Triruthenium clusters containing bridging dppm and capping sulfido and selenido ligands: (see abstract)

Article abstract of DOI:10.1016/j.jorganchem.2004.08.015

The reaction of [Ru₃(CO)₁₀(μ-dppm)] (1) with dppmSe at 66 °C affords [Ru₃(CO)₈(μ-dppm) ₂] (2), [Ru₃(CO)₇(μ₃-CO) (μ₃-Se)(μ-dppm)] (3), [Ru₃(CO)₅ (μ₃-CO)(μ₃-Se)(μ-dppm)₂] (4) and [Ru₃(CO)₆(μ₃-CO)(μ₃ -Se)(μ-dppm)(η¹-Ph₂PCH₂P(=O) Ph₂)] (5) in 7%, 5%, 9% and 33% yields, respectively. A similar reaction between 1 with dppmS gives [Ru₃ (CO)₇(μ₃-S)₂(μ-dppm)] (6), [Ru₃(CO)₇(μ₃-CO)(7μ₃-S) (μ-dppm)] (7) [Ru₃(CO)₅(μ₃-CO) (μ₃-S)(μ-dppm)₂] (8) and [Ru₃ (CO)₆(μ₃-CO)(μ₃-S)(μ-dppm) (η¹-Ph₂PCH₂P(=O)Ph₂)] (9) in 8%, 7%, 14% and 35% yields, respectively. Treatment of 1 with PhSeSePh at 66 °C affords the dinuclear compound [Ru₂(CO) ₄(μ-SePh)₂(μ-dppm)] (10) in 14% yield. Thermolysis of 5 and 9 in refluxing toluene at 110 °C gives 4 and 8, respectively. The molecular structures of 4, 9 and 10 have been determined by single-crystal X-ray diffraction studies. The cores of the new clusters 4, 5, 8 and 9 consist of metal triangles capped by μ₃-sulfur or selenium atoms with the bidentate ligand bridging in equatorial positions. In compounds 4 and 8, two bidentate dppm ligands bridge the Ru₃ triangle in such a way that each ligand bridges two ruthenium atoms and one Ru-Ru edge remains unbridged. Compounds 5 and 9 contain one bridging dppm ligand and one dangling dppm mono-oxide ligand Ph₂PCH₂P(=O)Ph₂ coordinated to the rear metal atom at an equatorial position. The molecular structure of 10 shows classical sawhorse structure with two bridging SePh ligands as well as the dppm ligand.

Full text of DOI:10.1016/j.jorganchem.2004.08.015

Journal of Organometallic Chemistry 689 (2004) 3412–3420
www.elsevier.com/locate/jorganchem
Triruthenium clusters containing bridging dppm and capping
sulfido and selenido ligands: X-ray structures of
[
Ru (CO) (l -CO)(l -Se)(l-dppm) ],
3
5
3
3
2
1
[
Ru (CO) (l -CO)(l -Se)(l-dppm)(g -Ph PCH P(@O)Ph )]
3
6
3
3
2
2
2
and [Ru (CO) (l-SePh) (l-dppm)]
2
4
2
a
a
a
a
Shariff E. Kabir * , Syed J. Ahmed , Md. Iqbal Hyder , Md. Arzu Miah ,
b
b
b
Dennis W. Bennett * , Daniel T. Haworth , Tasneem A. Siddiquee ,
c,
*
Edward Rosenberg
a
Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
Department of Chemistry, University of Wisconsin–Milwaukee, Wisconsin, WI 53211, USA
b
c
Department of Chemistry, The University of Montana, Missoula, MT 59812, USA
Received 25 May 2004; accepted 9 August 2004
Available online 11 September 2004
Abstract
The reaction of [Ru
3
(CO)10(l-dppm)] (1) with dppmSe at 66 ꢀC affords [Ru
3 8 2 3 7 3 3
(CO) (l-dppm) ] (2), [Ru (CO) (l -CO)(l -Se)(l-
1
dppm)] (3), [Ru (CO) (l -CO)(l -Se)(l-dppm) ] (4) and [Ru (CO) (l -CO)(l -Se)(l-dppm)(g -Ph PCH P(@O)Ph )] (5) in 7%,
3
5
3
3
2
3
6
3
3
2
2
2
5
%, 9% and 33% yields, respectively. A similar reaction between 1 with dppmS gives [Ru
3
(CO)
7
(l
3
-S)
2
(l-dppm)] (6),
1
[
Ru (CO) (l -CO)(l -S)(l-dppm)] (7) [Ru (CO) (l -CO)(l -S)(l-dppm) (8) and [Ru (CO)
3
7
3
3
3
5
3
3
2
]
3
(l
6 3
-CO)(l
3
-S)(l-dppm)(g -
Ph PCH P(@O)Ph )] (9) in 8%, 7%, 14% and 35% yields, respectively. Treatment of 1 with PhSeSePh at 66 ꢀC affords the dinuclear
2
2
2
compound [Ru
respectively. The molecular structures of 4, 9 and 10 have been determined by single-crystal X-ray diffraction studies. The cores
2
4 2
(CO) (l-SePh) (l-dppm)] (10) in 14% yield. Thermolysis of 5 and 9 in refluxing toluene at 110 ꢀC gives 4 and 8,
of the new clusters 4, 5, 8 and 9 consist of metal triangles capped by l -sulfur or selenium atoms with the bidentate ligand bridging
3
in equatorial positions. In compounds 4 and 8, two bidentate dppm ligands bridge the Ru triangle in such a way that each ligand
3
bridges two ruthenium atoms and one Ru–Ru edge remains unbridged. Compounds 5 and 9 contain one bridging dppm ligand and
one dangling dppm mono-oxide ligand Ph
ular structure of 10 shows classical ‘‘sawhorse’’ structure with two bridging SePh ligands as well as the dppm ligand.
2004 Elsevier B.V. All rights reserved.
2
PCH
2
2
P(@O)Ph coordinated to the rear metal atom at an equatorial position. The molec-
ꢁ
Keywords: Triruthenium carbonyl clusters; Sulfido and selenido ligands; Bis(diphenylphosphino)methane mono-oxide; Crystal structures
1
. Introduction
important chemical and structural significance, since
they can be regarded as discrete molecular models of ex-
tended inorganic solids [1]. The presence of chalcogen-
ido ligands often appears to be decisive in cluster
aggregation reactions and in generating new coordina-
tion modes and geometries [2,3]. Presently, different syn-
thetic routes are available for the preparation of sulfido
Transition metal carbonyl clusters containing chalco-
genide elements (S, Se or Te) as bridging ligands have
*
Corresponding author. Tel.: +1 406 243 2592; fax: +1 406 243
4227.
E-mail address: rosen@selway.umt.edu (E. Rosenberg).
