740 s, 690 m, 620 m.
The single crystal of 5 was used for X-ray analysis.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 183565 (2), 183564 (3), 183566
(4), 183567 (5), 172670 (6) and 172671 (7). Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
3.5. Preparation of [Cp?Cr(m-SPh)]2(m-Te) (6)
3.5.1. Preparation of [Cp?Cr(CO)(m-SPh)]2
UK (Fax: ꢃ44-1223-336033; e-mail: deposit@ccdc.cam.
/
Ph2S2 (1.06 g, 4.8 mmol) was added to the green
solution of 2.1 g (4.8 mmol) [Cp?Cr(CO)3]2 in 50 ml of
hexane at 0 8C and was stirred for 0.5 h. Resulting dark-
orange solution was refluxed for 1 h until the disappear-
ing of intermediate [Cp?Cr(CO)2]2(m-SPh)2 (TLC, Silu-
ac.uk or www: http://www.ccdc.cam.ac.uk).
Acknowledgements
fol: orange spot, Rf ꢂ0.6 in benzene). Black crystalline
/
We thank Dr. Zh.V. Dobrokhotova for the differ-
ential scanning calorimetric study and Russian Founda-
tion of Basic Research (grants 02-03-33075, 00-03-
32626, 02-03-06170, 02-03-06171) for financial support.
precipitate was filtered from green solution, extracted
with CH2Cl2 and after evaporation of cherry-brown
solution the resulting tar was crystallized at the treating
by benzene. The solid substance was separated, washed
by hexane and dried in vacuo. Yield [Cp?Cr(CO)(m-
SPh)]2 0.35 g (37%). IR spectra (cmꢂ1): 1870 s, 810 m,
730 s, 680 m.
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Organomet. Chem. 612 (2000) 9.
3.5.2. The reaction of [Cp?Cr(CO)(m-SPh)]2 with Te
To the solution of 0.35g (0.65 mmol) Cp?Cr(CO)(m-
SPh)]2 in 50 ml of THF 0.14 g (1.1mmol) of Te powder
was added and the mixture was stirred for 18 h at the
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/
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addition of hexane gave black crystals which were
washed by hexane and dried in vacuum. Yield 0.1 g
(23%). IR spectra (cmꢂ1): 1080 m, 1020 m, 810 s, 730 s,
680 m.
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