Reactivity of triruthenium furyne and thiophyne clusters: Multiple additions of thiolato and selenolato ligands through oxidative addition of S-H and SE-H bonds

Article abstract of DOI:10.1021/om201052u

Reactions of 50-electron furyne and thiophyne clusters Ru ₃(CO)₇(μ-H)(μ₃-η²-C ₄H₂E){μ-P(C₄H₃E) ₂}(μ-dppm) (1, 2; E = O, S) with thiols, dithiols, and benzeneselenol leads to the oxidative addition of the E-H bonds followed by concomitant elimination of the alkyne (probably as the alkene) to afford a range of new thiolato and selenolato triruthenium complexes. Addition of PhSH or ⁱPrSH in boiling benzene affords the 48-electron clusters Ru ₃(CO)₅(μ-SR)₂{μ-P(C₄H ₃E)₂}(μ-dppm)(μ-H) (3-6; E = O, S; R = Ph, ⁱPr) resulting from the addition of 2 equiv of thiol. In contrast, analogous reactions with 1,2-ethanedithiol and 1,3-propanedithiol yield the 50-electron clusters Ru₃(CO)₃{μ-S(CH₂) _nS)₂{μ-P(C₄H₃E) ₂}(μ-dppm)(μ-H) (7-10; E = O, S; n = 2, 3), in which four S-H bonds have been activated. A similar multiple addition reaction is seen upon addition of PhSeH to 1, affording the tetraselenolato complexes Ru ₃(CO)₄(κ¹-SePh)(μ-SePh) ₃{μ-P(C₄H₃O)₂}(μ-dppm)(μ-H) (11) and Ru₃(CO)₃(μ-SePh)₄{μ-P(C ₄H₃O)₂}(μ-dppm)(μ-H) (12). Reaction of 2 with PhSeH gave the tetraselenolato complex Ru₃(CO) ₄(κ¹-SePh)(μ-SePh)₃{μ-P(C ₄H₃S)₂}(μ-dppm)(μ-H) (13) together with bis(seleno)-capped Ru₃(CO)₅{PPh(C₄H ₃S)₂}(μ₃-Se)₂(μ-SePh) ₂(μ-dppm) (14) resulting from further cleavage of two selenium-carbon bonds and formation of a new carbon-phosphorus bond. The new clusters have been characterized by a combination of analytical and spectroscopic methods, and the molecular structures of 3, 4, 7, 8, and 11 have been determined by single-crystal X-ray diffraction studies. Complexes 7-10 are examples of 50-electron clusters containing three apparent metal-metal bonds; however, DFT calculations carried out for 7 show that the longest metal-metal interaction of 3.119 A is actually held in place by the bridging thiolato and diphosphine ligands and does not represent a direct metal-metal bonding interaction.

Full text of DOI:10.1021/om201052u

Article
pubs.acs.org/Organometallics
Reactivity of Triruthenium Furyne and Thiophyne Clusters: Multiple
Additions of Thiolato and Selenolato Ligands through Oxidative
Addition of S−H and Se−H Bonds
Md. Iqbal Hossain,† Md. Delwar H. Sikder,† Shishir Ghosh,† Shariff E. Kabir,*,† Graeme Hogarth,*,‡
and Luca Salassa§
†Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
‡Department of Chemistry, University College London, 20 Gordon Street, London WC1H OAJ, U.K.
§Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K.
S
* Supporting Information
ABSTRACT: Reactions of 50-electron furyne and thiophyne
clusters Ru3(CO)7(μ-H)(μ3-η2-C4H2E){μ-P(C4H3E)2}(μ-
dppm) (1, 2; E = O, S) with thiols, dithiols, and
benzeneselenol leads to the oxidative addition of the E−H
bonds followed by concomitant elimination of the alkyne
(probably as the alkene) to afford a range of new thiolato and
selenolato triruthenium complexes. Addition of PhSH or
iPrSH in boiling benzene affords the 48-electron clusters
Ru3(CO)5(μ-SR)2{μ-P(C4H3E)2}(μ-dppm)(μ-H) (3−6; E =
i
O, S; R = Ph, Pr) resulting from the addition of 2 equiv of
thiol. In contrast, analogous reactions with 1,2-ethanedithiol
and 1,3-propanedithiol yield the 50-electron clusters
Ru3(CO)3{μ-S(CH2)nS)2{μ-P(C4H3E)2}(μ-dppm)(μ-H) (7−10; E = O, S; n = 2, 3), in which four S−H bonds have been
activated. A similar multiple addition reaction is seen upon addition of PhSeH to 1, affording the tetraselenolato complexes
Ru3(CO)4(κ1-SePh)(μ-SePh)3{μ-P(C4H3O)2}(μ-dppm)(μ-H) (11) and Ru3(CO)3(μ-SePh)4{μ-P(C4H3O)2}(μ-dppm)(μ-H)
(12). Reaction of 2 with PhSeH gave the tetraselenolato complex Ru3(CO)4(κ1-SePh)(μ-SePh)3{μ-P(C4H3S)2}(μ-dppm)(μ-H)
(13) together with bis(seleno)-capped Ru3(CO)5{PPh(C4H3S)2}(μ3-Se)2(μ-SePh)2(μ-dppm) (14) resulting from further
cleavage of two selenium−carbon bonds and formation of a new carbon−phosphorus bond. The new clusters have been
characterized by a combination of analytical and spectroscopic methods, and the molecular structures of 3, 4, 7, 8, and 11 have
been determined by single-crystal X-ray diffraction studies. Complexes 7−10 are examples of 50-electron clusters containing
three apparent metal−metal bonds; however, DFT calculations carried out for 7 show that the longest metal−metal interaction
of 3.119 Å is actually held in place by the bridging thiolato and diphosphine ligands and does not represent a direct metal−metal
bonding interaction.
trinuclear cluster Re3(CO)9(μ3-SPh)3 when using more
vigorous conditions.8 Reaction of thiols with the heavier
group 8 trimetallic clusters M3(CO)12 (M = Os, Ru) and their
diphosphine-stabilized derivatives M3(CO)10(μ-dppm) (dppm
= Ph2PCH2PPh2) under mild conditions generally result in the
oxidative addition of a single thiol to produce M3(CO)10(μ-
SR)(μ-H)9 and M3(CO)8(μ-SR)(μ-H)(μ-dppm),10 respec-
tively. Under more forcing conditions and with excess thiol,
poorly characterized polymeric materials of the form [Ru-
(SR)2(CO)2]n result.11
INTRODUCTION
■
The chemistry of chalcogen-containing transition-metal clusters
remains an area of intense interest, due to the biological
relevance of thiolato and sulfido ligands and also the
applications of metal chalcogenides in microelectronics.1
Incorporation of chalcogenide moieties into low-valent clusters
can be achieved via several synthetic routes, including the
reaction of the elements themselves2 and the oxidative addition
of R3PE3 or RE−ER4 reagents to cluster centers. A further
route widely utilized toward the incorporation of thiolato
ligands is the oxidative addition of thiols.5 As early as 1937
Hieber and Spacu reported6 that oxidative addition of thiols to
Fe3(CO)12 afforded what are now known to be the
bis(thiolato) complexes Fe2(CO)6(μ-SR)2.7 In 1965 Osborne
and Stone developed this approach, isolating Re2(CO)8(μ-
SPh)2 upon room-temperature addition of thiophenol to
HRe(CO)5 and proposing the formation of the 48-electron
We have been interested in the reactivity of low-valent
triosmium and triruthenium clusters toward various chalcogen
Special Issue: F. Gordon A. Stone Commemorative Issue
Received: October 31, 2011
Published: February 22, 2012
© 2012 American Chemical Society
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Scheme 1
donor ligands such as thiols, dithiols, and RE−ER (R = alkyl,
aryl; E = S, Se, Te), primarily with the aim of preparing novel
chalcogen-containing clusters but also of understanding
reactivity patterns.12 We recently reported the synthesis of
triruthenium furyne and thiophyne clusters Ru3(CO)7(μ-
H)(μ3-η2-C4H2E){μ-P(C4H3E)2}(μ-dppm) (1, 2; E = O, S),
formed in high yields upon gentle heating of Ru3(CO)9{P-
(C4H3E)3}(μ-dppm) in the presence of Me3NO and have
found that they show intriguing reactivity patterns toward
various substrates.13,14 For instance, diphenyl ditelluride
undergoes ready oxidative addition to the furyne cluster 1 to
form an alkenyl complex, which in turn rearranges to an
unusual carbene cluster upon heating in toluene (Scheme 1).14
Inspired by the facile nature of the addition of the tellurium−
tellurium bond, we sought to investigate the incorporation of
related thiolato and selenolato ligands into the triruthenium
framework via reactions with thiols, dithiols, and benzenesele-
nol. Herein we report that this strategy is indeed successful and
leads to the rapid oxidative addition of up to four E−H bonds
to produce a range of otherwise inaccessible low-valent clusters.