0
022-328X/$ - see front matter ꢁ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.08.015

S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
3413
or selenido transition-metal clusters, among these, those
that involve the oxidative addition of tertiary phosphine
chalcogenide compounds to zero-valent metal centers
appear to be the most effective [4]. This method, takes
dppm)], the cubane like cage cluster [Ru (CO) (l -
4 10 3
Se) (l-dppm) [10]. Previously, we reported the synthesis
4
and reactivity of the capping sulfido compound
[Os (CO) (l -S) (l-dppm)] from the reaction of
3
7
3
2
advantage of the frailty of the Ph P@E (E = S or Se)
[Os (CO) (l-dppm)] with tetramethylthiourea [11] and
3 10
3
bond and has been successfully used by the Tiripicchio
group to synthesize tertiary phosphine substituted iron
and ruthenium clusters containing capping calcogenido
ligands [5]. Adams et al. [6] have recently reported some
manganese and mixed iron-manganese carbonyl clusters
bearing triphenylphosphine and triply bridging selenido
the capping selenido compounds [Os (CO) (l -Se) (l-
3 7 3 2
dppm)] and [Os (CO) (l -CO)(l -Se)(l-dppm)] from
3
7
3
3
the reaction between [Os (CO) (MeCN) ] and dppmSe
3
10
2
[12]. With the aim of synthesizing capping selenido and
sulfido triruthenium compounds containing more than
one edge bridging dppm ligand we have investigated
the reaction of [Ru (CO) (l-dppm)] (1) with dppmSe
ligands from the reactions of Ph P@Se with
3
3
10
[
Mn (CO) (MeCN)] and [CpFeMn(CO) ] while Braun-
and dppmS and the results are described in the present
paper. The proposed doubly edge bridged and chalcoge-
nide capped clusters should exhibit exceptional thermal
stability and could prove useful for cluster aggregation
transformations.
2
9
7
stein et al. [7] have reported a series of mixed metal
tri- and tetranuclear clusters containing capping selen-
ido ligands from the reactions between [(l-H)MCo3
(
as Ph PSe, Ph P(Se)CH PPh , (2-C H N)Ph PSe and
CO) ] (M = Fe or Ru) and phosphine selenides such
12
3
2
2
2
5
4
2
(
2-C H S)Ph PSe.
4 3 2
Bis(diphenylphosphino)methane (dppm) has been
extensively used as a ligand and the chemistry of its
dioxide (dppmO ), disulfide (dppmS ) and diselenide
2. Results and discussion
The reaction of [Ru (CO) (l-dppm)] (1) with dpp-
2
2
3
10
(
(
dppmSe ) and its monoxide (dppmO), monosulfide
2
mSe in refluxing THF gives two previously reported
compounds [Ru (CO) (l-dppm) ] (2) and [Ru3-
dppmS) and monoselenide (dppmSe) is known [8]. It
3
8
2
has been found that the reactions of [Fe (CO) ] with
3
(CO) (l -CO)(l -Se)(l-dppm)] (3) in 7% and 5% yields,
7 3 3
12
the diselenides dppmSe , dppeSe and dppfSe produce
2
respectively, and two new compounds [Ru (CO) (l -
3 5 3
2
2
the 50-electron, nido-clusters [Fe (CO) (l -Se) (l-
CO)(l -Se)(l-dppm) ] (4) and [Ru (CO) (l -CO)(l -
3 2 3 6 3 3
1
3
7
3
2
(
R = (C H ) Fe, dppf) as the main products [9]. In some
Ph P) R)] (R = CH2, dppm; R = (CH2)2, dppe;
Se)(l-dppm)(g -Ph PCH P(@O)Ph )] (5) in 9% and
2
2
2
2
2
33% yields, respectively (Scheme 1). Compound 2 was
reported from the reaction of [Ru (CO) ] with dppm
5
4 2
cases, these reactions lead to species not easily accessible
by other routes. For example, dppmSe2 reacts with
3
12
[13] and 3 from the reaction of 1 with elemental selenium
and was characterized by X-ray diffraction studies [14].
A similar reaction between 1 and dppmS in refluxing
[
Ru (CO) ] in refluxing toluene to give, in addition to
3 12
the expected primary product [Ru (CO) (l -Se) (l-
3
7
3
2
Ph P
2
Ru
Ru
O
Ru
C
E
PPh
2
dppmE
Ru
Ru
PPh
Ru
Ru
+
Ru
Ru
PPh
o
Ph P
66 C
Ph P
2
Ph P
2
2
2
PPh
2
2
3
7
, E = Se
, E = S
2
1
O
Ph P
2
Ph P
2
PPh
2
Ru
O
Ru
C
E
O
Ru
S
S
PPh
2
C
E
+
+
+
Ru
Ru
Ru
Ru
PPh
Ru
Ru
PPh
Ph P
2
PPh
2
Ph P
2
2
Ph P
2
2
4
8
, E = Se
, E = S
5, E = Se
, E = S
6
9
Scheme 1.

3414
S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
THF yields two known clusters [Ru (CO) (l -S) (l-
five terminal carbonyl groups, two each on Ru(2) and
Ru(3) and one on Ru(1). The Ru–P bond distances in
˚ ˚
4 (Ru(1)–P(1) = 2.382(6) A, Ru(1)–P(4) = 2.284(6) A,
3
7
3
2
dppm)] (6) and [Ru (CO) (l -CO)(l -S)(l-dppm)] (7)
3
7
3
3
in 8% and 7% yields and two new clusters [Ru3-
˚
˚
(
(
(
CO) (l -CO)(l -S)(l-dppm) ] (8) and [Ru (CO) -
Ru(3)–P(3) = 2.363(6) A and Ru(2)–P(2) = 2.302(6) A)
are comparable to the Ru–P distances in 2 [15] and 1
[13].
5
3
3
2
3
6
1
l -CO)(l -S)(l-dppm)(g -Ph PCH P(@O)Ph )]
(9)
Scheme 1) in 14% and 35% yields, respectively. Both
3
3
2
2
2
compounds 6 and 7 were also obtained from the reac-
tion of 1 with tetramethylthiourea and were character-
ized by X-ray diffraction studies [14].
The spectroscopic data for 4 are in accord with the
solid-state structure and the spectroscopic data for 8
indicate that it is a direct analog of 4 (Scheme 1). The
3
1
1
The compounds 4 and 8 have been characterized by
P{ H} NMR spectra of 4 and 8 contain two doublets
1
31
1
elemental analysis, IR, H NMR, P{ H} NMR and
mass spectroscopic data together with single-crystal
X-ray diffraction analysis for 4. The molecular structure
of 4 is depicted in Fig. 1, crystal data are given in Table
(d 29.5 (J = 57.3 Hz) and 27.8 (J = 57.3 Hz) for 4; d 29.2
(d, J = 57.3 Hz) and 27.3 (d, J = 57.3 Hz) for 8), indicat-
ing two different types of phosphorus atoms in the mol-
ecule. In addition to the usual phenyl resonances in the
1
1
and selected bond distances and angles are shown in
aromatic region, the aliphatic region of the H NMR
Table 2. The molecule consists of a triangular cluster
of three ruthenium atoms containing one triply bridging
selenido ligand, two edge bridging dppm ligands, five
terminal and one triply bridging carbonyl ligands. The
spectra of 4 and 8 show two equal intensity multiplets
(d 4.12 and 3.65 for 4 and d 3.87 and 3.59 for 8) due
to the methylene protons of the dppm ligands. The
FAB mass spectra of 4 and 8 show the molecular ion
peaks at m/z 1317 and 1270, respectively, and ions due
to stepwise loss of five carbonyls groups.
