Facile E-E and E-C bond activation of PhEEPh (E = Te, Se, S) by ruthenium carbonyl clusters: Formation of Di- And triruthenium complexes bearing bridging dppm and phenylchalcogenide and capping chalcogenido ligands

Article abstract of DOI:10.1021/om701042s

Reactions of [Ru₃(CO)₁₀(μ-dppm)] (1) and its ortho-metalated derivative [Ru₃(CO)₉{μ₃- η³-P(C₆H₅)CH₂P(C ₆H₅)(C₆H₄)}] (11) with PhEEPh (E = Te, Se, S) have been investigated. Treatment of 1 with PhTeTePh at room temperature afforded the dinuclear compound [Ru₂(CO) ₄(μ-TePh)₂(μ-dppm)] (2) and the 54-electron triruthenium compounds [Ru₃(CO)₆(μ₃-Te) ₂(μ-TePh)₂(μ-dppm)] (3) and [Ru₃(CO) ₆(μ₃-Te)(μ-TePh)₃(η¹-COPh) (μ-dppm)] (4). Analogous reactions of 1 with PhEEPh (E = Se, S) led to [Ru₂(CO)₄(μ-EP[Ru₃(CO)₆(μ ₃-E)₂(μ-EPh)₂(μ-dppm)]) ₂(μ-dppm)] (E = Se, 5; E = S, 8) and the 54-electron triruthenium compounds (E = Se, 6; E = S, 9), and [Ru₃(CO) ₆(μ₃-E)(μ-EPh)₃(Ph)(μ-dppm)] (E = Se, 7; E = S, 10). Reactions of the ortho-metalated complex 11 with PhEEPh (E = Te, Se, S) in refluxing THF gave exclusively [Ru₃(CO)₆(μ- EPh)₂{μ₃-η³-P(C₆H ₅)CH₂P(C₆H₅)(C₆H ₄)}] (E = Te, 12; E = Se, 13; E = S, 14). The new compounds have been characterized by a combination of analytical and spectroscopic methods, and molecular structures of 2-4, 7, 10, and 13 have been determined by single-crystal X-ray diffraction studies. Compounds 2, 5, and 8 have the classical sawhorse structure with two bridging EPh (E = Te, Se, S) moieties and one bridging dppm ligand. Compounds 3, 6, and 9 contain a Ru ₃ framework with two bridging EPh (E = Te, Se, S) groups, one bridging dppm ligand, and two capping chalcogenido ligands. Compound 4 contains an Ru₃ core with a capping tellurido ligand, three bridging TePh moieties, one bridging dppm ligand, and a terminally coordinated benzoyl group, formed from multiple fragmentation of the PhTeTePh ligand and migratory insertion of a Ph group into a CO ligand. Compounds 7 and 10 comprise a capping chalcogenido ligand, three bridging EPh (E = Se, 7; E = S, 10) moieties, a bridging dppm ligand, and a terminally coordinated σ-bonded phenyl group. In compounds 12-14, the coordination of ortho-metalated diphosphine ligand is the same as in 11 and both the EPh moieties bridge the same unbridged Ru-Ru edge. Compounds 3, 6, 7, and 10 exhibit restricted fluxional behavior involving the μ-EPh moieties.

Full text of DOI:10.1021/om701042s

1550
Organometallics 2008, 27, 1550–1560
Facile E-E and E-C Bond Activation of PhEEPh (E ) Te, Se, S)
by Ruthenium Carbonyl Clusters: Formation of Di- and
Triruthenium Complexes Bearing Bridging dppm and
Phenylchalcogenide and Capping Chalcogenido Ligands
Noorjahan Begum,† Md. Iqbal Hyder,† Mohammad R. Hassan,† Shariff E. Kabir,*,†
Dennis W. Bennett,‡ Daniel T. Haworth,‡ Tasneem A. Siddiquee,‡ Dalia Rokhsana,§
Ayesha Sharmin,§ and Edward Rosenberg*,§
Department of Chemistry, Jahangirnagar UniVersity, SaVar, Dhaka 1342, Bangladesh, Department of
Chemistry, UniVersity of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53211, and Department of
Chemistry, The UniVersity of Montana, Missoula, Montana 59812
ReceiVed October 17, 2007
Reactions of [Ru3(CO)10(µ-dppm)] (1) and its ortho-metalated derivative [Ru3(CO)9{µ3-η3-
P(C6H5)CH2P(C6H5)(C6H4)}] (11) with PhEEPh (E ) Te, Se, S) have been investigated. Treatment of 1
with PhTeTePh at room temperature afforded the dinuclear compound [Ru2(CO)4(µ-TePh)2(µ-dppm)]
(2) and the 54-electron triruthenium compounds [Ru3(CO)6(µ3-Te)2(µ-TePh)2(µ-dppm)] (3) and [Ru3(CO)6(µ3-
Te)(µ-TePh)3(η1-COPh)(µ-dppm)] (4). Analogous reactions of 1 with PhEEPh (E ) Se, S) led to
[Ru2(CO)4(µ-EP[Ru3(CO)6(µ3-E)2(µ-EPh)2(µ-dppm)])2(µ-dppm)] (E ) Se, 5; E ) S, 8) and the 54-electron
triruthenium compounds (E ) Se, 6; E ) S, 9), and [Ru3(CO)6(µ3-E)(µ-EPh)3(Ph)(µ-dppm)] (E ) Se, 7;
E ) S, 10). Reactions of the ortho-metalated complex 11 with PhEEPh (E ) Te, Se, S) in refluxing THF
gave exclusively [Ru3(CO)6(µ-EPh)2{µ3-η3-P(C6H5)CH2P(C6H5)(C6H4)}] (E ) Te, 12; E ) Se, 13; E )
S, 14). The new compounds have been characterized by a combination of analytical and spectroscopic
methods, and molecular structures of 2-4, 7, 10, and 13 have been determined by single-crystal X-ray
diffraction studies. Compounds 2, 5, and 8 have the classical “sawhorse” structure with two bridging
EPh (E ) Te, Se, S) moieties and one bridging dppm ligand. Compounds 3, 6, and 9 contain a Ru3
framework with two bridging EPh (E ) Te, Se, S) groups, one bridging dppm ligand, and two capping
chalcogenido ligands. Compound 4 contains an Ru3 core with a capping tellurido ligand, three bridging
TePh moieties, one bridging dppm ligand, and a terminally coordinated benzoyl group, formed from
multiple fragmentation of the PhTeTePh ligand and migratory insertion of a Ph group into a CO ligand.
Compounds 7 and 10 comprise a capping chalcogenido ligand, three bridging EPh (E ) Se, 7; E ) S,
10) moieties, a bridging dppm ligand, and a terminally coordinated σ-bonded phenyl group. In compounds
12–14, the coordination of ortho-metalated diphosphine ligand is the same as in 11 and both the EPh
moieties bridge the same unbridged Ru-Ru edge. Compounds 3, 6, 7, and 10 exhibit restricted fluxional
behavior involving the µ-EPh moieties.
cleavage of E-E bonds of diphenyl dichalcogenide ligands.14
Introduction
Applying this latter approach, Lewis et al.15 and Arce et al.16
Transition-metal–carbonyl compounds containing chalcogen
atoms have attracted much attention in recent years, owing to
their importance in fundamental research as well as in techno-
logical fields.1–3 The presence of chalcogen atoms appears to
often be decisive in cluster aggregation and condensation
reactions.4–10 In addition, interest in chalcogen-rich metal
compounds stems from their unusual structural and reactivity
patterns and application as precursors for new solid-state
materials.11,12 A potential route to prepare the chalcogenide
carbonyl species is by the facile oxidative addition of Ph3PdE
(E ) S, Se, Te) to zerovalent metal centers, which commonly
generates tertiary phosphine substituted clusters with capping
chalcogenide elements.13 Another method for the synthesis of
bridging chalcogenide metal–carbonyl clusters involves the
synthesized the 50-electron cluster [Os3(CO)10(µ-SePh)2], in
which one SePh group bridged an Os-Os edge and the other
an open Os-Os edge, from the reactions of [Os3(CO)12-n
-
(NCMe)n] with PhSeSePh. Recently, Leong and Zhang17
reported the corresponding tellurium analogue [Os3(CO)10(µ-
TePh)2] from the reaction between [Os3(CO)10(MeCN)2] and
PhTeTePh. Thermolysis of both [Os3(CO)10(µ-SePh)2] and
[Os3(CO)10(µ-TePh)2] at 80 °C was reported to lead to an isomer
in which both of the EPh (E ) Se, Te) moieties bridge the same
(1) (a) Mathur, P.; Philip, R.; Kumar, G. R.; Ghose, S. Opt. Commun.
2000, 178, 469. (b) Pushkarevsky, N. A.; Bashirov, D. A.; Terenteva, T. G.;
Virovets, A. V.; Peresypkina, E. V.; Krautscheid, H.; Konchenko, S. N.
Russ. J. Coord. Chem. 2006, 32, 416. (c) McDonough, J. E.; Weir, J. J.;
Sukcharoenphon, K.; Hoff, C. D.; Kryatova, O. P.; Rybak Akimova, E. V.;
Scott, B. L.; Kubas, G. J.; Mendiratta, A.; Cummins, C. C. J. Am. Chem.
Soc. 2006, 128, 10295. (d) Henkel, G.; Weissgraber, S. In Metal Clusters
in Chemistry; Braunstein, P., Oro, L. A., Raithby, P. R., Eds.; Wiley-VCH:
Weinheim, Germany, 1999; Vol. 1, p 163. (e) Casado, M. A.; Ciriano, M. A.;
Edwards, A. J.; Fernando, J. L.; Perez-Torrente, J. J.; Oro, L. A.