isostructural. Each 31P{1H} NMR spectrum displays two
doublets and a doublet of doublets, which confirms that all
three phosphorus atoms remain in the products. In order to
unambiguously determine their molecular structures, single-
crystal X-ray diffraction studies were carried out on 3 and 4, the
results of which are summarized in Figures 1 and 2,
respectively. Both consist of a triangle of ruthenium atoms
with two long (Ru−Ru (range) = 2.958(1)−3.018(1) Å) and
one comparatively short (Ru−Ru = 2.7504(9) and 2.787(9) Å)
ruthenium−ruthenium interactions, the latter in each case
being the metal−metal vector spanned by phosphido and
hydride ligands. The disposition of the latter along this edge is
1
confirmed by their H NMR spectra, which show a doublet of
doublets in the hydride region (δ −16.39 for 3 and δ −16.38
for 4). One thiolato ligand asymmetrically bridges the metal−
metal edge, which is also spanned by the diphosphine, while the
second spans the third ruthenium−ruthenium edge. A feature
of both structures is the tilting of the diphosphine out of the
trimetallic plane, presumably so as to minimize the steric
crowding created by phenyl groups with those of the thiolato
ligands. A second noteworthy feature is the relative anti
arrangement of the two thiolato substituents. Thus, the phenyl
group on the thiolato ligand which spans the edge also
occupied by the diphosphine is constrained to orient away from
the latter in order to minimize adverse steric interactions, and
this in turn results in the phenyl group of the second thiolato
ligand to do likewise. The relative anti orientation of the two
thiolato substituents is similar to the situation found in the
diiron complexes Fe2(CO)4(μ-SAr)2(μ-dppm).15
RESULTS AND DISCUSSION
■
Reactions of Ru3(CO)7(μ-H)(μ3-η2-C4H2E){μ-P(C4H3E)2}-
(μ-dppm) (1, 2; E = O, S) with Thiols. The furyne and
thiophyne clusters Ru3(CO)7(μ-H)(μ3-η2-C4H2E){μ-P-
(C4H3E)2}(μ-dppm) (1, 2; E = O, S) react with an excess of
thiophenol and 2-methyl-2-ethanethiol to afford Ru3(CO)5(μ-
i
SR)2{μ-P(C4H3E)2}(μ-dppm)(μ-H) (3−6; R = Ph, Pr) in
yields of between 33 and 66% (Scheme 2). The transformation
The relatively facile addition of 2 equiv of thiol is quite
distinct from the reactivity observed for M3(CO)12 or
M3(CO)10(μ-dppm).9,10 It has been shown that the first stage
in activation of the relatively strong hydrogen−sulfur bond is
precoordination of the sulfur to the metal center, which then
results in a large reduction in the hydrogen−sulfur bond
strength.16 We presume that this initially occurs for 1 and 2
upon loss of a carbonyl. Oxidative addition can then proceed,
but as seen in the related addition of Ph2Te2 to 1 (Scheme 1),14
this can be associated with a concomitant transfer of a hydride
to the coordinated alkyne, generating an alkenyl ligand. In the
absence of labeling studies we cannot ascertain whether this
hydrogen atom comes from the thiol or the cluster hydride, but
some type of alkenyl-thiolato intermediate seems likely. We
have not been able to detect this in the reaction mixture and
thus assume that a second carbonyl loss and thiol binding are
facile. A second oxidative addition and hydride transfer is then
proposed, the latter leading to formation of an alkene which is
not expected to bind strongly to the cluster, the loss of this two-
electron-donor ligand being compensated for by the formation
of a new metal−metal interaction.
Scheme 2
involves the net addition of 2 equiv of thiol and concomitant
loss of two carbonyls accompanied by the elimination of the
cluster-bound alkyne, most probably as furan or thiophene after
addition of hydrogen, although our experimental conditions did
not allow us to confirm this. Considering that the bridging
thiolato ligands act as three-electron-donor ligands, then
formation of a new metal−metal bond balances the total loss
of eight electrons, converting the 50-electron starting clusters
into electron-precise 48-electron clusters.
Reactions of 1 and 2 with Dithiols. Diiron complexes
containing bridging dithiolato ligands have attracted enormous
attention over the past decade, as they are biomimetics of the
All exhibit five bands in the carbonyl region of their IR
spectrum, the similar patterns suggesting that they are
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Figure 1. ORTEP diagrams of the two independent molecules of Ru3(CO)5{μ-P(C4H3O)2}(μ-SPh)2(μ-dppm)(μ-H) (3), showing 50% probability
thermal ellipsoids. Selected interatomic distances (Å) and angles (deg) for one molecule: Ru(1)−Ru(2) = 2.9580(10), Ru(1)−Ru(3) = 2.7587(9),
Ru(2)−Ru(3) = 3.0011(9), Ru(1)−P(3) = 2.279(2), Ru(3)−P(3) = 2.278(2), Ru(2)−P(2) = 2.335(2), Ru(1)−P(1) = 2.277(2), Ru(2)−S(1) =
2.419(2), Ru(1)−S(2) = 2.357(2), Ru(2)−S(2) = 2.417(2), Ru(3)−S(1) = 2.392(2); Ru(3)−Ru(1)−Ru(2) = 63.22(2), Ru(1)−Ru(2)−Ru(3) =
55.15(2), Ru(1)−Ru(3)−Ru(2) = 61.63(2), P(1)−Ru(1)−P(3) = 99.32(8), P(3)−Ru(1)−Ru(3) = 52.72(6), P(3)−Ru(1)−Ru(2) = 99.96(6),
Ru(3)−P(3)−Ru(1) = 74.52(7), S(2)−Ru(2)−S(1) = 90.99(7), S(1)−Ru(2)−Ru(3) = 51.01(5), P(3)−Ru(1)−S(2) = 150.68(8), S(1)−Ru(2)−
Ru(1) = 90.90(5), Ru(3)−S(1)−Ru(2) = 77.17(6), P(3)−Ru(3)−S(1) = 147.57(8), Ru(1)−S(2)−Ru(2) = 76.56(6).