complex displays a tetrahedral Ru Se core in which an
3
almost equilateral triangle of ruthenium atoms (Ru(1)–
˚
Ru(3) = 2.838(3) A, Ru(2)–Ru(3) = 2.816(3) A and
˚
Ru(1)–Ru(2) = 2.837(3) A) is symmetrically capped by
˚
the selenium atom (Ru(1)–Se(1) = 2.517(3) A, Ru(3)–
˚
The compounds 5 and 9 have been characterized by
1
31
1
elemental analysis, IR, H NMR, P{ H} NMR and
mass spectroscopic data together with single-crystal
X-ray diffraction analysis for 9. The molecular structure
of 9 is shown in Fig. 2, crystal data are given in Table 1
and selected bond distances and angles are given in
Table 3. The molecule consists of a triangular cluster
of three ruthenium atoms containing one triply bridging
˚
˚
Se(1) = 2.481(3) A and Ru(2)–Se(1) = 2.496(3) A). In
contrast, the triply bridging carbonyl group is bonded
asymmetrically to the Ru triangle with three distinctly
3
˚
different Ru–C distances (Ru(2)–C(28) = 2.19(2) A,
˚
Ru(1)–C(28) = 2.07(2) A and Ru(3)–C(28) = 2.26(2)
˚
A). The triply bridging carbonyl and selenido ligands
1
sulfido ligand, one bridging dppm ligand, one g -coordi-
lie on opposite faces of the Ru triangle resulting in a
3
nated dppm mono-oxide (Ph PCH P(@O)Ph ) ligand,
2
2
2
trigonal bipyramidal geometry for the Ru (Se)(CO)
3
one triply bridging and six terminal carbonyl ligands.
The two metal–metal bonds, Ru(1)–Ru(2) = 2.8201(10)
core. The dppm supported Ru–Ru bond lengths are sim-
ilar to the supported bond lengths in 2 (2.833(2) and
˚
˚
A and Ru(2)–Ru(3) = 2.8108(9) A are essentially equal
in length and slightly longer than the third bond,
˚
.826(2) A) but the unsupported bond distance is some-
2
what shorter than that in 2 (2.858(2) A) [15]. There are
˚
˚
Ru(1)–Ru(3) = 2.7892(10) A. All three metal–metal
bonds are shorter than those found in 1 (2.8341(1),
2
˚
.841(1) and 2.860(1) A) [13]. The compound 9 contains
a triply bridging sulfido ligand on one triangular face
and a triply bridging carbonyl ligand on the other.
The geometry of the Ru S core in which an isosceles tri-
3
angle of ruthenium atoms is almost symmetrically caped
˚
by the S atom (Ru(1)–S(1) = 2.3606(17) A, Ru(3)–
˚
˚
S(1) = 2.3636(15) A and Ru(2)–S(1) = 2.3536(15) A)
can be described as tetrahedral. In contrast the triply
bridging carbonyl ligand is bonded asymmetrically to
˚
the Ru3 triangle (Ru(2)–C(16) = 2.121(5) A, Ru(3)–
˚
˚
C(16) = 2.202(5) A and Ru(1)–C(16) = 2.198(5) A).
The three Ru–P bond distances in 9 are different
˚ ˚
(Ru(2)–P(1) = 2.3521(14) A, Ru(2)–P(2) = 2.3255(15) A
and Ru(3)–P(3) = 2.3522(14) A). An intriguing struc-
˚
tural feature of 9 is the presence of an unusual dangling
1
g -Ph PCH P(@O)Ph ligand. We believe that the
2
2
2
dppm mono-oxide ligand is formed by in situ oxidation
of one of the PPh groups of the dppm ligand. The
source of oxygen may be moisture in the solvent
Fig. 1. The solid-state structure of [Ru
3
(CO)
5
(l
3
-CO)(l
3
-Se)(l-
2
dppm) ] (4). Thermal ellipsoids are at the 50% probability level.
2

S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
3415
Table 1
Crystal data for compounds 4, 9 and 10
Compounds
4
9
10
Empirical formula
Formula weight
T (K)
C
56
H
44
O
6
P
4
Ru
3
Se
C
57
H
44
O
8
P
4
Ru
3
SCH
2
Cl
2
41 32 4 2 2 2
C H O P Ru Se
1318.96
293(2)
0.71073
1401.07
293(2)
0.71073
1010.67
293(2)
0.71073
k
Crystal system
Space group
Triclinic
ꢀ
Triclinic
ꢀ
Triclinic
ꢀ
P1
P1
P1
˚
a (A)
14.397(2)
14.444(2)
15.946(3)
79.15(1)
67.65(1)
77.80(1)
2976.2(8)
2
10.342(3)
13.695(3)
21.274(4)
72.48(2)
81.13(2)
89.81(3)
11.324(1)
18.567(2)
20.460(3)
110.24(1)
99.10(1)
92.34(1)
3964.1(8)
4
˚
b (A)
˚
c (A)
a (ꢀ)
b (ꢀ)
c (ꢀ)
˚
3
V (A )
2835.9(12)
2
Z
3
D
calc (mg/m )
1.472
1.514
1308
1.641
1.086
1400
1.693
2.719
1984
À1
Absorption coefficient (mm
F(000)
3
Crystal size (mm )
)
0.2 · 0.1 · 0.1
2.13–17.50
0.4 · 0.3 · 0.2
2.03–22.50
À1 6 h 6 11,
À14 6 k 6 14,
À22 6 l 6 22
8362
0.5 · 0.4 · 0.1
2.06–19.99
À1 6 h 6 9,
À16 6 k 6 16,
À19 6 l 6 19
8327
Theta range for data collection (ꢀ)
Index ranges
À10 6 h 6 À11,
À11 6 k 6 12,
0
3650
6 l 6 13
Reflections collected
Independent reflections (Rint
)
3650 (0.0401)
96.6 (17.50)
None
6910 (0.0323)
93.2 (22.50)
None
6858 (0.0218)
92.7 (19.99)
None
Completeness (%) (to theta (ꢀ))
Absorption correction
Data/restraints/parameters
3650/0/561
1.278
6910/0/685
1.076
6858/0/919
1.100
2
Goodness-of-fit on F
Final R indices [I > 2r(I)]
R indices (all data)
˚
Largest difference peak and hole (e A
R
R
1
1
= 0.0719, wR
= 0.0925, wR
2
= 0.2142
= 0.2318
R
R
1
1
= 0.0363, wR
= 0.0491, wR
2
= 0.0856
= 0.0916
R
R
1
1
= 0.0458, wR
= 0.0557, wR
2
= 0.1148
= 0.1211
2
2
2
À3
)
1.892 and À0.671
0.844 and À0.619
1.860 and À1.145
1
(
THF). Each of the ruthenium atoms contains two lin-
the usual phenyl resonances, the H NMR spectra of 5
and 9 show triplets integrating for two protons and
two multiplets each integrating for one proton (4.19
(m), 3.99 (t) and 3.50 (m) for 5; 4.20 (m), 3.98 (t) and
3.59 (m) for 9). The multiplets are due to the methylene
protons of the dppm mono-oxide ligand and the triplets
are due to the methylene protons of the bridging dppm
ligands. The FAB mass spectra of 5 and 9 show the
molecular ion peaks at m/z 1362 and 1315, respectively,
and ions due to the sequential loss of seven carbonyl
ligands.
ear terminal carbonyl ligands. The cluster 9 is a 48-elec-
tron system, as expected for an electron precise
trinuclear metal cluster containing three metal–metal
bonds. To the best of our knowledge compound 9 repre-
sents the first example of a triruthenium cluster contain-
ing a bridging dppm and a dangling oxygenated dppm
(
Ph PCH P(@O)Ph ) ligands.