Organometallics 1998, 17, 3414.
* To whom correspondence should be addressed. E-mail:
edward.rosenberg@mso.umt.edu (E.R.); skabir_ju@ yahoo.com (S.E.K.).
† Jahangirnagar University.
‡ University of Wisconsin-Milwaukee.
§ The University of Montana.
10.1021/om701042s CCC: $40.75
2008 American Chemical Society
Publication on Web 03/05/2008

Facile E-E and E-C Bond ActiVation of PhEEPh
Organometallics, Vol. 27, No. 7, 2008 1551
Chart 1
open metal-metal edge. The reactions of the dppm derivative
[Os3(CO)10(µ-dppm)] with PhEEPh (E ) Se, S, Te) resulted in
a wide variety of structures, depending on the ligand. For
example, the reaction of [Os3(CO)10(µ-dppm)] with PhSeSePh
at 110 °C afforded the dinuclear compound [Os2(CO)4(µ-
SePh)2(µ-dppm)], three 50-electron isomeric compounds with
the formula [Os3(CO)8(µ-SePh)2(µ-dppm)], and the benzyne
compound [Os3(CO)6(µ-CO)(µ-Se)2(µ-C6H4)(µ-dppm)],18 whereas
the corresponding reaction with PhSSPh furnished the three
trinuclear compounds [Os3(CO)7(µ-SPh)(µ3-η4-Ph2PCH(Ph)-
C6H4)(µ-H)], [Os3(CO)8(µ-SPh)2(µ-dppm)], and [Os3(CO)7(µ-
SPh)(µ-η2-SC6H4)(µ-dppm)(µ-H)]19 (Chart 1). In contrast, a
similar reaction of [Os3(CO)10(µ-dppm)] with PhTeTePh gave
the binuclear compound [Os2(CO)4(µ-TePh)2(µ-dppm)] and two
50-electron isomeric compounds with the formula [Os3(CO)8(µ-
TePh)2(µ-dppm)]19 (Chart 1).
To date, only a few examples of the reactivity of [Ru3(CO)12]
with diphenyl dichalcogenides are known. The first report was
apparently that involving the reactions of [Ru3(CO)12] with
PhEEPh (E ) Te, Se), from which were isolated the dinuclear
[Ru2(CO)6(µ-EPh)2] and the polymeric compounds [Ru(CO)2(µ-
EPh)]n, whose structures were based on spectroscopic data
only.20 The second report demonstrates the coordination of SePh
units on ruthenium carbide carbonyl clusters, affording [Ru6C-
(CO)14(µ-SePh)2] and other related derivatives.21 Another recent
report describes the synthesis of the dinuclear compound
[Ru2(CO)6(µ-TeC6H4OEt-4)2(µ-dppm)] and [Ru4(CO)8(µ-CO)(µ4-
Te)2(µ-dppm)] from the reaction of [Ru3(CO)10(µ-dppm)] (1)
with Te2(C6H4OEt-4)2 in refluxing toluene.22 Given the paucity
of information reported on the systematic investigation of the
reactivity of diphenyl dichalcogenide ligands toward ruthenium
carbonyl clusters and in line with our general interest in the
synthesis and reactivity of transition-metal-main-group-element
mixed-metal clusters, we have now investigated the reactions
of PhEEPh (E ) Te, Se, S) with [Ru3(CO)10(µ-dppm)] (1) and
obtained several novel chalcogenide-rich 54-electron ruthenium
carbonyl clusters resulting from the multiple fragmentation of
the PhTeTePh ligand as well as cleavage of all three Ru-Ru
bonds. In order to compare the reactivity of the ortho-metalated
compound [Ru3(CO)9{µ3-η3-P(C6H5)CH2P(C6H5)(C6H4)}] (11)
with that of the parent 1, we have also investigated the reactions
of 11 with PhEEPh (E ) Te, Se, S) and observed a significantly
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Trans. 1999, 237.
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M. G.; Huang, S. P. Coord. Chem. ReV. 1994, 130, 223.
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1990, 29, 4658 and references therein. (b) Mathur, P.; Reddy, V. D.; Das,
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1552 Organometallics, Vol. 27, No. 7, 2008
Begum et al.
Scheme 1
different reactivity leading to the formation of the 48-electron
telluride ligands, and six terminal carbonyl ligands, two bonded
to each ruthenium atom. A striking feature of the structure is
the occurrence of one bridging ligand across each open Ru-Ru
edge. One TePh ligand asymmetrically bridges the Ru(1) · · · Ru(3)
edge (Ru(1)-Te(3) ) 2.7058(19) and Ru(3)-Te(3) ) 2.651(2)
Å), and the other asymmetrically bridges the Ru(2) · · · Ru(3)
edge (Ru(2)-Te(4) ) 2.7110(18) and Ru(3)-Te(3) ) 2.652(2)
Å). The dppm ligand symmetrically spans the open Ru(1) · · · Ru(2)
edge (Ru(1)-P(1) ) 2.340(5) and Ru(2)-P(2) ) 2.341(5) Å)
and occupies axial coordination sites. The nonbonding Ru · · · Ru
distance associated with the dppm bridge (Ru(1) · · · Ru(2) )
4.124 Å) is significantly longer than those involving the TePh
bridge (Ru(1) · · · Ru(3) ) 3.581, Ru(2) · · · Ru(3) ) 3.582 Å).
Another interesting feature is that one tellurido ligand sym-
metrically caps the three Ru atoms (Ru(3)-Te(1) ) 2.7762(19),
Ru(2)-Te(1) ) 2.7803(18) and Ru(1)-Te(1) ) 2.7827(18) Å),
while the other ligand asymmetrically caps the Ru3 system
clusters [Ru3(CO)6(µ-EPh)2{µ3-η3-P(C6H5)CH2P(C6H5)(C6H4)}].
Results and Discussion
Reaction of [Ru3(CO)10(µ-dppm)] (1) with PhTeTePh. The
reaction of 1 with PhTeTePh at 25 °C, followed by thin-layer
chromatographic separation, furnished the binuclear compound
[Ru2(CO)4(µ-TePh)2(µ-dppm)] (2) and the trinuclear compounds
[Ru3(CO)6(µ3-Te)2(µ-TePh)2(µ-dppm)] (3) and [Ru3(CO)6(µ3-
Te)(µ-TePh)3(η1-COPh)(µ-dppm)] (4) (Scheme 1) in 14, 18, and
22% yields, respectively. When the reaction was conducted in
refluxing THF, the yield of the dinuclear compound 2 was
increased slightly but those of the trinuclear compounds 3 and
4 were decreased significantly. All these compounds are stable
in the solid state and decompose in solution over period of days.
The compounds were characterized by a combination of
elemental analysis, IR, 1H NMR, 31P{1H} NMR, mass spectral
data, and single-crystal X-ray diffraction studies.
An ORTEP diagram giving the molecular structure of 2 is
depicted in Figure 1, crystal data are collected in Table 1, and
selected bond distances and angles are listed in the caption to
the figure. The basic structure of 2 is comparable to that of
[Ru2(CO)4(µ-TeC6H4OEt-4)2(µ-dppm)].22 The metal core of
compound 2 contains a Te2Ru2 butterfly geometry with the
wingtips of Te atoms linked with two phenyl groups. The
ruthenium-ruthenium backbone is ligated by four terminal
carbonyl ligands and bridged by a dppm ligand. The TePh and
the dppm ligands are transoid to each other, and the Ru-Ru-Te
planes are perpendicular to each other. The Ru-Ru bond
distance of 2.7475(9) Å is comparable to the corresponding
distances in [Ru2(CO)4(µ-SePh)2(µ-dppm)] (2.8719(7) Å). The
Ru-Te bond distances (Ru(2)-Te(2) ) 2.6745(11), Ru(1)-Te(2)
) 2.6753(10), Ru(1)-Te(1) ) 2.6691(8), Ru(2)-Te(1) )
2.6988(8) Å) are comparable to those observed in [Ru2(CO)4(µ-
SePh)2(µ-dppm)].22 The spectroscopic data of 2 are consistent
with the solid-state structure. The carbonyl stretching frequencies
in the IR spectrum are very similar to those reported for
[Ru2(CO)4(µ-TeC6H4OEt-4)2(µ-dppm)].22 In addition to the
phenyl proton resonances of the dppm and TePh moieties in
the aromatic region, the 1H NMR spectrum contains two
multiplets at δ 4.57 and 2.49 assigned to the methylene protons
of the dppm ligand. The two phosphorus nuclei are equivalent,
and as expected, the 31P{1H} NMR spectrum of 2 shows a
singlet at δ 13.9. The mass spectrum confirms the stoichiometry
with a molecular ion peak at m/z 1108.