Figure 2. Solid-state molecular structure of Ru3(CO)5{μ-P(C4H3S)2}(μ-SPh)2(μ-dppm)(μ-H) (4), showing (a) 50% probability thermal ellipsoids
and (b) the cluster core with phenyl groups on the diphosphine removed. Selected interatomic distances (Å) and angles (deg): Ru(1)−Ru(2) =
2.7504(9), Ru(1)−Ru(3) = 3.0175(10), Ru(2)−Ru(3) = 2.9875(9), Ru(1)−P(1) = 2.292(2), Ru(2)−P(1) = 2.301(2), Ru(2)−P(2) = 2.288(2),
Ru(3)−P(3) = 2.368(2), Ru(3)−S(1) = 2.420(2), Ru(1)−S(1) = 2.387(2), Ru(2)−S(2) = 2.364(2), Ru(3)−S(2) = 2.439(2); Ru(3)−Ru(1)−
Ru(2) = 62.19(2), Ru(1)−Ru(2)−Ru(3) = 63.30(2), Ru(1)−Ru(3)−Ru(2) = 54.52(2), P(2)−Ru(2)−P(1) = 99.90(7), P(3)−Ru(3)−Ru(1) =
122.04(6), P(1)−Ru(1)−Ru(2) = 53.35(5), Ru(1)−P(1)−Ru(2) = 73.57(6), S(1)−Ru(3)−S(2) = 87.26(7), S(2)−Ru(3)−Ru(1) = 90.06(5),
P(1)−Ru(1)−S(1) = 147.63(8), S(1)−Ru(3)−Ru(2) = 89.52(5), Ru(2)−S(2)−Ru(3) = 76.91(6), P(1)−Ru(2)−S(2) = 149.65(8), Ru(1)−S(1)−
Ru(3) = 77.77(6).
active site of the iron-only hydrogenase enzyme,17 and recently
developing this theme, we have shown that related triiron
complexes can also act as proton reduction catalysts.18 Given
the relatively facile addition of 2 equiv of thiol to 1 and 2, we
aimed to synthesize similar products, viz. Ru3(CO)5{μ-
S(CH2)nS}{μ-P(C4H3E)2}(μ-dppm)(μ-H) (n = 2, 3), from
the respective reactions with 1,2-ethanedithiol (n = 2, edt) and
1,3-propane dithiol (n = 3, pdt). Indeed, both 1 and 2 react
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Scheme 3
Figure 3. Solid-state molecular structure of Ru3(CO)3{μ-pdt}2{μ-P(C4H3O)2}(μ-dppm)(μ-H) (7), showing (a) 50% probability thermal ellipsoids
and (b) the cluster core with phenyl and furyl groups removed for clarity. Selected interatomic distances (Å) and angles (deg): Ru(1)−Ru(2) =
3.1193(8), Ru(1)−Ru(3) = 2.9056(8), Ru(2)−Ru(3) = 2.8537(8), Ru(1)−P(1) = 2.3143(18), Ru(1)−P(3) = 2.3560(19), Ru(2)−P(2) =
2.3217(19), Ru(3)−P(3) = 2.3257(19), Ru(1)−S(1) = 2.4340(18), Ru(2)−S(1) = 2.4183(18), Ru(1)−S(2) = 2.4128(18), Ru(3)−S(2) =
2.3912(18), Ru(2)−S(3) = 2.4225(18), Ru(3)−S(3) = 2.4119(18), Ru(3)−S(4) = 2.4061(19), Ru(2)−S(4) = 2.4122(19); Ru(3)−Ru(1)−Ru(2) =
56.409(19), Ru(1)−Ru(2)−Ru(3) = 58.011(18), Ru(1)−Ru(3)−Ru(2) = 65.58(2), P(1)−Ru(1)−P(3) = 100.18(7), P(3)−Ru(1)−Ru(3) =
51.17(5), P(1)−Ru(1)−Ru(2) = 89.13(5), Ru(1)−P(3)−Ru(3) = 76.72(6), S(1)−Ru(2)−S(3) = 92.55(6), S(4)−Ru(2)−S(3) = 80.99(6), S(4)−
Ru(2)−S(1) = 147.34(6), Ru(3)−Ru(1)−S(1) = 95.30(5), S(2)−Ru(1)−Ru(2) = 93.01(5), S(1)−Ru(1)−Ru(2) = 49.77(4), Ru(3)−Ru(2)−S(1)
= 97.00(5), S(4)−Ru(2)−Ru(1) = 97.80(5), S(3)−Ru(2)−Ru(1) = 92.29(5), S(4)−Ru(3)−Ru(1) = 103.90(5), S(3)−Ru(3)−Ru(1) = 97.97(5),
S(1)−Ru(2)−S(3) = 92.55(6), Ru(3)−S(2)−Ru(1) = 74.43(5), Ru(3)−S(4)−Ru(2) = 72.64(5), Ru(2)−S(1)−Ru(1) = 80.01(5), Ru(3)−S(3)−
Ru(2) = 72.36(5), P(3)−Ru(3)−S(3) = 150.05(7), P(2)−Ru(2)−S(3) = 171.34(7).
smoothly with these dithiols, but the isolated products contain
two dithiolato ligands coordinated to the metal core using all
four sulfur atoms. Thus, heating 1 and 2 with an excess of
dithiol gave Ru3(CO)3(μ-pdt)2{μ-P(C4H3E)2}(μ-dppm)(μ-H)
(7, 8; E = O, S; yields 39 and 20%) and Ru3(CO)3(μ-edt)2{μ-
P(C4H3E)2}(μ-dppm)(μ-H) (9, 10; E = O, S; yields 50 and
30%), respectively (Scheme 3).
The IR spectra of clusters 7−10 are again very alike,
suggesting they have similar distributions of carbonyl ligands.
Each shows only two absorption bands below 1950 cm−1 due to
increased back-donation from metals, as each metal atom is
now bonded to a single CO ligand. While it was obvious that
more carbonyls had been lost than might be expected, the
precise attachment of ligands to the triruthenium center was
unclear, and consequently we have carried out X-ray structure
determinations of 7 and 8, the results of which are shown in
Figures 3 and 4, respectively. The main feature of the molecules
is the presence of two propanedithiolato ligands which take up
different coordination modes: one capping a face of the
ruthenium triangle, the sulfur atoms (S(1) and S(2)) bridging
two different ruthenium−ruthenium vectors, while the second
(S(3) and S(4)) bridges the third ruthenium−ruthenium bond
only. The two phosphorus-containing ligands and a hydride
also span metal−metal edges, and each ruthenium atom also
supports a terminal carbonyl. Thus, the loss of four carbonyls
and addition of the same number of sulfur−hydrogen bonds is
in keeping with the supposition that carbonyl loss and sulfur
coordination are prerequisites for the observed oxidative
addition reactions. Considering each dithiolato ligand to be a
six-electron donor, then the cluster has a TEC of 50 and as such
would be expected to have only two ruthenium−ruthenium
bonds. The ruthenium−ruthenium bond lengths in 7 and 8 fall
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Figure 4. Solid-state molecular structure of Ru3(CO)3(μ-pdt)2{μ-P(C4H3S)2}(μ-dppm)(μ-H) (8), showing (a) 50% probability thermal ellipsoids
and (b) the cluster core with phenyl and thienyl groups removed for clarity. Selected interatomic distances (Å) and angles (deg): Ru(1)−Ru(2) =
3.1095(4), Ru(1)−Ru(3) = 2.9002(4), Ru(2)−Ru(3) = 2.8539(4), Ru(1)−P(1) = 2.3111(7), Ru(1)−P(2) = 2.3648(7), Ru(2)−P(3) = 2.3218(7),
Ru(3)−P(2) = 2.3185(7), Ru(1)−S(1) = 2.4274(7), Ru(2)−S(1) = 2.4180(7), Ru(1)−S(2) = 2.4190(7), Ru(3)−S(2) = 2.3825(7), Ru(3)−S(3) =
2.4018(7), Ru(2)−S(3) = 2.3967(7), Ru(3)−S(4) = 2.4099(7), Ru(2)−S(4) = 2.4203(7); Ru(3)−Ru(1)−Ru(2) = 56.576(10), Ru(1)−Ru(2)−
Ru(3) = 58.010(7), Ru(1)−Ru(3)−Ru(2) = 65.414(9), P(1)−Ru(1)−P(2) = 100.57(2), P(2)−Ru(1)−Ru(3) = 51.023(17), P(1)−Ru(1)−Ru(2) =
89.133(18), Ru(1)−P(2)−Ru(3) = 76.52(2), S(1)−Ru(2)−S(3) = 147.65(2), S(4)−Ru(2)−S(1) = 92.42(2), Ru(3)−Ru(1)−S(1) = 95.599(17),
S(2)−Ru(1)−Ru(2) = 93.241(17), S(1)−Ru(1)−Ru(2) = 49.946(15), S(2)−Ru(1)−Ru(3) = 52.270(16), Ru(2)−Ru(1)−S(4) = 92.145(17),
S(1)−Ru(2)−Ru(3) = 97.014(17), S(3)−Ru(3)−Ru(1) = 103.958(19), S(4)−Ru(3)−Ru(2) = 53.950(16), S(4)−Ru(3)−Ru(1) = 97.692(18),
S(2)−Ru(1)−S(1) = 96.33(2), Ru(3)−S(2)−Ru(1) = 74.311(19), Ru(3)−S(4)−Ru(2) = 72.43(2), Ru(2)−S(1)−Ru(1) = 79.84(2), Ru(3)−S(3)−
Ru(2) = 72.99(2), P(3)−Ru(2)−S(4) = 170.95(2), P(2)−Ru(3)−S(2) = 74.51(2).