2
2
2
The spectroscopic data for 9 are consistent with its
solid state structure and are very similar to the spectro-
scopic data for 5 (Scheme 1). Both the solution and the
solid state IR spectra of 5 and 9 are superimposable,
The formation of the dppm mono-oxide ligand is
most interesting in that it is apparently associated with
the activation of the P–S and P–Se bonds by the cluster.
This is evidenced by the facts that no related compounds
are observed in the reactions of dppm with Ru (CO)
3
1
1
indicating that they are isostructural. The P{ H}
NMR spectra of 5 and 9 contain three sets of signals,
one integrating for 2 phosphorus atoms and two each
integrating for one phosphorus atom, indicating the
presence of three different types of phosphorus atoms
in the molecule. The doublets at d 25.4 and 41.2
3
12
and that the dppmS and dppmSe ligands are stable to-
wards hydrolysis under the reaction conditions associ-
ated with the formation of 5 and 9. Thus, one can
visualize a reaction pathway whereby initial coordina-
tion of phosphorus is followed by activation of the
P–S or P–Se bond by the cluster and then by nucleophi-
lic attack by trace water at the activated bonds. This
(
J = 28.6 Hz) for 5 and d 28.5 and 41.2 (J = 28.6 Hz)
for 9 are due to phosphorus atoms the dangling dppm
mono-oxide ligands whereas the singlets at d 28.3 (s)
for 5 and d 37.0 for 9 are due to the equivalent phospho-
rus atoms of the bridging dppm ligands. In addition to

3416
S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
Table 2
Selected bond distances (A) and angles (ꢀ) for [Ru
Se)(l-dppm) ] (4)
Table 3
Selected bond distances and angles for [Ru (CO) (l -CO)(l -S)(l-
˚
3
(CO)
(l
5 3
-CO)(l
3
-
3
6
3
3
1
2
dppm)(g -Ph PCH P(@O)Ph )] (9)
2
2
2
Bond distances
Ru(1)–C(28)
Ru(1)–P(4)
Bond distances
Ru(1)–C(16)
Ru(1)–P(1)
2.07(2)
P(2)–Ru(2)
O(28)–C(28)
C(28)–Ru(2)
C(28)–Ru(3)
Ru(2)–Se(1)
Ru(2)–Ru(3)
Ru(3)–Se(1)
2.302(6)
1.19(2)
2.19(2)
2.26(2)
2.496(3)
2.816(3)
2.481(3)
2.198(5)
Ru(2)–S(1)
2.3536(15)
2.8108(9)
2.202(5)
2.284(6)
2.382(6)
2.517(3)
2.837(3)
2.838(3)
2.363(6)
2.3521(14) Ru(2)–Ru(3)
2.3606(17) Ru(3)–C(16)
2.7892(10) Ru(3)–P(3)
2.8201(10) Ru(3)–S(1)
Ru(1)–P(1)
Ru(1)–S(1)
Ru(1)–Se(1)
Ru(1)–Ru(2)
Ru(1)–Ru(3)
P(3)–Ru(3)
Ru(1)–Ru(3)
Ru(1)–Ru(2)
Ru(2)–C(16)
Ru(2)–P(2)
2.3522(14)
2.3636(15)
1.484(4)
2.121(5) P(4)-O(3)
2.3255(15) O(16)–C(16)
1.190(6)
Bond angles
Bond angles
C(28)–Ru(1)–P(4)
C(28)–Ru(1)–P(1)
P(4)–Ru(1)–P(1)
C(28)–Ru(1)–Se(1)
P(4)–Ru(1)–Se(1)
P(1)–Ru(1)–Se(1)
C(28)–Ru(1)–Ru(2)
P(4)–Ru(1)–Ru(2)
P(1)–Ru(1)–Ru(2)
Se(1)–Ru(1)–Ru(2)
C(28)–Ru(1)–Ru(3)
P(4)–Ru(1)–Ru(3)
P(1)–Ru(1)–Ru(3)
Se(1)–Ru(1)–Ru(3)
117.4(6)
134.8(6)
107.3(2)
92.3(7)
P(2)–Ru(2)–Se(1)
C(28)–Ru(2)–Ru(3)
P(2)–Ru(2)–Ru(3)
Se(1)–Ru(2)–Ru(3)
C(28)–Ru(2)–Ru(1)
P(2)–Ru(2)–Ru(1)
Se(1)–Ru(2)–Ru(1)
96.24(16)
51.8(6)
C(16)–Ru(1)–P(1)
C(16)–Ru(1)–S(1)
P(1)–Ru(1)–S(1)
131.89(13) C(16)–Ru(3)–S(1)
87.61(14)
169.47(5)
50.60(13)
116.34(4)
53.76(4)
87.78(15)
91.97(6)
50.73(13)
145.18(4)
53.86(4)
48.07(14)
95.69(4)
53.15(4)
P(3)–Ru(3)–S(1)
144.69(17)
55.29(7)
46.4(6)
C(16)–Ru(3)–Ru(1)
P(3)–Ru(3)–Ru(1)
S(1)–Ru(3)–Ru(1)
C(16)–Ru(3)–Ru(2)
P(3)–Ru(3)–Ru(2)
S(1)–Ru(3)–Ru(2)
C(16)–Ru(1)–Ru(3)
P(1)–Ru(1)–Ru(3)
S(1)–Ru(1)–Ru(3)
C(16)–Ru(1)–Ru(2)
P(1)–Ru(1)–Ru(2)
S(1)–Ru(1)–Ru(2)
97.03(17)
87.93(16)
50.1(6)
87.25(17)
55.89(7)
48.21(13)
120.48(4)
53.26(4)
143.36(17) Ru(3)–Ru(2)–Ru(1) 60.26(6)
96.00(16)
55.20(7)
52.0(6)
C(28)–Ru(3)–P(3)
C(28)–Ru(3)–Se(1)
P(3)–Ru(3)–Se(1)
C(28)–Ru(3)–Ru(2)
133.6(6)
88.8(6)
Ru(1)–Ru(3)–Ru(2) 60.47(3)
Ru(3)–Ru(1)–Ru(2) 60.14(2)
Ru(2)–S(1)–Ru(1)
118.99(14) Ru(2)–S(1)–Ru(3)
73.48(5)
73.15(5)
72.37(5)
111.5(3)
126.3(3)
117.0(3)
124.4(5)
132.1(4)
131.3(4)
81.49(18)
132.0(4)
81.07(19)
85.98(16)
49.7(6)
C(16)–Ru(2)–P(2)
C(16)–Ru(2)–S(1)
P(2)–Ru(2)–S(1)
85.51(16)
89.79(14)
98.73(5)
50.72(14)
145.70(4)
53.59(4)
50.44(13)
88.55(4)
53.37(4)
Ru(1)–S(1)–Ru(3)
P(2)–C(1)–P(1)
P(3)–C(40)–P(4)
142.23(17) P(3)–Ru(3)–Ru(2)
141.32(17)
55.80(7)
46.1(6)
54.82(7)
Se(1)–Ru(3)–Ru(2)
C(28)–Ru(3)–Ru(1)
P(3)–Ru(3)–Ru(1)