Figure 1. ORTEP diagram of [Ru2(CO)4(µ-TePh)2(µ-dppm)] (2)
with 50% probability thermal ellipsoids. Selected interatomic
distances (Å) and angles (deg): Ru(2)-Ru(1) ) 2.7475(9),
Ru(2)-Te(2))2.6745(11),Ru(1)-Te(2))2.6753(10),Ru(1)-Te(1)
) 2.6691(8), Ru(2)-Te(1) ) 2.6988(8), Ru(2)-C(27) ) 1.880(7),
Ru(2)-C(26) ) 1.888(7), Ru(2)-P(2) ) 2.3172(17), Ru(1)-C(29)
) 1.872(6), Ru(1)-C(28) ) 1.894(6), Ru(1)-P(1) ) 2.3162(18);
Ru(2)-Te(2)-Ru(1) ) 61.80(3), Ru(1)-Te(1)-Ru(2) ) 61.57(2),
P(2)-Ru(2)-Te(2) )153.47(4), P(2)-Ru(2)-Te(1) ) 92.31(4),
Te(2)-Ru(2)-Te(1) ) 79.88(2), P(2)-Ru(2)-Ru(1) ) 95.12(4),
Te(2)-Ru(2)-Ru(1) ) 59.113(19), Te(1)-Ru(2)-Ru(1) ) 58.68(2),
Te(1)-Ru(1)-Te(2) ) 80.40(2), P(1)-Ru(1)-Ru(2) ) 94.17(4),
Te(1)-Ru(1)-Ru(2) ) 59.747(16), Te(2)-Ru(1)-Ru(2) ) 59.08(2),
P(2)-C(1)-P(1) ) 114.9(3).
An ORTEP diagram of the molecular structure of 3 is shown
in Figure 2, crystal data are collected in Table 1, and selected
bond distances and angles are listed in the caption to the figure.
The molecule consists of three ruthenium atoms arranged in an
open fashion with no metal-metal bonds containing one
bridging dppm ligand, two bridging TePh groups, two capping

Facile E-E and E-C Bond ActiVation of PhEEPh
Organometallics, Vol. 27, No. 7, 2008 1553
Table 1. Crystal Data for Compounds 2-4, 7, 10, and 13
2
3
4
empirical formula
fw
C41H32O4P2Ru2Te2
1106.71
C43H32O6P2Ru3Te4
1517.74
C56H42O7P2Ru3Te4
1699.95
temp, K
293(2)
293(2)
293(2)
wavelength (Å)
cryst syst
space group
a (Å)
b (Å)
c (Å)
0.710 73
monoclinic
P21/2
11.015(5)
18.542(5)
19.843(5)
90.000(5)
92.340(5)
90.000(5)
0.710 73
orthorhombic
Pbca
19.621(5)
22.168(5)
23.948(5)
90.000(5)
90.000(5)
90.000(5)
0.710 73
monoclinic
P21/c
14.324(4)
20.600(5)
20.514(3)
90
103.01(2)
90
R (deg)
ꢀ (deg)
γ (deg)
V (Å3)
4049(2)
10416(4)
5898(2)
Z
4
8
5
calcd density (Mg/m3)
1.817
2.276
2128
2.141
3.546
6246
1.917
2.800
3216
abs coeff (mm-1
F(000)
)
cryst size (mm3)
0.37 × 0.18 × 0.24
2.05-25.01
-13 e h e 1
-1 e k e 22
-23 e 1 e 23
8880
7121 (R(int) ) 0.0401)
7121/0/460
0.934
R1 ) 0.0379
wR2 ) 0.0941
R1 ) 0.0492
wR2 ) 0.1522
2.698 and –0.679
0.30 × 0.16 × 0.15
1.84-24.99
-23 e h e 1
-21 e k e 1
-1 e 1 e 23
5950
4883 (R(int) ) 0.0324)
4883/0/523
1.033
R1 ) 0.0529
wR2 ) 0.1332
R1 ) 0.0821
wR2 ) 0.1559
1.117 and -0.778
0.44 × 0.13 × 0.13
1.76-22.49
-1 e h e 15
-1 e k e 22
-22 e l e 21
9339
7671 (R(int) ) 0.0263)
7671/0/649
1.062
R1 ) 0.0477
wR2 ) 0.1467
R1 ) 0.0610
wR2 ) 0.1020
4.994 and –0.781
θ range for data collecn (deg)
index ranges
no. of rflns collected
no. of indep rflns
no. of data/restraints/params
goodness of fit on F2
final R indices (I > 2σ(I))
R indices (all data)
largest diff peak and hole (e Å-3
)
7
10
13
empirical formula
fw
C55H42O6P2Ru3Se4
1479.88
C55H42O6P2Ru3S4
1517.74
C37H26O6P2Ru3Se2
1089.65
temp, K
293(2)
293(2)
293(2)
wavelength (Å)
cryst syst
space group
a (Å)
b (Å)
c (Å)
0.710 73
0.710 73
0.710 73
triclinic
P21/c
13.2641(6)
18.3099(8)
16.7128(8)
90
109.9050(10)
90
3816.5(3)
4
1.896
3.207
triclinic
triclinic
j
j
P1
P1
13.103(2)
13.604(2)
17.044(3)
95.790(10)
93.410(10)
115.750(10)
2704.3(7)
13.243(5)
13.758(5)
16.578(5)
97.570(5)
R (deg)
ꢀ (deg)
91.790(5)
γ (deg)
117.290(5)
2646.4(16)
2
1.448
1.064
V (Å3)
Z
2
calcd density (Mg/m3)
1.817
3.626
abs coeff (mm-1
)
F(000)
1436
1148
2104
crystal size (mm3)
0.27 × 0.18 × 0.16
1.80-22.49
-14 e h e 1
-12 e k e 12
-16 e 1 e 16
5986
5102 (R(int) ) 0.0484)
5102/0/631
1.059
R1 ) 0.0474
wR2 ) 0.1049
R1 ) 0.0820
wR2 ) 0.094
0.614 and –0.639
0.19 × 0.17 × 0.06
1.77-22.37
-1 e h e 7
-13 e k e 12
-15 e 1 e 15
4624
3759 (R(int) ) 0.0274)
3759/36/631
0.844
R1 ) 0.0319
wR2 ) 0.0855
R1 ) 0.0486
wR2 ) 0.0938
0.340 and -0.386
0.51 × 0.16 × 0.06
1.63-28.31
-17 e h e 17
-23 e k e 23
-22 e l e 22
33 620
9079 (R(int) ) 0.0357)
9079/0/451
0.854
R1 ) 0.0362
wR2 ) 0.0842
R1 ) 0.0525
wR2 ) 0.1205
0.714 and –0.333
θ range for data collecn (deg)
index ranges
no. of rflns collected
no. of indep rflns
no. of data/restraints/params
goodness of fit on F2
final R indices (I > 2σ(I))
R indices (all data)
largest diff peak and hole (e Å-3
)
(Ru(1)-Te(2) ) 2.7675(18), Ru(2)-Te(2) ) 2.7639(18), and
Ru(3)-Te(2) ) 2.7907(19) Å). Overall, compound 3 contains
a total of 54 cluster valence electrons, which is precisely the
number expected for an open cluster of three metal atoms with
each ruthenium atom having an 18-electron configuration.23 The
formulation of the cluster is supported by its FAB mass
spectrum, which exhibits a molecular ion peak at m/z 1522. The
31P{1H} NMR spectrum at room temperature displays two
singlets at δ 14.4 and 13.9, indicating that the molecule exhibits
some sort of isomerism in solution (see VT NMR studies
1
section), which is also supported by the H NMR spectrum.
An ORTEP diagram of the molecular structure of 4 is shown
in Figure 3, crystal data are given in Table 1, and selected bond
distances and angles are collected in the caption to the figure.
(23) Mingos, D. M. P. Acc. Chem. Res. 1984, 17, 311.

1554 Organometallics, Vol. 27, No. 7, 2008
Begum et al.
Figure 3. ORTEP diagram of [Ru3(CO)6(µ3-Te)(µ-TePh)3(COPh)(µ-
dppm)] (4) with 50% probability thermal ellipsoids. Selected
interatomic distances (Å) and angles (deg): Ru(1) · · · Ru(6) )
3.991, Ru(6) · · · Ru(7) ) 4.017, Ru(1) · · · Ru(7) ) 4.156,
Ru(1)-Te(1) ) 2.7220(12), Ru(6)-Te(1) ) 2.7440(14),
Ru(7)-Te(2) ) 2.7366(13), Ru(1)-Te(2) ) 2.7410(14),
Ru(6)-Te(2) ) 2.7452(12), Ru(7)-Te(3) ) 2.7355(14),
Ru(1)-Te(3) ) 2.7503(12), Ru(1)-P(8) ) 2.363(3), Ru(6)-Te(4)
) 2.7412(13), Ru(7)-Te(4) ) 2.7909(13), Ru(6)-P(9) )
2.363(3), Ru(7)-C(24) ) 2.080(13); P(8)-C(1)-P(9) ) 121.0(6),
Ru(1)-Te(1)-Ru(6) ) 93.81(4), Ru(7)-Te(2)-Ru(1) ) 98.69(4),
Ru(7)-Te(2)-Ru(6) ) 97.06(4), Ru(1)-Te(2)-Ru(6) ) 93.36(4),
Ru(7)-Te(3)-Ru(1) ) 98.49(4), Te(1)-Ru(1)-Te(2) ) 83.98(4),
P(8)-Ru(1)-Te(3) ) 172.14(8), Te(1)-Ru(1)-Te(3) ) 86.79(4),
Te(2)-Ru(1)-Te(3) ) 80.75(4), Ru(6)-Te(4)-Ru(7) ) 95.88(4),
Te(4)-Ru(6)-Te(1) ) 76.00(3), P(9)-Ru(6)-Te(2) ) 88.61(8),
Te(4)-Ru(6)-Te(2) ) 83.67(4), Te(1)-Ru(6)-Te(2) ) 83.49(4),
Te(3)-Ru(7)-Te(2) ) 81.10(3), Te(3)-Ru(7)-Te(4) ) 95.57(4),
Te(2)-Ru(7)-Te(4) ) 82.91(4).