into two distinct categories; those bridged by the phosphido
and μ2-dithiolato ligands are in the standard range (Ru(1)−
Ru(3) = 2.9056(8) Å and Ru(2)−Ru(3) = 2.8537(8) Å in 7;
Ru(1)−Ru(3) = 2.9002(4) Å and Ru(2)−Ru(3) = 2.8539(4) Å
in 8), while the vector spanned by the diphosphine is
significantly longer (Ru(1)−Ru(2) = 3.1193(8) and
3.1095(4) Å). Similar patterns of ruthenium−ruthenium bond
lengths have been noted in 64-electron butterfly clusters, such
an arrangement of metal atoms generally being associated with
a 62-electron count.19 EHMO calculations on model complexes
suggest that in this case the additional electron pair occupies an
orbital which has ruthenium−ruthenium antibonding charac-
ter.19,20 In order to gain more insight into the bonding in 7−10,
we have carried out density functional theory (DFT)
calculations on 7. The computed geometry of 7 is in good
agreement with the X-ray structure and the trend in
ruthenium−ruthenium distances is confirmed, although they
are overestimated by ca. 0.06−0.12 Å. The calculated Ru(1)−
Ru(2) distance is 3.244 Å, while Ru(1)−Ru(3) and Ru(2)−
Ru(3) are 2.970 and 2.936 Å, respectively. The longer Ru(1)−
Ru(2) distance is consistent with a nonbonding interaction
between the two ruthenium atoms, which are held close
together by the bridging thiolate and diphosphine ligands.
Clusters 7 and 8 are rare examples of triruthenium clusters
containing two dithiolato ligands. The direct reaction between
Ru3(CO)12 and dithiols affords two product types: binuclear
complexes Ru2(CO)6(μ-S−L−S)21 resulting from loss of one
metal atom and hexanuclear clusters {(μ-H)Ru3(CO)10}2(μ-S−
L−S) (L = alkyl, aryl) in which the dithiolato ligand spans two
separate trirthenium cores. Introduction of a dppm ligand
generally results in a stabilization of the triruthenium core,22
but Ru3(CO)10(μ-dppm) gives only the dinuclear complexes
Ru2(CO)4(μ-S−L−S)(μ-dppm)21b upon reaction with dithiols.
To our knowledge there are only two other examples of
triruthenium carbonyl clusters containing two dithiolato
ligands: Ru3(CO)7(μ-edt)2,23 reported by Adams from the
reaction between Ru3(CO)12 and 1,2,5,6-tetrathiacylooctane,
and a related diphosphine derivative, Ru3(CO)5(μ-pdt)2(κ2-
dppe)24 (dppe = Ph2PCH2CH2PPh2), prepared from the
reaction of Ru3(CO)10(μ-dppe) and 1,3-propanedithiol. Both
of these, like 7−10, are characterized by a TEC of 50, but
unlike the former they contain a linear trinuclear core with two
short and one long (nonbonding) ruthenium−ruthenium
interaction.
The mode of formation of 7−10 is unclear. In no instance
did we find evidence of a product resulting from the addition of
a single dithiol, which suggests that binding of the first ligand
activates the resultant product toward further carbonyl loss and
thus dithiol addition. In light of the isolated structures of 3−6 it
is tempting to suggest that a related dithiolato-capped
triruthenium cluster is the initial reaction product. Unlike 3−
6, the anti arrangement of substituents cannot be achieved with
the bridging ligands and it may be this constraint which further
activates the initial products toward later reactivity.
Reactions of 1 and 2 with Benzeneselenol. The
reactivity of selenols toward low-valent metal centers has not
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been extensively studied. Addition of PhSeH to
Os3(CO)10(MeCN)2 affords the expected Se−H oxidative
addition product Os3(CO)10(μ-H)(μ-SePh),25 and an analo-
gous transformation is noted with Os3(CO)10(μ-dppm).26
Reactions of Ru3(CO)12 or its derivatives with PhSeH appear
not to have been reported, although triruthenium selenolato
complexes are available upon addition of Ph2Se2 to both
substituent on Se(2) is oriented at approximately right angles
to the others. This is the group which spans the same
ruthenium−ruthenium edge as the diphosphine, and thus we
have a situation akin to that seen in 7 and 8, whereby the
geometry is controlled by the need to minimize steric
interactions with the phenyl groups of the diphosphine. The
latter thus spans across the long ruthenium−ruthenium edge,
while the phosphido ligand symmetrically bridges the Ru(1)−
Ru(2) edge (Ru(2)−P(3) = 2.313(3) Å and Ru(1)−P(3) =
2.318(3) Å). The position of the hydride was not determined
by crystallographic analysis but is believed to bridge across the
Ru(2)−Ru(3) edge, as this is spanned by only a single
benzeneselenolato ligand. The coordination sphere is com-
pleted by four carbonyl ligands. Considering the bridging
selenolato ligands to be 3-electron donors but the terminally
bound only a 1-electron donor, the cluster is characterized by a
TEC of 50 electrons. The situation is then akin to that found in
7 and 8 and highlights the flexibility of the ruthenium−
ruthenium bonds in these multibridged systems. It also
highlights the danger of interpreting bonding and nonbonding
contacts in terms of lines drawn between atoms, as each
program has a semiarbitrary cutoff for all types of element−
element interactions. Spectroscopic data for 11 are consistent
with the solid-state structure. Specifically, the hydride was
observed as a doublet at δ −20.04 (J = 29.0 Hz) and three
inequivalent phosphorus environments were observed in the
31P{1H} NMR spectrum. The thienyl cluster 13 was
spectroscopically very similar to 11; both showed three clear
carbonyl absorptions in the IR spectrum and again a single
27
Ru3(CO)12 and Ru3(CO)10(μ-dppm).28 Addition of PhSeH
to Fe3(CO)12 is reported to proceed smoothly in the presence
of triethylamine, affording [Fe2(CO)6(μ-CO)(μ-SePh)]-
[NEt3H] possibly via a hydride intermediate.29 Reactions of 1
and 2 with PhSeH do not parallel those with thiols. Thus,
under similar conditions the furyne cluster 1 reacts with PhSeH
to give Ru3(CO)4(κ1-SePh)(μ-SePh)3{μ-P(C4H3O)2}(μ-
dppm)(μ-H) (11; 20% yield) and Ru3(CO)3(μ-SePh)4{μ-
P(C4H3O)2}(μ-dppm)(μ-H) (12; 27% yield), while the
thiophyne cluster 2 afforded Ru3(CO)4(κ1-SePh)(μ-SePh)3{μ-
P(C4H3S)2}(μ-dppm)(μ-H) (13; 14% yield), an analogue of
11, together with Ru3(CO)5{PPh(C4H3S)2}(μ3-Se)2(μ-
SePh)2(μ-dppm) (14) (16% yield), which results from
selenium−carbon bond cleavage (Scheme 4).
Scheme 4
1
hydride resonance was seen in the H NMR spectrum (δ
−19.63 (d, J = 27.0 Hz)). On this basis it is clear that 13 is an
analogue of 11.
The characterization of 12, the second product of the
reaction of PhSeH with 1, proved more problematic, as
repeated attempts to grow single crystals were unsuccessful.
The IR spectrum contains only two carbonyl bands at 1941 and
1922 cm−1, being very similar to the situation found in 7 and 8,
indicating they have a similar distribution of carbonyl ligands.