Se(1)–Ru(3)–Ru(1)
C(16)–Ru(2)–Ru(3)
P(2)–Ru(2)–Ru(3)
S(1)–Ru(2)–Ru(3)
C(16)–Ru(2)–Ru(1)
P(2)–Ru(2)–Ru(1)
S(1)–Ru(2)–Ru(1)
Ru(2)–Ru(1)–Ru(3) 59.51(6)
O(3)–P(4)–C(40)
C(58)–C(53)–P(4)
O(16)–C(16)–Ru(2)
O(16)–C(16)–Ru(1)
Ru(2)–C(16)–Ru(1)
O(16)–C(16)–Ru(3)
Ru(2)–C(16)–Ru(3)
P(2)–C(13)–P(1)
P(3)–C(43)–P(4)
112.2(12)
109.9(11)
133.8(17)
129.9(16)
83.5(9)
95.24(16)
56.01(7)
O(28)–C(28)–Ru(1)
O(28)–C(28)–Ru(2)
Ru(1)–C(28)–Ru(2)
O(28)–C(28)–Ru(3)
Ru(1)–C(28)–Ru(3)
Ru(2)–C(28)–Ru(3)
Ru(2)–Ru(3)–Ru(1) 60.23(6)
Ru(3)–Se(1)–Ru(2)
Ru(3)–Se(1)–Ru(1)
Ru(2)–Se(1)–Ru(1)
C(28)–Ru(2)–P(2)
C(28)–Ru(2)–Se(1)
68.91(8)
69.17(8)
68.91(8)
115.9(6)
89.9(6)
Ru(3)–Ru(2)–Ru(1) 59.38(3)
C(16)–Ru(3)–P(3)
Ru(1)–C(16)–Ru(3)
129.5(16)
81.9(9)
78.5(8)
82.48(14)
78.67(17)
We have recently reported [16] that the reaction of
Os (CO) (l-dppm)] with PhSeSePh at 110 ꢀC affords
process must also be associated with the formation of
capping sulfur and selenium clusters under relatively
mild conditions relative to the reaction of elemental sul-
fur or selenium with related clusters.
[
3
10
the dinuclear compound [Os (CO) (l-SePh) (l-dppm)],
2
4
2
three 50 electron, isomeric compounds with the formula
[
Os (CO) (l-SePh) (l-dppm)] and two benzyne com-
3
8
2
2
pounds [Os (CO) (l-SePh) (l-g -C H )(l-dppm)] and
3
8
2
6
4
2
[
Os (CO) (l-CO)(l -Se) (l-g -C H )(l-dppm)].
Fol-
3
6
3
2
6
4
lowing this observation we decided to investigate the
reaction of 1 with PhSeSePh, with the intent of synthe-
sizing the different isomers of [Ru (CO) (l-SePh) (l-
3
8
2
dppm)] and to establish whether starting from the more
reactive 1 (compared to [Os (CO) (l-dppm)]) influences
3
10
the course of the reaction. In contrast to the above
observation, the reaction of 1 with PhSeSePh in reflux-
ing THF at 66 ꢀC gives only the dinuclear compound
[
Ru (CO) (l-SePh) (l-dppm)] (10) in 14% yield
2 4 2
(
terized products.
Scheme 2) along with some other very minor, uncharac-
1
Compound 10 has been characterized by IR,
H
3
1
1
NMR, P{ H} NMR and mass spectroscopic data to-
gether with single-crystal X-ray diffraction study. The
molecular structure of 10 is depicted in Fig. 3, crystal
data are given Table 1, selected bond distances and an-
gles are shown in Table 4. There are two molecules in
Fig. 2. The solid-state structure of [Ru
1
3
(CO)
6 3 3
(l -CO)(l -S)(l-
dppm)(g -Ph
2
PCH
2
P(@O)Ph
2
)] (9). Thermal ellipsoids are at the
50% probability level.

S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
3417
Table 4
Ph
Se
Ph
Se
˚
Selected bond distances (A) and angles (ꢀ) for [Ru
dppm)] (10)
2
(CO)
4
(l-SePh)
2
(l-
o
Bond distances
6
6 C
1
+
PhSeSePh
Ru
Ru
PPh
Ru(3)–P(4)
Ru(3)–Se(4)
Ru(3)–Se(3)
Ru(3)–Ru(4)
Ru(2)–P(1)
Ru(2)–Se(1)
Ru(2)–Se(2)
Ru(2)–Ru(1)
Ru(4)–P(3)
2.317(3)
Ru(4)–Se(3)
Ru(4)–Se(4)
Ru(1)–P(2)
Ru(1)–Se(1)
Ru(1)–Se(2)
Se(3)–C(58)
Se(4)–C(64)
Se(2)–C(17)
Se(1)–C(23)
2.5180(12)
2.5190(12)
2.311(2)
2.5284(12)
2.5468(12)
2.7001(10)
2.314(2)
Ph P
2
2
2.5217(12)
25253(12)
1.941(9)
10
2.5150(13)
2.5155(12)
2.6929(11)
2.328(2)
Scheme 2.
1.927(10)
1.950(11)
1.929(9)
Bond angles
P(4)–Ru(3)–Se(4)
P(4)–Ru(3)–Se(3)
Se(4)–Ru(3)–Se(3)
P(4)–Ru(3)–Ru(4)
Se(4)–Ru(3)–Ru(4)
Se(3)–Ru(3)–Ru(4)
P(1)–Ru(2)–Se(1)
P(1)–Ru(2)–Se(2)
Se(1)–Ru(2)–Se(2)
P(1)–Ru(2)–Ru(1)
Se(1)–Ru(2)–Ru(1)
Se(2)–Ru(2)–Ru(1)
P(3)–Ru(4)–Se(3)
P(3)–Ru(4)–Se(4)
Se(3)–Ru(4)–Se(4)
151.07(7)
92.76(7)
77.23(4)
94.17(6)
57.49(3)
57.27(3)
89.88(7)
154.79(7)
78.05(4)
96.95(6)
57.80(3)
57.89(3)
88.60(7)
152.58(7)
77.93(4)
P(3)–Ru(4)–Ru(3)
Se(3)–Ru(4)–Ru(3)
Se(4)–Ru(4)–Ru(3)
P(2)–Ru(1)–Se(1)
P(2)–Ru(1)–Se(2)
Se(1)–Ru(1)–Se(2)
P(2)–Ru(1)–Ru(2)
Se(1)–Ru(1)–Ru(2)
Se(2)–Ru(1)–Ru(2)
Ru(4)–Se(3)–Ru(3)
Ru(4)–Se(4)–Ru(3)
Ru(2)–Se(2)–Ru(1)
Ru(2)–Se(1)–Ru(1)
P(4)–C(43)–P(3)
94.77(6)
58.30(3)
57.83(3)
85.94(7)
151.71(7)
77.75(4)
94.21(6)
57.56(3)
57.53(3)
64.43(3)
64.68(3)
64.58(3)
64.64(3)
113.9(5)
116.4(4)
P(2)–C(1)–P(1)
tively shortened Ru–Ru bond, in comparison to that ob-
served in parent compound 1 is presumably due to the
Fig. 3. The solid-state structure of [Ru
2
4 2
(CO) (l-SePh) (l-dppm)] (10).