Figure 2. ORTEP diagram of [Ru3(CO)6(µ3-Te)2(µ-TePh)2(µ-
dppm)] (3) with 50% probability thermal ellipsoids. Selected
interatomic distances (Å) and angles (deg): Ru(1) · · · Ru(2) ) 4.124,
Ru(2) · · · Ru(3) ) 3.582, Ru(1) · · · Ru(3) ) 3.581, Ru(3)-Te(1) )
2.7762(19), Ru(2)-Te(1) ) 2.7803(18), Ru(1)-Te(1) ) 2.7827(19),
Ru(2)-Te(2))2.7639(18),Ru(1)-Te(2))2.7675(18),Ru(3)-Te(2)
) 2.7907(19), Ru(2)-P(2) ) 2.341(5), Ru(1)-P(1) ) 2.340(5)
Ru(2)-Te(4))2.7110(18),Ru(1)-Te(3))2.7058(19),Ru(3)-Te(4)
) 2.655(2), Ru(3)-Te(3) ) 2.651(2); Ru(3)-Te(1)-Ru(2) )
80.30(5), Ru(3)-Te(1)-Ru(1) ) 80.20(5), Ru(2)-Te(1)-Ru(1) )
95.67(5), Ru(2)-Te(2)-Ru(1) ) 96.39(6), Ru(2)-Te(2)-Ru(3) )
80.33(5), Ru(1)-Te(2)-Ru(3) ) 80.21(5), Te(4)-Ru(2)-Te(2)
) 85.83(5), Te(4)-Ru(2)-Te(1) ) 82.74(5), Te(2)-Ru(2)-Te(1)
) 75.97(5), Te(3)-Ru(1)-Te(2) ) 85.97(5), Te(3)-Ru(1)-Te(1)
) 82.66(5), Te(2)-Ru(1)-Te(1) ) 75.87(5), Ru(3)-Te(4)-Ru(2)
) 83.77(5), Ru(3)-Te(3)-Ru(1) ) 83.88(5), Te(3)-Ru(3)-Te(4)
) 166.95(7), Te(3)-Ru(3)-Te(1) ) 83.78(6), Te(4)-Ru(3)-Te(1)
) 83.84(6), Te(3)-Ru(3)-Te(2) ) 86.56(5), Te(4)-Ru(3)-Te(2)
) 86.37(5), Te(1)-Ru(3)-Te(2) ) 75.60(5), P(1)-C(1)-P(2) )
118.5(8).
C(24)-O(24) bond distance of 1.232(15) Å, respectively, are
shorter and longer than those observed for the terminally
coordinated benzoyl unit in ruthenium compounds.24 Compound
4 contains a total of 54 cluster valence electrons, as expected
for a triruthenium complex with no metal-metal bonds, and
each ruthenium atom formally has an 18-electron configura-
tion.23 The formulation of 4 is confirmed by its FAB mass
spectrum, which exhibits the molecular ion peak at m/z 1704,
and the IR spectrum contains an absorption at 1735 cm-1
assignable to ν(CO) of the benzoyl moiety. The two phosphorus
atoms in 4 are nonequivalent, since the 31P{1H} NMR spectrum
exhibits two doublets at δ 12.1 and 11.1 with a phosphorus-
phosphorus coupling constant of 11.7 Hz, indicating the presence
of a single isomer.
Reactions of [Ru3(CO)10(µ-dppm)] (1) with PhSeSePh
and PhSSPh. Similar reactions of 1 with PhSeSePh and PhSSPh
took a slightly different course, affording the dinuclear com-
pounds [Ru2(CO)4(µ-EPh)2(µ-dppm)] (5, E ) Se, 11%; 8, E )
S, 15%) and the trinuclear compounds [Ru3(CO)6(µ3-E)2(µ-
EPh)2(µ-dppm)] (6, E ) Se, 25%; 9, E ) S, 18%) and
[Ru3(CO)6(µ3-E)(µ-EPh)3(η1-Ph)(µ-dppm)] (7, E ) Se, 35%;
10, E ) S, 14%) (Scheme 2). It is interesting to note that we
It is a structurally unique open cluster of three ruthenium atoms
with a TePh ligand asymmetrically bridging each of the three
nonbonded Ru · · · Ru edges and a capping telluride ligand. It
also contains a diaxially coordinated dppm ligand that sym-
metrically spans (Ru(1)-P(8) ) Ru(6)-P(9) ) 2.363(3) Å) one
of the Ru(1) · · · Ru(6) edges, which is simultaneously bridged
by a TePh moiety. Each of the ruthenium atoms has two terminal
carbonyl ligands. An interesting feature is that the tellurido
ligand symmetrically caps the three Ru atoms (Ru(7)-Te(2) )
2.7366(13), Ru(1)-Te(2) ) 2.7410(14), Ru(6)-Te(2) )
2.7452(12) Å). The TePh-bridged nonbonded Ru · · · Ru edges
(Ru(6) · · · Ru(7) ) 4.017, Ru(1) · · · Ru(7) ) 4.156 Å) are
significantly longer than the corresponding nonbonded edges
in 3. Interestingly, the dppm-bridged Ru(1) · · · Ru(6) distance
(3.991 Å) is shorter than the corresponding distance in 3.
The reason for this shortness is most probably due to the
presence of the bridging TePh ligand along the same edge. The
Ru-Te bond distances involving the TePh bridges that span
from 2.7220(12) to 2.7909(13) Å are in good agreement with
those observed in 3. An intriguing feature of the structure is
the η1 coordination of a benzoyl group to Ru(3), which is formed
by insertion of a phenyl group into the C(24)-O(24) carbonyl
group. The Ru(3)-C(24) bond distance of 2.080(13) Å and the
(24) R Charmant, J. P. H.; Dickson, H. A. A.; Grist, N. J.; Keister, J. B.;
Knox, S. A. R.; Morton, D. A. V.; Orpen, A. G.; Vinas, J. M. J. Chem.
Soc., Chem. Commun. 1991, 1393.

Facile E-E and E-C Bond ActiVation of PhEEPh
Organometallics, Vol. 27, No. 7, 2008 1555
Scheme 2
were not able to isolate any benzoyl-coordinated compound
analogous to 4; instead, we obtained the σ-bonded phenyl
compounds 7 and 10. The new compounds were characterized
by IR, 1H NMR, 31P{1H} NMR, mass spectral data, and
elemental analyses together with single-crystal diffraction studies
for 7 and 10. The carbonyl stretching frequencies in the infrared
spectra of 5 and 8 are similar to those of 2, indicating that they
are isostructural. The mass spectra of 5 and 8 show the molecular
ion peaks (m/z 1012 for 5 and 818 for 8) with successive loss
of four carbonyl groups. The 31P{1H} NMR spectra contain a
singlet at δ 24.2 for 5 and δ 29.3 for 8, indicating equivalent
31P nuclei. As expected, the dppm methylene protons show two
multiplets at δ 4.42 and 3.87 for 5 and at δ 4.34 and 3.59 for
8, and these solution data fit a structure similar to that found in
2. The patterns of the IR spectra of 6 and 9 are similar to that
of 3, indicating a similar distribution of the carbonyl ligands.
The mass spectra of 6 and 9 confirm the stoichiometry with
ion peaks at m/z 1326 and 1139. The 31P{1H} NMR spectrum
of 3 at room temperature exhibits two singlets δ at 27.8 and
27.4, indicating isomerism similar to that of 6. The 31P{1H}
NMR spectrum of 9 at room temperature exhibits a singlet at δ
27.8, implying a dynamic behavior different from that of 3 and
6 (see Variable-Temperature NMR Studies).
σ-bonded to the Ru atom not bridged by the dppm ligand:
Ru(2)-C(50) ) 2.125(13) Å for 7 and Ru(3)-C(44) )
2.129(11) Å for 10. The diaxially coordinated dppm ligand spans
the Ru(1) · · · Ru(3) nonbonded edge in 7 and the Ru(1) · · · Ru(2)
nonbonded edge in 10 with Ru-P distances (Ru(3)-P(1) )
2.351(3), Ru(1)-P(2) ) 2.348(3) Å for 7; Ru(1)-P(1) )
2.344(3), Ru(2)-P(2) ) 2.348(3) Å for 10) comparable to those
observed in 1.25
Because of their close structural similarity, the IR spectra of
7 and 10 in the carbonyl region are similar to that of 4, except
that the ν(CO) absorption of the benzoyl moiety observed in 4
is absent in 7 and 10. The 31P{1H} NMR spectra of 7 and 10
The ORTEP drawings of the molecular structures of 7 and
10 are depicted in Figures 4 and 5, respectively, crystal data
are given in Table 1, and selected bond distances and angles
are collected in the captions to the figures. Both complexes are
open triruthenium clusters with three bridging phenylchalco-
genido groups, each bridging across one open Ru · · · Ru edge,
a σ-Ru-C-bonded phenyl group, a bridging dppm, and a
capping chalcogenido ligand. Each ruthenium atom has two
terminally coordinated CO groups. Compounds 7 and 10 are
structurally similar to 4 except in place of a terminally
coordinated benzoyl group there are terminally coordinated
phenyl groups. The nonbonding Ru-Ru distances in 10
(Ru(1) · · · Ru(6) ) 3.670, Ru(2) · · · Ru(3) ) 3.682, Ru(1) · · · Ru(3)
)3.723Å)aresignificantlyshorterthanthosein7(Ru(1) · · · Ru(2)
) 3.843, Ru(2) · · · Ru(3) ) 3.872, Ru(1) · · · Ru(3) ) 3.796 Å),
which in turn are significantly shorter than those observed in 4.