The FAB mass spectrum displays an ion at m/z 1561 and
further ions due to sequential loss of three carbonyls, which
supports the proposed formulation. Hence, we propose that 12
is related to 11 by carbonyl loss. There are a number of possible
structures for 12, among the most obvious being (i) a 48-
electron cluster with retention of the terminal selenolato ligand
and formation of a new metal−metal bond and (ii) a 50-
electron cluster with four bridging selenolato ligands. We favor
this second scenario, and one plausible structure is shown in
Scheme 4, whereby loss of a carbonyl is compensated for by the
conversion of the terminal selenolato ligand to a bridging
mode. This requires a concomitant shift of the hydride as
shown. Thus, the structure is envisaged to be very similar to
Characterization of 11 and 13 was based predominantly on
the single-crystal X-ray diffraction analysis of 11, the results of
which are summarized in Figure 5. The molecule consists of a
triangular array of ruthenium atoms characterized by three
distinct ruthenium−ruthenium interactions: Ru(1)−Ru(2) =
2.958(1) Å, Ru(2)−Ru(3) = 3.131(1) Å, and Ru(1)−Ru(3) =
3.242(1) Å. The first two of these are within the expected range
for ruthenium−ruthenium bonds, while the latter falls outside
of this (see later). There are four benzeneselenolato ligands:
three span ruthenium−ruthenium vectors and lie on the same
face of the triruthenium center. The fourth is an extremely rare
example of a monodentate selenolato bound to a cluster
center.16c The ruthenium−selenium distances for the bridging
selenolato ligands range from 2.535(2) to 2.576(2) Å, and
while that to the terminal ligand (Ru(3)−Se(4) = 2.514(2) Å)
is shorter, the difference is only slight. The four selenium atoms
lie approximately in a plane which sits parallel to the
triruthenium plane, and there are a series of relatively short
selenium−selenium contacts (Se···Se = 3.226(3)−3.619(3) Å).
The phenyl groups of three of them (Se(1), Se(3), and Se(4))
also lie approximately in this plane, with the lone pairs thus
being oriented away from the cluster core, while in contrast the
1
those of 7−10. Both the H and 31P{1H} NMR spectra of 12
show the existence of two isomeric forms in solution. The
31P{1H} NMR spectrum displays six resonances in two sets: a
singlet and two doublets at δ 42.2, 35.3, and −5.5 having similar
intensities, with three equally intense multiplets at δ 38.1, 35.6,
and −7.6. The intensity ratio between the two sets is
approximately 5:1. In accord with this, the hydride region of
1
the H NMR spectrum shows two doublets at δ −14.15 and
−15.28 with an intensity ratio of 5:1, but the JP−H values for
these are similar (JP−H = 34.0 Hz). The migration of the
hydride ligand along the ruthenium−ruthenium edges is
unlikely for 12, as each edge of the metal triangle is bridged
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Figure 5. Solid-state molecular structure of one molecule of Ru3(CO)4(SePh)(μ-SePh)3{μ-P(C4H3S)2}(μ-dppm)(μ-H) (11), showing (a) the full
molecule and (b) the cluster core with phenyl and thienyl groups removed from the phosphines for clarity. Selected interatomic distances (Å) and
angles (deg): Ru(2)−Ru(3) = 3.1311(14), Ru(1)−Ru(2) = 2.9575(13), Ru(1)−P(1) = 2.320(3), Ru(2)−P(3) = 2.313(3), Ru(1)−P(3) = 2.318(3),
Ru(3)−P(2) = 2.326(3), Ru(1)−Se(2) = 2.5511(16), Ru(2)−Se(1) = 2.5381(16), Ru(3)−Se(2) = 2.5760(15), Ru(3)−Se(4) = 2.5143(15),
Ru(1)−Se(1) = 2.5415(15), Ru(2)−Se(3) = 2.5351(16), Ru(3)−Se(3) = 2.5567(15); Ru(1)−Ru(2)−Ru(3) = 64.27(3), Ru(1)−Se(2)−Ru(3) =
78.44(5), Ru(2)−Se(1)−Ru(1) = 71.22(4), Ru(2)−Se(3)−Ru(3) = 75.89(4), Se(1)−Ru(1)−Ru(2) = 54.34(4), Se(1)−Ru(2)−Ru(1) = 54.45(4),
Se(3)−Ru(3)−Ru(2) = 51.74(4), Se(3)−Ru(2)−Ru(3) = 52.36(3), Se(2)−Ru(1)−Ru(2) = 101.18(4), Se(1)−Ru(2)−Ru(3) = 88.28(4), Se(4)−
Ru(3)−Ru(2) = 142.79(5), Se(2)−Ru(3)−Ru(2) = 96.20(4), Se(3)−Ru(2)−Ru(1) = 100.15(5), Se(3)−Ru(2)−Se(1) = 78.97(5), Se(4)−Ru(3)−
Se(2) = 88.88(5), Se(1)−Ru(1)−Se(2) = 85.11(5), Se(4)−Ru(3)−Se(3) = 91.05(5), Se(3)−Ru(3)−Se(2) = 99.29(5), Ru(2)−P(3)−Ru(1) =
79.38(11), P(3)−Ru(1)−P(1) = 98.92(11), P(1)−Ru(1)−Ru(2) = 122.65(8), P(3)−Ru(1)−Ru(2) = 50.24(8), P(3)−Ru(2)−Ru(1) = 50.38(8),
P(2)−Ru(3)−Ru(2) = 121.20(8).
Figure 6. Two views of the molecular structure of Ru3(CO)5{PPh(C4H3S)2}(μ3-Se)2(μ-SePh)2(μ-dppm) (14).
by at least two bridging ligands. Therefore, we speculate that
the different orientation of the phenyl groups on the selenium
atoms is responsible for this isomerization.
selenido ligand to be a 4-electron donor, then the cluster has a
TEC of 54 electrons and thus metal−metal interactions are not
expected. The structure of 14 is very similar to that of
Ru3(CO)6(μ3-Se)2(μ-SePh)2(μ-dppm),12a except that a carbon-
yl group is replaced by monodentate phosphine. The 31P{1H}
NMR spectrum of 14 shows two multiplets at δ 27.0 and 23.4
with a relative intensity of 2:1. In addition to aromatic proton
resonances, the 1H NMR spectrum displays two multiplets at δ
3.74 and 3.38, each integrating to one proton, attributable to
the methylene protons of the dppm ligand.
Characterization of 14 was made on the basis of a partially
resolved single-crystal X-ray diffraction analysis (Figure 6).