Thermal ellipsoids are at the 50% probability level.
‘
‘pincer’’ effect exerted by the bridging phenylselenido
ligands. Considering the l-SePh as a three electron do-
nor ligand, the molecule is a normal 34-electron species
with each ruthenium atom in a distorted octahedral envi-
ronment determined by the other ruthenium atom, the
bridging phenylselenido groups and three appropriate
two-electron donor ligands.
the unit cell which have the same overall geometry but
differ mainly in the lengths of the Ru–Se bonds, probably
due to crystal packing effects. The molecule consists of a
ruthenium–ruthenium back-bone, ligated terminally by
four carbonyl ligands adopting the Ru (CO) classical
ÔsawhorseÕ arrangement and bridged by two phenylselen-
ido ligands as well as a dppm ligand. The phenylselenido
and the dppm ligands are transoid to each other and the
selenido ligands are perpendicular each other to the Ru–
Ru vector. The P–C–P angle of the short-bite dppm lig-
and {P(1)–C(1)–P(2) = 116.4(4)ꢀ} is very similar to that
found for the dinuclear dppm substituted complexes
The infrared spectrum of 10 in the carbonyl stretch-
ing region in CH Cl exhibits absorption bands at
2
4
2
2
À1
1
2002s, 1979vs and 1940s cm . The H NMR spec-
trum of 10 shows signals at d 7.39 (m), 4.41 (dt) and
3.88 (dt) with a relative intensity of 30:1:1. The dou-
blet of triplets at d 4.41 and 3.88 are due to the meth-
ylene protons of the dppm ligand. The multiplet
centered at d 7.39 has been assigned to the phenyl pro-
3
1
1
[
Ru (CO) (l-SCH CH CH S)(l-dppm)] (114.4(2)ꢀ) [17]
tons of both the dppm and SePh ligands. The P{ H}
NMR spectrum shows a singlet at d 24.2, which indi-
2
4
2
2
2
and [Os (CO) (l-SePh) (l-dppm)] (114.0(10)ꢀ) [16].
2
4
2
3
1
The interesting feature of the molecular structure 10 is
short Ru–Ru distance. The Ru(1)–Ru(2) distance of
˚
cates that the two P nuclei of the dppm ligand are in
an equivalent environment. The mass spectrum of 10
shows a molecular ion peak at m/z 1010 which is con-
sistent with the proposed molecular formula [Ru2
(CO) (l-SePh) (l-dppm)]. Thus, the spectroscopic data
2
.6929(11) A is significantly shorter than the correspond-
˚
ing Ru–Ru distances (2.8564(10) A) in the parent com-
pound 1 [13] but are comparable to the corresponding
distances found for the other related diruthenium com-
4
2
of 10 are consistent with the solid-state structure. As is
generally the case, fragmentation of the starting trinu-
clear cluster is less pronounced with osmium than
with ruthenium where formation of several selenido
˚
plexes such as, [Ru (CO) (l-SCH CH S)] (2.679(8) A)
2
6
2
2
˚
[
18], [Ru (CO) (l-SC H S)(PPh ) ] (2.677(5) A) [19]
2 4 6 4 3 2
and [Ru (CO) (l-SC H S)] (2.650(2) A) [20]. This rela-
˚
2
6
6
4

3418
S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
trinuclear clusters is observed. Also, the osmium ana-
log of 10 exists as two isomers in solution which differ
by the relative disposition of the phenyl groups on the
selenium whereas only one isomer of 10 is observed in
solution.
3.2. Reaction of 1 with dppmS
A similar reaction to that above of 1 (0.200 g, 0.210
mmol) with dppmS (0.192 g, 0.415 mmol) followed by
similar chromatographic separation developed four
bands. The first and second bands afforded the previ-
ously reported compounds [Ru (CO) (l -S) (l-dppm)]
3
7
3
2
(
(
6) (0.017 g, 8%) and [Ru (CO) (l -CO)(l -S)(l-dppm)]
3 7 3 3
3
. Experimental
7) (0.015 g, 7%). The third band yielded [Ru (CO) (l -
3
5
3
CO)(l -S)(l-dppm) ] (8) (0.036 g, 14%) as yellow crys-
3
2
All the reactions were routinely performed under a
tals after recrystallization from CH Cl /hexane at 4 ꢀC
2
2
nitrogen atmosphere using standard Schlenk techniques
although no special precautions were taken to exclude
air during work-up. Reagent grade solvents were dried
and distilled prior to use by standard methods (CH Cl
(
Anal. Calc. for C H O P Ru S: C, 55.19; H, 3.64.
56 44 6 4 3
Found: C, 54.90; H, 3.38%). IR (mCO, CH Cl ): 2017
2
2
À1
vs, 1987 s, 1958 vs cm ; IR (mCO, KBr): 1647 w
cm ; H NMR (CD Cl ): d 7.11 (m, 40H), 3.87 (m,
2H), 3.59 (m, 2H); P{ H} NMR (CD Cl ): d 29.2 (d,
2 2
2P, J = 57.3 Hz) 27.3 (d, 2P, J = 57.3 Hz); mass spec-
2
2
À1
1
2
2
over CaH2 and THF from sodium benzophenone).
Infrared spectra were recorded on a Shimadzu FT-IR
31
1
1
31
1
8
101 spectrophotometer. H and P{ H} NMR spectra
were recorded on a Varian Unity Plus 400 and a Bruker
trum: m/z 1270. The fourth band gave [Ru (CO)
3
6
1
31
1
(l
3
-CO)(l
3
-S)(l-dppm)(g -Ph
2
PCH
CH Cl (0.102 g, 35%) as yellow crystals from
2
P(@O)Ph )] (9).
2
DPX 400 spectrometers. Chemical shifts for the P{ H}
NMR spectra are relative to 85% H PO . Mass spectra
were recorded on Varian Mat 312 mass spectrometer.
2
2
3
4
CH Cl /hexane at 4 ꢀC (Anal. Calc. for C Cl H O P
2
2
58
2
46
8 4
Ru S: C, 49.72; H, 3.32. Found: C, 49.98; H, 3.51%). IR
À1
3
The starting cluster [Ru (CO) (l-dppm)] (1) [21] and
3
10
(
mCO, CH Cl ): 2029 s, 2009 vs, 1992 vs, 1958 s cm
;
2
2
the ligands dppmS and dppmSe [22] were prepared
by the literature procedures.