The lengthening of all the nonbonded Ru-Ru distances from
10 to 7 to 4 can be attributed to the increase in the size of the
bridging atom across these edges. In 7, the Ru3 framework is
symmetrically capped by the selenido ligand (Ru(1)-Se(1) )
2.5646(16), Ru(2)-Se(1) ) 2.5646(16), Ru(3)-Se(1) )
2.5539(16) Å), and in 10, the Ru3 core is almost symmetrically
capped by the sulfido ligand (Ru(1)-S(4) ) 2.428(3), Ru(2)-S(4)
) 2.440(2), Ru(3)-S(4) ) 2.451(2) Å) with average Ru-Se
and Ru-S distances of 2.561(2) and 2.489(2) Å, respectively,
whicharelongerthanthecorrespondingdistancesin[Ru3(CO)7(µ3-
CO)(µ3-Se)(µ-dppm)] (average 2.4893(4) Å) and [Ru3(CO)7(µ3-
CO)(µ3-Se)(µ-dppm)] (average 2.366(3) Å).13c An interesting
feature of the structures is the presence of a phenyl group
Figure 4. ORTEP diagram of [Ru3(CO)6(µ3-Se)(µ-SePh)3(Ph)(µ-
dppm)] (7) with 50% probability thermal ellipsoids. Selected
interatomic distances (Å) and angles (deg): Ru(1) · · · Ru(2) )
3.843, Ru(2) · · · Ru(3) ) 3.872, Ru(1) · · · Ru(3) ) 3.796,
Ru(3)-P(1) ) 2.351(3), Ru(1)-P(2) ) 2.348(3), Ru(1)-Se(4)
) 2.5516(16), Ru(1)-Se(1) ) 2.5646(16), Ru(1)-Se(3) )
2.5916(16),Ru(2)-Se(1))2.5646(16),Ru(2)-Se(3))2.5689(16),
Ru(2)-Se(2))2.6440(17),Ru(3)-Se(1))2.5539(16),Ru(3)-Se(4)
) 2.5669(16), Ru(3)-Se(2) ) 2.5810(16), Ru(2)-C(50) )
2.125(13); P(2)-C(15)-P(1) ) 121.0(6), P(2)-Ru(1)-Se(4) )
93.95(9), Se(4)-Ru(1)-Se(1) ) 82.32(5), Se(4)-Ru(1)-Se(3)
) 85.15(5), Se(1)-Ru(1)-Se(3) ) 83.07(5), Se(1)-Ru(2)-Se(3)
) 83.52(5), Se(1)-Ru(2)-Se(2) ) 82.13(5), Se(3)-Ru(2)-
Se(2))93.71(5),Se(1)-Ru(3)-Se(4))82.23(5),Se(1)-Ru(3)-Se(2)
) 83.59(5), Se(4)-Ru(3)-Se(2) ) 77.96(5), Ru(3)-Se(1)-Ru(1)
) 95.73(5), Ru(3)-Se(1)-Ru(2) ) 98.32(5), Ru(1)-Se(1)-Ru(2)
) 97.06(5), Ru(2)-Se(3)-Ru(1) ) 96.27(5), Ru(3)-Se(2)-Ru(2)
) 95.65(5), Ru(1)-Se(4)-Ru(3) ) 95.73(5).

1556 Organometallics, Vol. 27, No. 7, 2008
Begum et al.
addition, a careful inspection of the baseline surrounding these
main resonances reveals at least three additional doublets of
very low intensity. As the temperature is increased, all of the
resonances broaden and coalesce, until at room temperature two
sharp singlets are observed at 27.8 and 27.4 ppm. Further heating
of the solution to 100 °C resulted in no significant changes in
the spectrum and the onset of decomposition. The weighted
average chemical shift of the two singlets is 27.4 ppm at room
temperature, while the weighted average chemical shift of the
two doublets is 27.2 ppm. The former is in good agreement
with the low-temperature data, while the latter is not. However,
it should be borne in mind that two of the low-intensity doublets
observed are at 30.2 and 31.2 ppm and these could contribute
significantly at higher temperatures to the observed weighted
average of the two major doublets of 27.8 ppm. It would appear
that there are two sets of isomers: one that is symmetrical with
respect to the dppm ligand (A an dB in Scheme 4) and two that
are unsymmetrical with respect to the dppm ligand (C and D
in Scheme 4). There is dynamic exchange within each set, but
not across sets within the temperature range examined. We
assign the isomers that are symmetrical with respect to the dppm
ligand to conformational isomers, which differ with respect to
the relative disposition of the phenyl groups on the µ-EPh
ligands. In isomer A the phenyl groups are transoid, and in
isomer B they are cisoid. The two µ-EPh groups in A are related
by an axis of symmetry and those in B by a plane of symmetry;
thus, neither isomer destroys the magnetic equivalence of the
phosphorus atoms in the dppm ligand. As the temperature is
increased, a wagging motion of the µ-EPh ligands could
equilibrate A and B. We propose that the unsymmetrical isotopes
C and D are equilibrated by an edge-to-edge migration involving
the edge of the Ru triangle not bridged by the dppm ligand.
This process would also equilibrate conformational isomers
associated with the µ-EPh ligands, only two of which are shown
in Scheme 4. The small doublets seen in the low-temperature
limiting spectrum can be assigned to the additional conforma-
tional isomers associated with the µ-EPh ligands (i.e., both
µ-EPh anti with respect to the dppm ligand, both µ-EPh syn
with respect to the dppm ligand, and two with the µ-EPh transoid
with respect to each other and syn or anti with respect to the
dppm ligand). It seems reasonable to propose that equilibration
of all of these isomers which are unsymmetrical with respect
to the dppm ligand would take place by edge hopping across
the longer edges (weaker bonds) of the Ru triangle, not bridged
by the dppm ligand. It is interesting to note that only isomers
of type A are observed in the solid-state structure of 3, while
in the case of complex 9 two doublets are observed in the low-
Figure 5. ORTEP diagram of [Ru3(CO)6(µ3-S)(µ-SPh)3(Ph)(µ-
dppm)] (10) with 50% probability thermal ellipsoids. Selected
interatomic distances (Å) and angles (deg): Ru(1) · · · Ru(6) ) 3.670,
Ru(2) · · · Ru(3) ) 3.682, Ru(1) · · · Ru(3) ) 3.723, Ru(1)-P(1) )
2.344(3), Ru(2)-P(2) ) 2.348(3), Ru(2)-S(4) ) 2.440(2),
Ru(2)-S(2) ) 2.480(2), Ru(3)-C(44) ) 2.129(11), Ru(3)-S(4)
) 2.451(2), Ru(3)-S(2) ) 2.456(2), Ru(1)-S(4) ) 2.428(3),
Ru(1)-S(3) ) 2.456(3), Ru(1)-S(1) ) 2.473(3), Ru(2)-S(3) )
2.438(3), Ru(3)-S(1) ) 2.540(3); P(1)-Ru(1)-S(4) ) 87.42(10),
S(4)-Ru(1)-S(3) ) 80.91(9), S(4)-Ru(1)-S(1) ) 82.95(10),
S(3)-Ru(1)-S(1) ) 79.24(8), S(3)-Ru(2)-S(4) ) 81.03(9),
S(3)-Ru(2)-S(2) ) 85.91(9), S(4)-Ru(2)-S(2) ) 82.79(8),
S(4)-Ru(3)-S(2) ) 83.04(8), S(4)-Ru(3)-S(1) ) 81.11(9),
S(2)-Ru(3)-S(1) ) 92.02(9), Ru(1)-S(4)-Ru(2) ) 97.87(9),
Ru(1)-S(4)-Ru(3) ) 99.46(10), Ru(2)-S(4)-Ru(3) ) 97.67(8),
Ru(2)-S(3)-Ru(1) ) 97.16(9), Ru(1)-S(1)-Ru(3) ) 95.92(10),
Ru(3)-S(2)-Ru(2) ) 96.50(8), P(2)-C(1)-P(1) ) 119.4(5).
are very similar and exhibit two doublets (δ 22.2 and 19.9, J )
12.6 Hz for 7; δ 25.9 and 23.9, J ) 12.6 Hz for 10) and a
singlet (δ 20.2 for 7; δ 23.5 for 10) clearly indicating the
presence of two isomers in solution (see below), one having
equivalent 31P nuclei which are nonequivalent in the other.
Consistent with the 31P NMR spectra, the aliphatic region of
the 1H NMR spectra show four sets of multiplets for the
diastereotopic methylene protons (δ 4.12, 3.96, 3.86, and 3.40
for 7; δ 4.76, 3.80, 3.44, and 3.21 for 10), which are also
attributed to the presence of two isomers in solution
(Scheme 5).
Variable-Temperature NMR Studies of 3, 6, 7, and 10.