While the refinement of this structure is poor (ca. 10%), it gives
sufficient information about the geometry of the cluster and the
orientation of the ligands on the cluster surface. It consists of an
Ru3Se2 core, the two selenido ligands capping the open
triruthenium moiety. Selenolate ligands bridge two of the
edges, while the third is spanned by the diphosphine. Five
terminal carbonyls and a phenylbis(2-thienyl)phosphine ligand
complete the coordination sphere. Thus considering each
Clusters 11−14 all result from the oxidative addition of 4
equiv of PhSeH to the triruthenium center. In light of the
addition of PhSH to 1 and 2, it is envisaged that bis(selenolato)
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Scheme 5
complexes of the type Ru3(CO)5(μ-SeR)2{μ-P(C4H3E)2}(μ-
dppm)(μ-H) are intemediates. Formation of 14 results from
further carbon−selenium bond cleavage and carbon−phospho-
rus bond formation. The cluster-mediated scission of carbon−
selenium bonds is precedented. Adams has reported that
heating Os3(CO)10(μ-H)(μ-SePh) at 160 °C affords
Os3(CO)9(μ3-Se)2 along with benzene and Os(CO)5.25 Even
more pertinent to this work is the report by Deeming and co-
workers30 that Os3(CO)10(μ-SePh)2 rearranges in refluxing
cyclohexane to afford Os3(CO)8(μ3-Se2)(μ-Ph){μ-PhC(O)}, in
which the two cleaved phenyl groups are captured by the
cluster. In the case of 14 only one of the cleaved phenyl groups
is maintained via formation of a new carbon−phosphorus bond,
the fate of the second remaining unknown. Interestingly,
Deeming’s acyl cluster is also characterized by a TEC of 54
electrons.30
Thus as already discussed, initial CO loss and coordination of
the thiol leads to activation of the S−H bond. This can then
undergo oxidative addition to the metal center, and the later
rearrangement of the terminal thiolato ligand into the bridging
site activates proton transfer to the alkyne, generating an
alkenyl ligand. Such species are not isolated from reactions of 1
and 2 but are seen upon addition of Ph2Te2 to 1 (Scheme 1).14
In the related dimolybdenum chemistry they are accessible via a
different route, namely the insertion of an alkyne into Mo2(μ-
H)(μ-SR)(CO)4Cp2, but are difficult to isolate, as they are
readily oxidized.35 A repeat of these transformations upon
addition of another 1 equiv of thiol then generates a metal-
bound alkene which is likely to be readily lost, producing a
bis(thiolato) complex, examples of which are Ru3(CO)5(μ-
SR)2{μ-P(C4H3E)2}(μ-dppm)(μ-H) (3−6). Morris does not
generally isolate related species, Mo2(μ-SR)2(CO)2Cp2,
although again they are known,36 but in one instance an alkene
complex, viz. [Mo2(μ-S)2(μ-MeO2CCHCHCO2Me)Cp2], is
isolated33 although carbon−sulfur bond scission has also
occurred. In the case of the reactions of 1 and 2 with dithiols
and PhSeH, then these putative intermediates must undergo
further facile reactions with E−H bonds. The likely course of
these reactions is less clear. Oxidative addition of the E−H
bond adds a further two electrons to the cluster center, and this
may well be compensated for by the temporary cleavage of a
metal−metal bond. What is clear from the chemistry desribed
herein is that the ruthenium−ruthenium interactions are
extremely soft and easily deformed, with lengths ranging over
ca. 0.5 Å. Molybdenum−molybdenum interactions are similarly
known to vary over a similar range, and thus it is tempting to
suggest that this is a necessary prerequisite for the facile
oxidative addition reactions. A further requirement is the ready
loss of CO. Generally as carbonyls are lost from a low-valent
metal center, the degree of π back-bonding to those remaining
increases and thus the metal−carbon bond becomes stronger.
Thiolato and selenolato groups are relatively poor donor
ligands and hence may not affect the remaining carbonyls to a
great extent. It is useful to contrast this with Morris’s
observation that reaction of Mo2(μ-C2R2)(CO)4Cp2 (R =
CO2Me) with Ph2PH affords only a product from the addition
of a single P−H bond, presumably since the remaining
carbonyls are now too strongly held to the dimolybdenum
core.34 A further observation by Morris is that addition of
iPrSH to Mo2(μ-C2Ph2)(CO)4Cp2 affords as the only product
the parallel alkyne complex Mo2(μ-C2Ph2)(μ-SiPr)2(μ-S)Cp2,32
being possibly rationalized by the known reversibility of the
SUMMARY AND COMMENTS
■
We have demonstrated in this work that the triruthenium
furyne and thiophyne clusters Ru3(CO)7(μ-H)(μ3-η2-
C4H2E){μ-P(C4H3E)2}(μ-dppm) (1, 2; E = O, S) display
high reactivity toward reagents with group 16 E−H bonds at
moderate temperatures. Thus, while Ru3(CO)12 and its dppm
derivative Ru3(CO)10(μ-dppm) react with 1 equiv of thiol
under moderate conditions,10,11 these clusters add at least two
thiolate ligands, while with dithiols and PhSeH the oxidative
addition of four E−H bonds is noted. The reason for this
enhanced reactivity is almost certainly the presence of the
coordinated alkyne. Morris and co-workers have extensively
studied reactions of dimolybdenum alkyne complexes Mo2(μ-
C2R2)(CO)4Cp2 (Cp = η-C5H5) with thiols,31−34 the products
of which are strongly dependent upon the nature of the alkyne
substituents. Thus, when one of these is −CO2Me, alkenyl
complexes are isolated resulting from oxidative addition of the
sulfur−hydrogen bond and transfer of the proton to the
alkyne.33,34 Generally such complexes are not isolated with
t
other alkyne substituents, but notably reaction of BuSH with
Mo2(μ-C2Me2)(CO)4Cp2 does afford Mo2(μ-MeCCHMe)-
(μ-StBu)(CO)3Cp2.31 With less sterically demanding thiols (R
= Et, iPr) the same alkyne complex reacts with an excess at 110
°C to afford Mo2(μ-SR)2(μ-S)2Cp2, resulting from the
complete displacement of all four carbonyls.31 This behavior
is akin to that observed in our work. On the basis of our work
and that of Morris, we propose a general scheme for the
reactivity of such alkyne complexes with thiols (Scheme 5).
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plates prepared from silica gel GF254 (type 60, E. Merck). All new
complexes are air-stable in the solid state and in solution over
moderate periods.
proton addition to an alkyne, as previously noted at a diiron
center.37 The latter also results from a sulfur−carbon bond
scission process which mirrors the double selenium−carbon
bond cleavage noted in the formation of Ru3(CO)5{PPh-
(C4H3S)2}(μ3-Se)2(μ-SePh)2(μ-dppm) (14).
Reaction of 1 with PhSH. Excess thiophenol (ca. 10-fold) was
added to a benzene solution (10 mL) of 1 (50 mg, 0.045 mmol), and
the mixture was heated to reflux for 24 h. The solvent was removed
under reduced pressure and the residue separated by TLC on silica gel.
Elution with hexane/CH2Cl2 (3/2, v/v) developed four bands. The
first band was unreacted 1 (trace), while the second band yielded
Ru3(CO)5(μ-SPh)2{μ-P(C4H3O)2}(μ-dppm)(μ-H) (3; 18 mg, 33%)
as orange crystals after recrystallization from hexane/CH2Cl2 at 4 °C.
The contents of the other two bands were too small for
characterization. Data for 3 are as follows. Anal. Calcd for
C50H39O7P3Ru3S2: C, 49.55; H, 3.09. Found: C, 49.88; H, 3.15. IR
The variations in reactivity observed by Morris and co-
workers as a function of the substituents on the coordinated
alkyne31−34 led us to consider if the furyne and thiophyne
ligands in 1 and 2, respectively, were a prerequisite for the
reactivity observed or whether any alkyne complex of the type
Ru3(CO)7(μ-H)(μ3-η2-C2R2){μ-P(C4H3E)2}(μ-dppm) would
suffice. At this time we cannot answer this question, since
analogues of 1 and 2 are currently inaccessible, although some
of our earlier work with 1 and 2 suggests that they are highly
flexible ligands. More generally, complexes with a Ru3(μ3-
alkyne) core might be expected to show this behavior: viz., the
multiple oxidative addition of E−H bonds. One candidate
worthy of exploration is Ru3(CO)7(μ3-η2-C2Ph2)(μ-dppm),38
which like 1 and 2 contains a 6-electron-donor alkyne and has
been shown to add H2 to afford Ru3(CO)7(μ-H)2(μ3-η2-
C2Ph2)(μ-dppm). This demonstrates that oxidative addition is
facile but perhaps in the absence of the extra lone pair of the
thiolato/selenolato ligand proton transfer to the alkyne is not
activated. We are currently exploring reactions of this type.
As far as we aware, clusters 1 and 2 are the first examples of
triruthenium systems that facilitate multiple additions of thiols,
ditiols, and selenols through S−H and Se−H bond activation.