À1
1
IR (mCO, KBr): 1626 w cm ; H NMR (CD Cl ): d
2
2
7
.26 (m, 40H), 4.20 (m, 1H), 3.98 (m, 2H), 3.59 (m,
3
1
1
1
Hz) 37.0 (s, 2P) 28.5 (d, 1P, J = 28.6 Hz); mass spec-
H); P{ H} NMR (CD Cl ): d 41.4 (d, 1P, J = 28.6
2
2
3
.1. Reaction of 1 with dppmSe
trum: m/z 1315.
A THF solution (35 mL) of 1 (0.200 g, 0.210 mmol)
and dppmSe (0.192 g, 0.415 mmol) was heated to reflux
3
.3. Reaction of 1 with PhSeSePh
under N for 2 h. The solvent was removed under re-
2
duced pressure and the residue was dissolved in a mini-
mal amount of CH Cl and separated by TLC on silica
gel. Elution with cyclohexane/CH Cl (3:2, v/v) devel-
A solution of 1 (0.200 g, 0.210 mmol) and PhSeSePh
0.129 g, 0.414 mmol) in THF (35 ml) was heated to re-
2
2
(
2
2
flux for 1h. The solvent was removed under reduced
pressure and the residue was dissolved in a minimal am-
out of CH Cl and separated by TLC on silica gel. Elu-
oped four bands. The first band and the second bands
gave the known compounds [Ru (CO) (l-dppm) ] (2)
3
8
2
2
2
(
(
(
0.020 g, 7%) and [Ru (CO) (l -CO)(l -Se)(l-dppm)]
3 7 3 3
tion with cyclohexane/CH Cl (7:3, v/v) developed one
2
2
3) (0.010 g, 5%). The third band yielded [Ru3
CO) (l -CO)(l -Se)(l-dppm) ] (4) (0.025 g, 9%) as yel-
major and three very minor bands. The major band af-
forded [Ru (CO) (l-SePh) (l-dppm)] (10) (0.030 g,
5
3
3
2
2
4
2
low crystals after recrystallization from CH Cl /hexane
2
2
1
ane/CH Cl (Anal. Calc. for C H O P Ru Se : C,
4%) as yellow crystals after recrystallization from hex-
at 4 ꢀC (Anal. Calc. for C H O P Ru Se: C, 51.01;
5
6
44
6
4
3
2
2
40 30
4
2
2
2
H, 3.37. Found: C, 50.98; H, 3.33%). IR (mCO, CH Cl ):
2
2
À1
48.20; H, 3.04. Found: C, 48.38; H, 3.24%). IR (mCO,
2
cm
(
017 vs, 1986 s, 1958 vs cm ; IR (mCO, KBr): 1647 w
À1
1
À1
1
CH
2
Cl
2
): 2002 s, 1979 vs, 1940 s, cm
): d 7.39 (m, 30H), 4.41 (m, 1H), 3.88 (m, 1H);
P{ H} NMR (CD Cl ): d 24.2 (s); mass spectrum: m/
; H NMR
;
H NMR (CD Cl ): d 7.18 (m, 40H), 4.11
2 2
31 1
(CD
31
Cl
2
1
2
m, 2H), 3.65 (m, 2H); P{ H} NMR (CD Cl ): d
2 2
2
2
2
spectrum: m/z 1317. The fourth band gave [Ru (CO)
9.5 (d, 2P, J = 57.3 Hz) 27.9 (d, 2P, J = 57.3 Hz); mass
z 1010. The minor bands were too small for complete
characterization.
3
6
1
(
(
l -CO)(l -Se)(l-dppm)(g -Ph PCH P(@O)Ph )] (5)
3
3
2
2
2
0.090 g, 33%) as yellow crystals from CH Cl /hexane
2
2
at 4 ꢀC (Anal. Calc. for C H O P Ru Se: C, 50.22;
3.4. Conversion of 5 to 4
5
7
44
8
4
3
H, 3.26. Found: C, 50.45; H, 3.15%). IR (mCO, CH Cl ):
2
2
À1
2
1
4
029 s, 2008 vs, 1992 vs, 1958 s cm ; IR (mCO, KBr):
A toluene solution (15 ml) of 5 (0.010 g, 0.007 mmol)
was refluxed for 1 h. The solvent was removed under re-
duced pressure and the residue was chromatographed by
TLC on silica gel. Elution with cyclohexane/CH Cl
2
À1
1
624 w cm ; H NMR (CD Cl ): d 7.26 (m, 40H),
2
2
31
1
.19 (m, 1H), 3.99 (m, 2H), 3.50 (m, 1H); P{ H}
NMR (CD Cl ): d 41.2 (d, 1P, J = 28.6 Hz), 28.3 (s,
2
2
2
2
P), 25.4 (d, 1P, J = 28.6 Hz); mass spectrum: m/z 1362.
developed a single band which afforded 5 (0.004 g, 41%).

S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
3419
3
.5. Conversion of 9 to 8
(c) S.W. Audi Fong, T.S.A. Hor, J. Chem. Soc., Dalton Trans.
(
(
(
(
1999) 639;
d) T. Shibihara, Coord. Chem. Rev. 123 (1993) 73;
e) K.H. Whitmire, J. Coord. Chem. 17 (1988) 95;
f) G. Longoni, M.C. Iapalucci, in: Clusters and Colloids, VCH,
A similar thermolysis to that above of a heptane solu-
tion of 9 (0.015 g, 0.011 mmol) followed by similar chro-
matographic separation gave 8 (0.006 g, 43%).
Weinheim, 1994, p. 132;
g) M.L. Steigerwald, T. Siegrist, E.M. Gyorgy, B. Hessen, Y.-U.
Kwon, S.M. Tanzler, Inorg. Chem. 33 (1994) 3389;
h) S. Ulvenlund, A. Bengtsson-Kloo, in: P. Braunstein, L.A.
(
3
.6. X-ray structure determinations
(
Oro, P.R. Raithby (Eds.), Metal Clusters in Chemistry, vol. 1,
VCH, Weinheim, 1999, p. 561;
Crystals of 4, 9 and 10 for X-ray examination were
obtained from saturated solutions of each in hexane/
dichloromethane solvent at À20 ꢀC. Crystallographic
data for 4, 9 and 10 were collected at 296 K, using Bru-
(i) D. Fenske, J.F. Corrigan, in: P. Braunstein, L.A. Oro, P.R.
Raithby (Eds.), Metal Clusters in Chemistry, vol. 3, VCH,
Weinheim, 1999, p. 1302.
[
3] (a) R.D. Adams, M. Tasi, J. Cluster Sci. 1 (1990) 249;
ker P4 diffractometer with Mo Ka radiation
(
(
b) R.D. Adams, Polyhedron 4 (1985) 2003;
c) R.D. Adams, I.T. Horvath, L.W. Yang, J. Am. Chem. Soc.
˚
(
k = 0.71073 A). Data collection and processing were
carried out using XSCANS [23]. The unit cells were in-
dexed on low angle reflections and refined from 25
reflections in a range of 12–13ꢀ. The structures were
solved by direct methods (SHELXS-97) [24] and refined
105 (1983) 1533;
(d) R.D. Adams, I.T. Horvath, P. Mathur, B.E. Segmuller,
Organometallics 2 (1983) 996;
(
e) R.D. Adams, I.T. Horvath, P. Mathur, B.E. Segmuller, L.W.