The VT 31P NMR spectra for compounds 3 and 6 are virtually
identical. At the low -temperature limit of -80 °C compound
6 shows four 31P NMR resonances: a singlet at 28.2 ppm, a
doublet at 28.0 ppm (JP-P ) 32.2 Hz), a singlet at 27.0 ppm,
and a doublet at 26.4 ppm (JP-P ) 32.2 Hz) with approximate
relative intensity 1:2:2:2 (Figure 7). In the case of compound
3, the 31P NMR shows the same pattern with chemical shifts as
temperature limiting spectrum at 31.2 and 28.5 ppm (JP-P
)
30.3 Hz) at -80 °C in a relative intensity of 1:1 along with
two additional tiny doublets at 34.0 and 29.7 ppm (JP-P ) 31.3
Hz), suggesting that only unsymmetrical isomers related to C
and D (Scheme 4) are populated in solution. At room temper-
ature these doublets average to a singlet at 31.2 ppm, indicating
the same fluxional process is operative for 9 as for the C and
D isomers in 3 and 6. As for 3, the minor isomers are
contributing to the temperature-averaged chemical shift. That
only the most symmetrical isomer A is observed for 3 in the
solid state can be attributed to crystal-packing effects, while
the greater stability of isomers related to C and D in the case
of 9 in solution is probably the result of the smaller sulfur atom
preferring to bridge the shorter dppm-bridged edge of the Ru
triangle in the case of one of the µ-EPh ligands. That all four
isomers equilibrate in solution by dissolving a pure sample of
3a means that although 3a and 3b can be equilibrated on the
follows: a singlet at 14.5 ppm, a doublet at 14.3 ppm (JP-P
)
34.8 Hz), a singlet at 13.8 ppm, and a doublet at 13.5 ppm (JP-P
) 34.8 Hz) with approximate relative intensity 1:2:2:2. In
(25) Coleman, J. P.; Jones, D. F.; Dixneuf, P. H.; Brisson, C.; Bonnet,
J.-J.; Lavigne, G. Inorg. Chem. 1984, 23, 952.

Facile E-E and E-C Bond ActiVation of PhEEPh
Organometallics, Vol. 27, No. 7, 2008 1557
Scheme 3
NMR time scale (milliseconds to seconds in this case) the
formation of 3c (or 3d) takes place at a much slower rate not
accessible on the NMR time scale up to 100 °C, but rapidly
enough to form at ambient temperatures over the longer time
scales associated with dissolution and standing in solution over
the course of hours.
Compound 7 shows the presence of two isomers in solution,
as evidenced by the presence of two doublets at 26.9 and 24.9
ppm (JP-P ) 12.6 Hz) and a singlet at 24.3 ppm with relative
intensities of 1:1:3 (Figure 8). As the temperature is increased
to 100 °C, the doublet at 24.9 ppm and the singlet at 24.3 ppm
begin to broaden. Further increases in temperature were limited
by the solvent and the onset of slow decomposition of the
cluster. Compound 7 is apparently a very rigid molecule, and
we assign the minor changes in the spectrum to the onset of
axial radial exchange on the phenyl-substituted ruthenium atom
(Scheme 5). Compound 10 shows similar behavior.
Reactions
of
[Ru3(CO)9{µ3-η3-P(C6H5)CH2P(C6H5)-
(C6H4)}] (11) with PhEEPh (E ) Te, Se, S). The new
compounds [Ru3(CO)6(µ-EPh)2{µ3-η3-P(C6H5)CH2P(C6H5)-
(C6H4)}] (E ) Te, 12, 24%; E ) Se, 13, 28%; E ) S, 14, 28%)
were obtained as the only products from the reactions of the
ortho-metalated compound 11 with PhEEPh in refluxing THF
(Scheme 3). Compounds 12–14 were characterized by a
combination of elemental analysis, IR, 1H NMR, 31P{1H} NMR,
and mass spectral data as well as single-crystal X-ray diffraction
analysis of one of the representative compounds, 13.
An ORTEP diagram of the molecular structure of 13 is shown
in Figure 6, crystal data are given in Table 1, and selected bond
distances and angles are collected in the caption to the figure.
The molecule consists of a triangular cluster of ruthenium atoms
with two bridging SePh ligands, a triply bridging PhPCH2P-
(C6H4)Ph ligand, five terminal carbonyl ligands, and a semibridg-
ing carbonyl ligand. The Ru3 triangle is significantly distorted
and has one long bond (Ru(1)-Ru(3) ) 3.0566(4) Å) one
significantly short bond (Ru(1)-Ru(2) ) 2.7470(4) Å),
and one fairly short bond, (Ru(2)-Ru(3) ) 2.7909(4) Å). The
Scheme 4
Figure 6. ORTEP diagram of Ru3(CO)5(µ-CO)(µ-SePh)2-
{PhPCH2P(C6H4)Ph}] (13) with 50% probability thermal ellipsoids.
Selected interatomic distances (Å) and angles (deg): Ru(1)-Ru(2)
) 2.7470(4), Ru(1)-Ru(3) ) 3.0566(4), Ru(2)-Ru(3) ) 2.7909(4),
Ru(1)-Se(1) ) 2.5504(5), Ru(2)-Se(1) ) 2.5049(5), Ru(1)-Se(2)
) 2.5322(5), Ru(2)-Se(2) ) 2.5297(5), Ru(2)-C(22) ) 1.907(5),
Ru(3)-C(22) ) 2.579(4), Ru(2)-P(1) ) 2.3209(10), Ru(1)-P(2) )
2.3334(9), Ru(3)-P(1) ) 2.3044(10); Ru(1)-Ru(2)-Ru(3) )
66.995(11), Ru(2)-Ru(1)-Ru(3) ) 57.189(11), Ru(2)-Ru(3)-Ru(1)
) 55.816(10), Ru(2)-Se(1)-Ru(1) ) 65.822(14), Ru(2)-Se(2)-Ru(1)
) 65.733(13), Se(1)-Ru(2)-Ru(1) ) 57.887(13), Se(2)-Ru(2)-Ru(1)
) 57.178(12), Se(1)-Ru(2)-Ru(3) ) 113.881(16), Se(2)-Ru(2)-Ru(3)
) 100.137(15), Se(1)-Ru(1)-Ru(2) ) 56.290(13), Se(2)-Ru(1)-Ru(2)
) 57.089(13), Se(1)-Ru(1)-Ru(3) ) 104.396(15), Se(2)-Ru(1)-Ru(3)
) 93.403(14), Ru(2)-C(22)-Ru(3) ) 75.28(14), C(41)-P(1)-C(1)
) 106.76(18), P(1)-C(1)-P(2) ) 103.00(18), P(1)-Ru(3)-Ru(1) )
77.96(3), P(1)-Ru(3)-Ru(2) ) 53.16(3), P(1)-Ru(2)-Ru(3) )
52.62(3), P(2)-Ru(1)-Ru(3) ) 70.97(3).

1558 Organometallics, Vol. 27, No. 7, 2008
Begum et al.
semblance to that of the starting compound 11.28 One of the
phosphorus atoms, P(1), asymmetrically bridges the Ru(3)-Ru(2)
edge (Ru(2)-P(1) ) 2.3209(10) and Ru(3)-P(1) ) 2.3044(10)
Å), while P(2) is coordinated to Ru(1) (Ru(1)-P(2) ) 2.3334(9)
Å). The compound contains 48 valence electrons and is electron
precise with three metal-metal bonds.23
The spectroscopic data of 13 are consistent with the solid-
state structure, and the spectroscopic data of 12 and 14 indicate
that they are isostructural. The patterns of the carbonyl stretching
frequencies in the IR spectra of 12-14 are very similar,
indicating that they have very similar distributions of the
carbonyl ligands. In addition to the phenyl proton resonance of
the dppm and TePh moieties in the aromatic region, the 1H NMR
spectra exhibit well-separated signals for the ortho-metalated
phenyl group and the methylene protons of the dppm ligand.
The 31P{1H} NMR spectra of 12–14 exhibit two doublets (δ
67.5 and 1.0, JP-P ) 55.1 Hz for 12; δ 86.8 and 4.0, JP-P
)
54.3 Hz for 13; δ 85.6 and 4.6, JP-P ) 51.3 Hz for 14) consistent
with their structures. Their mass spectra confirm the stoichi-
ometry with molecular ion peaks (m/z 1188 for 12, m/z 1090
for 13, and m/z 997 for 14).
Conclusions
The work presented here demonstrates that the dppm-bridged
triruthenium cluster 1 exhibits high reactivity toward diphenyl
dichalcogenides at room temperature, which often leads to
metal-metal bond cleavage. Not only can EPh groups, formed
by facile cleavage of E-E bonds, be inserted into the Ru-Ru
bond but also capping chalcogenido ligands are formed by
further cleavage of E-C bonds. Furthermore, in contrast to the
reactions of the parent dodecacarbonyl, which furnished only
dinuclear compounds, and to [Os3(CO)10(µ-dppm)], which
afforded the di- and trinuclear complexes given in Chart 1 when
treated with PhEEPh, the reactions of 1 with PhEEPh (E ) Te,
Se, S) gave clusters with all three Ru-Ru bonds opened,
containing bridging EPh groups and capping chalcogenido
ligands, in spite of the presence of the bridging dppm ligand.
Notably, the osmium analogues of compounds 3, 4, 6, 7, 9,
and 10 were not detected from the reactions of [Os3(CO)10(µ-
dppm)] with PhEEPh, even under forcing reaction conditions.
This is probably due to the relatively high lability of the
ruthenium clusters compared with that of osmium. The ortho-
metalated compound 11 has been shown to react with PhEEPh
through oxidative cleavage of the E-E bond by adding both
EPh moieties across the unbridged Ru-Ru edge of the cluster.