Hitherto such multiple additions of thiolato or selenolato
ligands into triruthenium carbonyl clusters were only achieved
by the oxidative addition of RE−ER (E = S, Se).12g,h,28 In
somewhat related work over the past decade, Adams and co-
workers have introduced multiple tin and germanium atoms
into transition-metal cluster cores using Ph3SnH and Ph3GeH
as the main-group-element source.39 For example, heating
H4Ru4(CO)12 with excess Ph3GeH at 175 °C produces
Ru4(CO)8(μ-GePh2)4(μ4-GePh)2 in high yields.39g Such
clusters are potentially useful as precursors to heterometallic
nanoparticles, as the ratio of different metal types is tunable in
order to optimize catalytic performance. Likewise, related
sulfur- and/or selenium-containing clusters may be valuable
precursors to ruthenium sulfides or selenides for applications in
microelectronics or heterogeneous catalysis.11c
1
(ν(CO), CH2Cl2): 2024 s, 2000 s, 1964 s, 1946 m, 1924 m cm−1. H
NMR (CDCl3): δ 7.75 (m, 2H), 7.62 (m, 5H), 7.46 (m, 2H), 7.31−
7.14 (m, 14H), 7.09 (m, 3H), 7.01 (m, 4H), 6.90 (m, 2H), 6.58 (m,
2H), 6.42 (m, 1H), 6.15 (m, 1H), 4.00 (m, 1H), 3.15 (m, 1H), −16.39
(dd, J = 40.0, 22.0 Hz, 1H). 31P{1H} NMR (CDCl3): δ 115.5 (d, J =
22.4 Hz, 1P), 36.5 (dd, J = 51.5, 22.4 Hz, 1P), 19.2 (d, J = 51.5 Hz,
1P).
Reaction of 2 with PhSH. Excess PhSH (ca. 10-fold) was added
to a benzene solution (10 mL) of 2 (50 mg, 0.043 mmol), and the
mixture was heated to reflux for 8 h. The solvent was removed under
vacuum and the residue chromatographed by TLC on silica gel.
Elution with hexane/CH2Cl2 (7/3, v/v) developed only one band,
which gave Ru3(CO)5(μ-SPh)2{μ-P(C4H3S)2}(μ-dppm)(μ-H) (4; 30
mg, 56%) as orange crystals after recrystallization from hexane/
CH2Cl2 at 4 °C. Data for 4 are as follows. Anal. Calcd for
C50H39O5P3Ru3S4: C, 48.27; H, 3.16. Found: C, 48.53; H, 3.23. IR
(ν(CO), CH2Cl2): 2021 s, 1998 s, 1963 m, 1944 m, 1922 m cm−1. 1H
NMR (CDCl3): δ 7.88 (m, 2H), 7.84 (m, 5H), 7.77−7.50 (m, 26H),
7.42 (m, 2H), 7.31 (m, 1H), 3.94 (m, 1H), 3.23 (m, 1H), −16.38 (dd,
J = 39.6, 22.4 Hz, 1H). 31P{1H} NMR (CDCl3): δ 128.2 (d, J = 16.0
Hz, 1P), 35.3 (dd, J = 51.8, 16.0 Hz, 1P), 16.6 (d, J = 51.8 Hz, 1P).
i
i
Reaction of 1 with PrSH. Excess PrSH (ca. 10-fold) was added
to a benzene solution of 1 (50 mg, 0.045 mmol) and heated to reflux
for 15 h. The solvent was removed under reduced pressure and the
residue chromatographed by TLC on silica gel. Elution with hexane/
CH2Cl2 (1/1, v/v) developed two bands. The second band was
unreacted 1 (trace), while the first band afforded Ru3(CO)5{μ-
SCH(CH3)2}2{μ-P(C4H3O)2}(μ-dppm)(μ-H) (5; 30 mg, 59%) as red
crystals after recrystallization from hexane/CH2Cl2 at 4 °C. Data for 5
are as follows. Anal. Calcd for C44H43O7Ru3P3S2: C, 46.20; H, 3.80.
Found: C, 46.82; H, 3.98. IR (νCO, CH2Cl2): 2017 s, 1994 s, 1957 s,
1
1937 m, 1918 m cm−1. H NMR (CDCl3): δ 7.60 (m, 4H), 7.50 (m,
2H), 7.25 (m, 11H), 6.99 (m, 3H), 6.88 (m, 2H), 6.55 (m, 2H), 6.37
(m, 1H), 6.16 (m, 1H), 4.0 (m, 1H), 3.02 (m, 1H), 2.71 (m, 1H), 2.50
(m, 1H), 1.55 (m, 12H), −16.70 (dd, J = 40.4, 22.0 Hz, 1H). 31P{1H}
NMR: δ 113.6 (d, J = 18.0 Hz, 1P), 38.6 (dd, J = 52.0, 18.0 Hz, 1P),
17.7 (d, J = 52.0 Hz, 1P). MS (FAB): m/z 1143 (M+).
EXPERIMENTAL SECTION
■
All reactions were carried out under a nitrogen atmosphere using
standard Schlenk techniques unless otherwise stated. Reagent-grade
solvents were dried using appropriate drying agents and distilled by
standard methods prior to use. Infrared spectra were recorded on a
Shimadzu FTIR 8101 spectrophotometer. NMR spectra were recorded
on Bruker DPX 400 and Varian Inova 500 instruments. Elemental
analyses were performed by Microanalytical Laboratories, University
College London. Fast atom bombardment mass spectra were obtained
on a JEOLSX-102 spectrometer using 3-nitrobenzyl alcohol as matrix
and CsI as calibrant. Ru3(CO)12 was purchased from Strem Chemicals
Inc. and used without further purification. Me3NO·2H2O was
purchased from Lancaster; the water was removed using a Dean−
Stark apparatus by azeotropic distillation from benzene, and the
anhydrous Me3NO was stored under nitrogen. Tris(2-furyl)phosphine
and tris(2-thienyl)phosphine were purchased from E. Merck and
bis(diphenylphosphino)methane, PhSH, 1,3-propanedithiol, 1,2-etha-
nedithiol and PhSeH from Aldrich, and all were used as received. The
starting clusters Ru3(CO)7(μ-H)(μ3-η2-C4H2O){μ-P(C4H3O)2}(μ-
dppm) (1) and Ru3(CO)7(μ-H)(μ3-η2-C4H2S){μ-P(C4H3S)2}(μ-
dppm) (2) were prepared according to literature methods.13
Preparative thin-layer chromatography was carried out on 1 mm
i
i
Reaction of 2 with PrSH. Excess PrSH (ca. 10-fold) was added
to a benzene solution of 2 (30 mg, 0.027 mmol) and heated to reflux
for 15 h. The solvent was removed under reduced pressure and the
residue chromatographed by TLC on silica gel. Elution with hexane/
CH2Cl2 (1/1, v/v) developed two bands. The second band was
unreacted 2 (trace), while the first band afforded Ru3(CO)5{μ-
SCH(CH3)2}2{μ-P(C4H3S)2}(μ-dppm)(μ-H) (6; 20 mg, 66%) as red
crystals after recrystallization from hexane/CH2Cl2 at 4 °C. Data for 6
are as follows. Anal. Calcd for C44H43O5Ru3P3S4: C, 44.92; H, 3.69.
Found: C, 44.80; H, 3.45. IR (νCO, CH2Cl2): 2015 s, 1994 s, 1956 s,
1
1936 m, 1917 m cm−1. H NMR (CDCl3): δ 7.66−6.61 (m, 26H),
3.89 (m, 1H), 3.09 (m, 1H), 2.79 (m, 1H), 2.85 (m, 1H), 1.64 (m,
12H), −16.64 (dd, J = 41.2, 22.8 Hz, 1H). 31P{1H} NMR: δ 125.5 (d,
J = 28.0 Hz, 1P), 36.3 (dd, J = 86.0, 28.0 Hz, 1P), 13.6 (d, J = 86.0 Hz,
1P). MS (FAB): m/z 1175 (M+).
Reaction of 1 with 1,3-Propanedithiol. 1 (75 mg, 0.067 mmol)
was dissolved in benzene (15 mL), and to the resultant solution was
added excess 1,3-propanedithiol (ca. 10-fold). The mixture was boiled
under reflux for 15 h. The solvent was removed by rotary evaporation
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Organometallics
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and the residue separated by TLC on silica gel. Elution with hexane/
CH2Cl2 (3/2, v/v) developed two bands. The second band afforded
Ru3(CO)3(μ-pdt)2{μ-P(C4H3O)2}(μ-dppm)(μ-H) (7; 30 mg, 39%)
as orange crystals after recrystallization from hexane/CH2Cl2 at 4 °C.