Yang, Organometallics 2 (1983) 1078;
f) R.D. Adams, Z. Dawoodi, D.F. Foust, Organometallics 1
(1982) 411.
2
on F by full-matrix lest-squares (SHELXL-97) [25], uti-
(
lized as incorporated in the WINGX [26] program pack-
age using all unique data. All nonhydrogen atoms
were refined anisotropically. Hydrogen atoms were in-
cluded in calculated positions (riding model) with Uiso
set at 1.2 times the Ueq of the parent atom. Selected
bond lengths and angles for 4, 9 and 10 are given in Ta-
bles 2–4, respectively. Crystallographic and other exper-
imental data are summarized in Table 1.
[4] D. Cauzzi, C. Graiff, G. Predieri, A. Tiripicchio, in: P. Braunstein,
L.A. Oro, P.R. Raithby (Eds.), Metal Clusters in Chemistry, vol.
3
, VCH, Weinheim, 1999, p. 193.
[
5] (a) P. Baistrocchi, D. Cauzzi, M. Lanfranchi, G. Predieri,
A. Tiripicchio, M.T. Camellini, Inorg. Chim. Acta 235
(1995) 173;
(b) P. Baistrocchi, M. Careri, D. Cauzzi, C. Graiff, M.
Lanfranchi, P. Manini, G. Predieri, A. Tiripicchio, Inorg.
Chim. Acta 252 (1996) 367;
(
c) D. Cauzzi, C. Graiff, C. Massera, G. Predieri, A.
Tiripicchio, J. Cluster Sci. 12 (2001) 259;
d) D. Cauzzi, C. Graiff, C. Massera, G. Predieri, A.
4
. Supplementary material
(
Tiripicchio, Inorg. Chim. Acta 300–302 (2000) 471.
6] R.D. Adams, O.-S. Kwon, S. Sanyl, J. Organomet. Chem. 681
(2003) 258.
Crystallographic data have been deposited with the
[
Cambridge Crystallographic Data Centre, CCDC
Nos.: 238219 for compound 4, 238220 for compound 9
and 238221 for compound 10. Copies of this informa-
tion may be obtained free of charge from The Director,
CCDC, 12 Union Road Cambridge, CB2 1EZ, UK (fax:
[7] P. Braunstein, C. Graiff, C. Massera, G. Predieri, J. Rose, A.
Tiripicchio, Inorg. Chem. 41 (2002) 1372.
[
8] (a) W. Levason, C.A. McAuliffe, Adv. Inorg. Chem. Radiochem.
4 (1972) 173;
b) S.O. Grim, L.C. Satek, J. Coord. Chem. 6 (1976) 39;
1
(
+44 1336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
(c) P.A.W. Dean, Can. J. Chem. 57 (1979) 754;
(d) S.O. Grim, L.C. Satek, C.A. Tolman, J.P. Jesson, Inorg.
Chem. 14 (1975) 656;
(
e) S.O. Grim, J.D. Mitchell, Inorg. Chem. 36 (1991) 1762.
Acknowledgements
[9] D. Cauzzi, C. Graiff, M. Langranchi, G. Predieri, A. Tiripicchio,
J. Organomet. Chem. 536–537 (1995) 497.
10] (a) D. Cauzzi, C. Graiff, M. Langranchi, G. Predieri, A.
[
We gratefully acknowledge the University Grants
Commission of Bangladesh for support of this work.
We also acknowledge the support of the National Sci-
ence Foundation EPSCoR program at the University
of Montana for support of this research.
Tiripicchio, J. Chem. Soc., Dalton Trans. (1995) 2321;
(b) D. Cauzzi, C. Graiff, C. Massera, G. Mori, G. Predieri, A.
Tiripicchio, J. Chem. Soc., Dalton Trans. (1998) 321.
[11] K.A. Azam, G.M.G. Hossain, S.E. Kabir, K.M.A. Malik, Md.A.
Mottalib, S. Pervin, N.C. Sarkar, Polyhedron 21 (2002) 38.
[
12] S.E. Kabir, S. Pervin, N.C. Sarker, A. Yesmin, A. Sharmin, T.A.
Siddiquee, D.T. Haworth, D.W. Bennett, K.M.A. Malik, J.
Organomet. Chem. 681 (2003) 237.
References
[
[
13] G. Lavigne, J.J. Bonnet, Inorg. Chem. 20 (1981) 2713.
14] Md.I. Hyder, Ph.D. Thesis, Jahangirnagar University, 2003.
[
[
1] M.L. Steigerwald, Polyhedron 13 (1994) 1245.
2] (a) M. Shieh, M.-H. Hsu, J. Cluster Sci. 15 (2004) 91;
[15] G. Lavigne, N. Lugan, J.J. Bonnet, Acta Crystallogr., Sect. B 38
(1982) 1911.
(
b) T. Akter, N. Begum, D.T. Haworth, D.W. Bennett, S.E.
[16] S.E. Kabir, N. Begum, Md.M. Hassan, Md.I. Hyder, H. Nur,
D.W. Bennett, T.A. Siddiquee, D.T. Haworth, E. Rosenberg, J.
Organomet. Chem. 689 (2004) 1569.
Kabir, Md.M. Miah, N.C. Sarker, T.A. Siddiquee, E. Rosenberg,
J. Organomet. Chem. 689 (2004) 257;

3420
S.E. Kabir et al. / Journal of Organometallic Chemistry 689 (2004) 3412–3420
[
[
[
[
[
17] G.M.G. Hossain, Md.I. Hyder, S.E. Kabir, K.M.A. Malik,
Md.A. Miah, T.A. Siddiquee, Polyhedron 22 (2003) 633.
18] K.M. Hanif, S.E. Kabir, M.A. Mottalib, M.B. Hursthouse,
K.M.A. Malik, E. Rosenberg, Polyhedron 19 (2000) 1073.
19] K.-B. Shiu, C.-H. Li, T.-J. Chan, S.-M. Peng, M.-C. Cheng, M.-
C. Wang, F.L. Liao, Organometallics 14 (1995) 524.
[22] (a) A.M. Bond, R. Cotton, P. Panagiotidou, Organometallics 7
(1988) 1767;
(b) S.O. Grim, E.D. Walton, Inorg. Chem. 19 (1980) 1982.
[23] XSCANS: Data Collection Software, Release 2.10b. Bruker AXS
Inc., Madison, WI, USA, 1994.
[24] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
[25] G.M. Sheldrick, SHELXL-97: Program for Crystal Structure
Refinement, University of Gottingen, Germany, Germany,
1997.
20] J.A. Cabeza, M.A. Martinez-Garcia, V. Riera, D. Ardura, S.
Garcia-Granda, Organometallics 17 (1998) 1471.
21] M.I. Bruce, B.K. Nicholson, M.L. Williams, Inorg. Synth. 28
(1990) 225.
[26] L.J. Farrugia, J. Appl. Crystallogr. 32 (1999) 837.