Most likely, the capping µ3-η3-P(C6H5)CH2P(C6H5)(C6H4)
ligand in 12–14 helps to keep the metal triangle intact. It would
appear that the relative stability of the isomers of compounds
3, 6, and 9 in solution and their ability to interconvert is
governed by the size of the chalcogenide atom as it relates to
the strength of the µ-EPh bridge. Finally, the unusual chalcogen-
rich 54-electron compounds 3, 4, 6, 7, 9, and 10 reported in
this study should be useful precursors for the preparation of
solid-state materials.
Figure 7. VT 31P{1H} NMR spectra of [Ru3(CO)6(µ3-Se)2(µ-
SePh)2(µ-dppm)] (6) in CD2Cl2.
Scheme 5
last one is also shorter than the average Ru-Ru distances in
[Ru3(CO)12] (2.8564(10) Å).26 An intriguing feature of the
structure is the occurrence of two of the phenylselenido ligands
across the same Ru(1)-Ru(2) vector. The shortening of this
ruthenium-ruthenium bond is most probably due to the “pincer”
effect exerted by the bridging SePh ligands rather than the
strength of the metal-metal interaction. It is remarkable that
one SePh ligand asymmetrically bridges the Ru(1)-Ru(2) edge
(Ru(2)-Se(1) ) 2.5049(5) and Ru(1)-Se(1) ) 2.5504(5) Å)
while the other bridges symmetrically (Ru(1)-Se(2) ) 2.5322(5)
Å and Ru(2)-Se(2) ) 2.5297(5) Å). Among the six carbonyl
ligands attached to the metals of the skeleton, one carbonyl
(C(22)-O(22)) is semibridging to the Ru(3) atom (Ru(3)-C(22)
)2.579(4)andRu(2)-C(22))1.907(5)Å)withRu(3)-C(22)-O(22)
and Ru(2)-C(22)-O(22) angles of 117.4(4) and 166.8(4)°,
respectively, and the R value of 0.35 supports the description
of C(22)-O(22) as semibridging.27 The bonding mode of the
ortho-metalated PhPCH2P(C6H4)Ph ligand bears a strong re-
Experimental Section
All reactions and manipulations were carried out under an
atmosphere of prepurified nitrogen by using standard Schlenk
techniques. All solvents were purified by distillation from an
appropriate drying agent. Infrared spectra were recorded on a
(26) Churchill, M. R.; Hollander, F. J.; Hatchinson, J. P. Inorg. Chem.
1977, 16, 2655.
(27) Curtis, M. D.; Han, K. R.; Butler, W. M. Inorg. Chem. 1980, 19,
(28) Lugan, N.; Bonnet, J. J.; Ibers, J. A. J. Am. Chem. Soc. 1985, 107,
4484.
2096.

Facile E-E and E-C Bond ActiVation of PhEEPh
Organometallics, Vol. 27, No. 7, 2008 1559
Figure 8. VT 31P{1H} NMR spectra of [Ru3(CO)6(µ3-Se)(µ-SePh)3(Ph)(µ-dppm)] (7) in CD2Cl2.
Shimadzu FTIR 8101 spectrophotometer. NMR spectra were
recorded on a Bruker DPX 400 spectrometer. Chemical shifts for
the 31P{1H} NMR spectra are relative to 85% H3PO4. The starting
clusters [Ru3(CO)10(µ-dppm)]29 and [Ru3(CO)9{µ3-η3-P(C6H5)-
CH2P(C6H5)(C6H4)}]28 were prepared according to the published
procedures.
31P{1H} NMR (CD2Cl2) δ 12.1(JP-P ) 11.7 Hz), 11.1 (d, JP-P
)
11.7 Hz); FAB mass spectrum m/z 1704. Anal. Calcd for
C56H42O7P2Ru3Te4: C, 39.51; H, 2.49. Found: C, 39.68; H, 2.58.
Reaction of 1 with PhSeSePh. A reaction similar to that above
of 1 (200 mg, 0.207 mmol) with PhSeSePh (129 mg, 0.413 mmol)
in THF (35 mL) followed by similar chromatographic separation
afforded the following compounds, in order of elution: [Ru2(CO)4-
(µ-SePh)2(µ-dppm)] (5; 22 mg, 11%), [Ru3(CO)6(µ3-Se)2(µ-SePh)2(µ-
dppm)] (6; 69 mg, 25%), and [Ru3(CO)6(µ3-Se)(µ-SePh)3(Ph)(µ-
dppm)] (7; 107 mg, 35%) as yellow crystals after recrystallization
from hexane/CH2Cl2 by slow evaporation of the solvents at -4
°C. Spectral data for 5: IR (ν(CO), CH2Cl2) 2004 vs, 1981 vs,
Reaction of [Ru3(CO)10(µ-dppm)] (1) with PhTeTePh. A
CH2Cl2 solution (30 mL) of 1 (205 mg, 0.212 mmol) and PhTeTePh
(174 mg, 0.425 mmol) was stirred at room temperature for 72 h.
The solvent was removed under reduced pressure and the residue
chromatographed by TLC on silica gel. Elution with cyclohexane/
CH2Cl2 (1/1, v/v) developed three bands, which afforded the
following three compounds, in order of elution: [Ru2(CO)4(µ-
TePh)2(µ-dppm)] (2; 33 mg, 14%) as orange crystals from hexane/
CH2Cl2 at -4 °C, [Ru3(CO)6(µ3-Te)2(µ-TePh)2(µ-dppm)] (3; 58 mg,
18%) as red crystals, and [Ru3(CO)6(µ3-Te)(µ-TePh)3(COPh)(µ-
dppm)] (4; 81 mg, 22%) as red crystals after recrystallization from
hexane/CH2Cl2 at -20 °C. Spectral data for 2: IR (ν(CO), CH2Cl2)
1999 s, 1973 vs, 1937 s cm-1; 1H NMR (CD2Cl2) δ 7.74–7.01 (m,
30H), 4.57 (m, 1H), 4.29 (m, 1H); 31P{1H} NMR (CD2Cl2) δ 13.9
(s); mass spectrum m/z 1108. Anal. Calcd for C41H32O4P2Ru2Te2:
C, 44.44; H, 2.91. Found: C, 44.46; H, 3.01. Spectral data for 3:
IR (ν(CO), CH2Cl2) 2021 vs, 2010 vs, 1970 vs, 1953 m cm-1; 1H
NMR (CD2Cl2) δ 8.15–7.03 (m, 30H), 4.07 (m, 2H); 31P{1H} NMR
(CD2Cl2, -80 °C) δ 14.5 (s), 14.3 (d, JP-P ) 34.8 Hz), 13.8 (s),
13.5 (d, JP-P ) 34.8 Hz); FAB mass spectrum m/z 1522. Anal.
Calcd for C43H32O6P2Ru3Te4: C, 33.97; H, 2.12. Found: C, 34.06;
H, 2.17. Spectral data for 4: IR (ν(CO), CH2Cl2) 2022 vs, 2004 s,
1
1942 s cm-1; H NMR (CD2Cl2) δ 7.69–7.09 (m, 30H), 4.42 (m,
1H), 3.87 (m, 1H); 31P{1H} NMR (CD2Cl2) δ 24.2 (s); FAB mass
spectrum m/z 1012. Anal. Calcd for C41H32O4P2Ru2Se2: C, 48.72;
H, 3.19. Found: C, 48.78; H, 3.25. Spectral data for 6: IR (ν(CO),
CH2Cl2) 2031 vs, 2020 s, 1975 s, 1958 m cm-1; 1H NMR (CD2Cl2)
δ 8.28–8.23 (m, 5H), 7.45 (br, 10H), 7.26–7.10 (m, 15H), 3.73
(m, 2H); 31P{1H} NMR (CD2Cl2, -80 °C) δ 28.2 (s), 28.0 (d, JP-P
) 32.2 Hz), 27.0 (s), 26.4 (d, JP-P ) 32.2 Hz); FAB mass spectrum
m/z 1326. Anal. Calcd for C43H32O6P2Ru3Se4: C, 38.96; H, 2.43.
Found: C, 39.11; H, 2.59. Spectral data for 7: IR (ν(CO), CH2Cl2)
2033 vs, 2010 s, 1978 s, 1947 m cm-1 1H NMR (CD2Cl2) δ
;
8.03–6.88 (m, 40 H), 4.12 (m, 1H), 3.96 (m, 1H), 3.86 (m, 1H),
3.40 (m, 1H); 31P{1H} NMR (toluene-d8) δ 26.9 (d, JP-P ) 12.6
Hz), 24.3 (s), 24.9 (d, JP-P ) 12.6 Hz); FAB mass spectrum m/z
1480. Anal. Calcd for C55H42O6P2Ru3Se4: C, 44.64; H, 2.86. Found:
C, 44.69; H, 2.90.
Reaction of 1 with PhSSPh. A reaction similar to that above
between 1 (200 mg, 0.207 mmol) and PhSSPh (90 mg, 0.413 mmol)
in THF (35 mL) followed by similar chromatographic separation
developed five bands. The first three bands afforded, in order of
elution, [Ru2(CO)4(µ-SPh)2(µ-dppm)] (8; 28 mg, 15%) and
[Ru3(CO)6(µ3-S)2(µ-SPh)2(µ-dppm)] (9; 42 mg, 18%) as yellow
crystals and [Ru3(CO)6(µ3-S)(µ-SPh)3(Ph)(µ-dppm)] (10; 38 mg,
1
1972 s, 1945 m cm-1; IR (ν(CO), KBr) 1735 s cm-1; H NMR
(CD2Cl2) δ 7.93 (d, 1H, J ) 7.4 Hz), 7.85 (d, 1H, J ) 7.2 Hz),
7.71 (d, 1H, J ) 7.2 Hz), 7.65 (d, 1H, J ) 7.2 Hz), 7.57 (dd, 1H,
J ) 7.2, 3.2 Hz), 7.48–6.83 (m, 35H), 4.12 (t, 2H, J ) 12.4 Hz);
(29) Bruce, M. I.; Nicholson, B. K.; Williams, M. L. Inorg. Synth. 1990,
26, 265.

1560 Organometallics, Vol. 27, No. 7, 2008
Begum et al.
14%) as orange crystals after recrystallization from hexane/
CH2Cl2 at -4 °C. Spectral data for 8: IR (ν(CO), CH2Cl2) 2006 s,
1983 vs, 1945 s cm-1; 1H NMR (CD2Cl2) δ 7.67–7.63 (m, 3H),
7.50–7.44 (m, 5H), 7.38–7.26 (m, 8H), 7.16–7.02 (m, 4H), 4.34
(m, 1H), 3.59 (m, 1H); 31P{1H} NMR (CD2Cl2) δ 29.3 (s); FAB
mass spectrum m/z 918. Anal. Calcd for C41H32O4P2Ru2S2: C,
53.71; H, 3.52. Found: C, 53.75; H, 3.58. Spectral data for 9:
Data collection and processing were carried out using XSCANS.30
The unit cells were indexed on low-angle reflections and refined
from 25 reflections in a range of 12–13°. The structures were solved
by direct methods (SHELXS-97)31 and refined on F2 by full-matrix
least squares (SHELXL-97),32 utilized as incorporated in the
WINGX33 program package using all unique data. All non-hydrogen
atoms were refined anisotropically for all structures except 9, for
which all carbon atom thermal parameters were refined isotropically.
Hydrogen atoms were included in calculated positions (riding
model) with the Uiso value set at 1.2 times the Ueq value of the
parent atom. Initially for all the crystals, data collection was set to
50° (2θ). During the data collection process it became evident that,
as some of the crystals diffracted poorly, therefore the data
collection was set to a smaller 2θ. Because of this, “completeness
to theta” values for 3, 7, and 9 were 53.2%, 72.2% and 55.2%,
respectively. Crystallographic and other experimental data are
summarized in Table 1.
IR (ν(CO), CH2Cl2) 2027 s, 2008 vs, 1989 vs, 1954 vs cm-1
;
1H NMR (CD2Cl2) δ 7.88 (d, J ) 7.2 Hz, 2H), 7.65 (m, 2H),
7.48 (m, 2H), 7.39–7.29 (m, 18H), 7.21 (m, 2H), 7.10 (m, 2H),
7.01 (m, 2H), 4.28 (m, 1H), 3.76 (m, 1H); 31P{1H} NMR
(CDCl2, -80 °C) δ 31.2 (JP-P ) 30.3 Hz), 28.5 (JP-P ) 30.3
Hz), 34.0 (JP-P ) 31.3 Hz), 29.7 (JP-P ) 31.3 Hz); FAB mass
spectrum m/z 1139. Anal. Calcd for C43H32O6P2Ru3S4: C, 45.38;
H, 2.83. Found: C, 45.46; H, 2.80. Spectral data for 10: IR
(ν(CO), CH2Cl2): 2041 vs, 2014 s, 1985 s, 1946 m cm-1 1H
;
NMR (CD2Cl2) δ 7.99–6.73 (m, 40 H), 4.76 (m, 1H), 3.80 (m,
1H), 3.44 (m, 1H), 3.21(m, 1H); 31P{1H} NMR (toluene-d8) δ
25.9 (d, JP-P ) 12.6 Hz), 23.9 (d, JP-P ) 12.6 Hz), 23.5 (s);
FAB mass spectrum m/z 1293. Anal. Calcd for C55H42O6P2Ru3S4:
C, 51.12; H, 3.28. Found: C, 51.16; H, 3.33.
X-ray Structure Determination of 13. Single crystals of
compound 13 were mounted on glass fibers, and all geometric
intensity data were obtained from these samples on a Bruker
SMART APEX CCD diffractometer using graphite-monochromated
Mo KR radiation (λ) 0.710 73 Å) at 150 ( 2 K. Data reduction
and integration were carried out with SAINT+ and absorption
corrections applied using the program SADABS.34 Structures were
solved by direct methods and developed using alternating cycles
of least-squares refinement and difference-Fourier synthesis. All
non-hydrogen atoms were refined anisotropically. Hydrogen atoms
were placed in calculated positions and their thermal parameters
linked to those of the atoms to which they were attached (riding
model). The SHELXTL PLUS V6.10 program package was used
for the structure solution and refinement.34
Reactions of [Ru3(CO)9{µ3-η3-P(C6H5)CH2P(C6H5)(C6H4)}]
(11) with PhEEPh (E ) Te, Se, S). To a THF solution (25 mL)
of 11 (80 mg, 0.093 mmol) was added 2 equiv of PhEEPh, and the
reaction mixture was heated to reflux for 2–6 h. The solvent was
removed under reduced pressure and the residue chromatographed
by TLC on silica gel. Elution with hexane/CH2Cl2 (2/1, v/v)
developed two bands. The first band gave unreacted 11 (∼10 mg),
while the second band afforded [Ru3(CO)5(µ-EPh)2(µ-CO){µ3-η3-
PPhCH2PPh(C6H4)}] (12, E ) Te, 26 mg, 24%; 13, E ) Se, 28
mg, 28%; 14, E ) S, 26 mg, 28%) as red crystals from hexane/
CH2Cl2 at -5 °C. Spectral data for 12: IR (ν(CO), CH2Cl2) 2031 s,
Crystallographic data for the structural analyses have been
deposited with the Cambridge Crystallographic Data Centre:
CCDC Nos. 251653 for 2, 251654 for 3, 251655 for 4, 251656
for 7, 251653 for 10, and 259011 for 13. Copies of this
information may be obtained free of charge from The Director,
CCDC, 12 Union Road Cambridge CB2 1EZ, U.K. (fax, +44-
1223-336033; email, deposit@ccdc.cam.ac.uk; web, http://
www.ccdc.cam.ac.uk).
2002 vs, 1985 vs, 1967 m, 1952 m, 1925 w cm-1 1H NMR
;
(CD2Cl2) δ 7.77–7.06 (m, 21H), 6.82 (m, 1H), 6.56 (m, 1H), 6.10
(m, 1H), 4.90 (m, 1H), 4.49 (m, 1H).; 31P{1H} NMR (CD2Cl2) δ
67.5 (d, JP-P ) 55.1 Hz), 1.0 (d, JP-P ) 55.1 Hz); FAB mass
spectrum m/z 1188. Anal. Calcd for C37H26O6P2Ru3Te2: C, 37.44;
H, 2.21. Found: C, 37.47; H, 2.19. Spectral data for 13: IR (ν(CO),
CH2Cl2) 2035 vs, 2010 vs, 1991 vs, 1970 w, 1954 s, 1931 w
Acknowledgment. We thank Professor A. J. Deeming
(Department of Chemistry, University College London) for
obtaining X-ray data on compound 13. N.B. acknowledges
Sher-e-Bangla Agricultural University, for study leave.
1
cm-1; H NMR (CD2Cl2) δ 7.43 (m, 21H), 6.88 (m, 1H), 6.74
(m, 1H), 6.15 (m, 1H), 4.57 (m, 1H), 3.86 (m, 1H); 31P{1H}
NMR (CD2Cl2) δ 86.8 (d, JP-P ) 54.3 Hz), 4.0 (d, JP-P ) 54.3
Hz); FAB MS m/z 1090. Anal. Calcd for C37H26O6P2Ru3Se2: C,
40.78; H, 2.40. Found: C, 41.82; H, 2.46. Spectral data for 14:
IR (ν(CO), CH2Cl2) 2030 vs, 2011 vs, 1993 vs, 1954 s, 1931 w
Supporting Information Available: CIF files giving crystal-
lographic data for 2-4, 7, 10, and 13. This material is available
free of charge via the Internet at http://pubs.acs.org.
1
cm-1; H NMR (CD2Cl2) δ 7.45 (m, 21H), 6.85 (m, 1H), 6.17
(m, 1H), 6.12 (m, 1H), 4.53 (m, 1H), 3.88 (m, 1H); 31P{1H}
NMR (CD2Cl2) δ 85.6 (d, JP-P ) 51.3 Hz), 4.6 (d, JP-P ) 51.3);
FAB mass spectrum m/z 997. Anal. Calcd for C37H26O6P2Ru3S2:
C, 44.62; H, 2.63. Found: C, 44.67; H, 2.69.
OM701042S
(30) XSCANS: Data Collection Software, Release 2.10b; Bruker AXS
Inc., Madison, WI, 1994.
X-ray Structure Determination of 2-4, 7, and 10. Crystals
of 2-4, 7, and 10 for X-ray structural determination were obtained
from saturated solutions of each in hexane/dichloromethane solvent
at -20 °C. Crystallographic data for compounds 2-4, 7, and 10
were collected at 296 K with Mo KR radiation (λ ) 0.710 73 Å).
(31) Sheldrick, G. M. Acta Crystallogr. 1990, 46, 467.
(32) Sheldrick, G. M. SHELXL-97: Program for Crystal Structure
Refinement; University of Gottingen, Gottingen, Germany, 1997.
(33) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837.
(34) SMART and SAINT Software for CCD Diffractometers, Version
6.1; Bruker AXS Inc., Madison, WI, 2000.