Data for 7 are as follows. Anal. Calcd for C42H41O5P3Ru3S4: C, 43.86;
H, 3.60. Found: C, 44.13; H, 3.65. IR (ν(CO), CH2Cl2): 1942 s, 1917
m cm−1. 1H NMR (CDCl3): δ 7.67 (m, 3H), 7.51 (m, 2H), 7.39−7.06
(m, 14H), 6.96 (m, 2H), 6.82 (m, 2H), 6.41 (m, 1H), 6.09 (m, 1H),
6.02 (m, 1H), 3.65 (m, 1H), 3.10 (m, 1H), 2.69 (m, 1H), 2.53 (m,
1H), 2.47 (m, 1H), 2.19 (m, 3H), 2.06 (m, 1H), 1.99 (m, 1H), 1.88
(m, 1H), 1.42 (m, 1H), 1.28 (m, 2H), −14.92 (ddt, J = 42.5, 13.5, 3.4
Hz, 1H). 31P{1H} NMR (CDCl3): δ 37.1 (dd, J = 71.7, 21.8 Hz, 1P),
33.8 (d, J = 71.7 Hz, 1P), −0.4 (d, J = 21.8 Hz, 1P).
δ 8.29 (m, 4H), 7.68 (m, 5H), 7.29 (m, 7H) 6.91 (m, 24H), 6.62 (m,
2H), 6.24 (m, 1H), 6.06 (m, 1H), 5.90 (m, 1H), 5.04 (m, 1H), 3.79
(m, 1H), 3.65 (m, 1H), −20.04 (d, J = 29.0 Hz, 1H). 31P{1H} NMR
(CDCl3): δ 36.5 (s, 1P), 21.2 (d, J = 49.0 Hz, 1P), 1.6 (d, J = 49.0 Hz,
1P). Data for 12 are as follows. Anal. Calcd for C60H49O5P3Ru3Se4: C,
46.15; H, 3.17. Found: C, 46.49; H, 3.23. IR (ν(CO), CH2Cl2): 1941
1
s, 1922 m cm−1. H NMR (CDCl3): major isomer: δ 7.93 (m, 2H),
7.61 (m, 4H), 7.45 (m, 11H) 7.27 (m, 4H), 7.07 (m, 8H), 6.91 (m,
6H) 6.71 (m, 2H), 6.64 (m, 2H), 6.52 (m, 3H), 6.21 (m, 1H), 5.94
(m, 1H), 5.76 (m, 1H), 5.10 (m, 1H), 3.83 (m, 1H), 3.72 (m, 1H);
hydride region, major isomer, −14.15 (d, J = 34.0 Hz, 1H), minor
isomer, −15.28 (d, J = 34.0 Hz, 1H). 31P{1H} NMR (CDCl3): major
isomer, δ 42.2 (s, 1P), 35.3 (d, J = 53.3 Hz, 1P), −5.5 (d, J = 53.3 Hz,
1P); minor isomer, δ 38.1 (m), 35.6 (m), −7.6 (m). MS (FAB): m/z
1561 (M+).
Reaction of 2 with 1,3-Propanedithiol. 2 (50 mg, 0.043 mmol)
was dissolved in benzene (15 mL), and to the resultant solution was
added excess 1,3-propanedithiol (ca. 10-fold). The mixture was boiled
under reflux for 15 h. Chromatographic separation and workup similar
to those for the above reaction developed two bands. The second band
afforded Ru3(CO)3(μ-pdt)2{μ-P(C4H3S)2}(μ-dppm)(μ-H) (8; 10 mg,
20%) as orange crystals after recrystallization from hexane/CH2Cl2 at
4 °C. Data for 8 are as follows. Anal. Calcd for C42H41O3P3Ru3S6: C,
42.67; H, 3.50. Found: C, 42.93; H, 3.54. IR (ν(CO), CH2Cl2): 1940
Reaction of 2 with PhSeH. A benzene solution (15 mL) of 2 (50
mg, 0.043 mmol) and excess PhSeH was boiled under reflux for 15 h.
The solvent was removed under vacuum and the residue separated by
TLC on silica gel. Elution with hexane/CH2Cl2 (3/2, v/v) developed
three bands. The second and fourth bands yielded Ru3(CO)5{PPh-
(C4H3S)2}(μ3-Se)2(μ-SePh)2(μ-dppm) (14; 11 mg, 16%) as orange
crystals and Ru3(CO)4(κ1-SePh)(μ-SePh)3{μ-P(C4H3S)2}(μ-dppm)-
(μ-H) (13; 10 mg, 14%) as green crystals after recrystallization from
hexane/CH2Cl2 at 4 °C. The content of the third band was too small
for characterization. Data for 13 are as follows. Anal. Calcd for
C61H49O4P3Ru3S2Se4: C, 45.17; H, 3.05. Found: C, 45.51; H, 3.12. IR
(ν(CO), CH2Cl2): 2032 s, 1977 m, 1947 m cm−1. 1H NMR (CDCl3):
δ 8.35 (m, 2H), 8.24 (m, 2H), 7.66 (m, 4H), 7.46 (m, 2H), 7.38 (m,
2H), 7.29 (m, 2H), 7.19 (m, 10H), 7.04 (m, 10H), 6.95 (m, 6H) 6.73
(m, 6H), 3.72 (m, 1H), 3.43 (m, 1H), −19.63 (d, J = 27.0 Hz, 1H).
31P{1H} NMR (CDCl3): δ 36.5 (s, 1P), 21.2 (d, J = 49.0 Hz, 1P), 1.6
(d, J = 49.0 Hz, 1P). Data for 14 are as follows. Anal. Calcd for
C56H43O5P3Ru3S2Se4: C, 42.79; H,2.76. Found: C,43.13; H, 2.83. IR
(ν(CO), CH2Cl2): 2023 s, 1966 m, 1934 w cm−1. 1H NMR (CDCl3):
δ 8.31 (m, 1H), 8.21 (m, 5H), 7.51 (m, 6H), 7.39 (m, 10H), 7.22 (m,
8H), 7.18 (m, 2H), 7.02 (m, 8H), 6.66 (m, 1H), 3.74 (m, 1H), 3.38
(m, 1H). 31P{1H} NMR (CDCl3): δ 27.0 (d, J = 15.2 Hz, 2P), 23.4 (t,
J = 15.2 Hz, 1P).
1
s, 1913 m cm−1. H NMR (CDCl3): δ 7.56−6.81 (m, 26H), 3.60 (m,
1H), 2.94 (m, 1H), 2.71 (m, 1H), 2.62 (m, 1H), 2.53 (m, 1H), 2.17
(m, 4H), 2.02 (m, 2H), 1.46 (m, 3H), −14.99 (ddt, J = 40.5, 10.0, 1.1
Hz, 1H). 31P{1H} NMR (CDCl3): δ 33.6 (m, 2P), 13.7 (m, 1P).
Reaction of 1 with 1,2-Ethanedithiol. To a benzene solution
(20 mL) of 1 (100 mg, 0.089 mmol) was added excess 1,2-
ethanedithiol (ca. 10-fold), and the mixture was heated to reflux for 15
h. The solvent was removed under reduced pressure and the residue
separated by TLC on silica gel. Elution with hexane/CH2Cl2 (1/1, v/
v) developed two bands. The second band afforded Ru3(CO)3(μ-
edt)2{μ-P(C4H3O)2}(μ-dppm)(μ-H) (9; 50 mg, 50%) as orange
crystals after recrystallization from hexane/CH2Cl2 at 4 °C. Data for 9
are as follows. Anal. Calcd for C40H37O5P3Ru3S4: C, 42.82; H, 3.30.
Found: C, 43.17; H, 3.36. IR (ν(CO), CH2Cl2): 1943 s, 1920 m cm−1.
1H NMR (CDCl3): δ 7.63 (m, 1H), 7.49 (m, 2H), 7.38 (m, 8H), 7.33
(m, 2H), 7.19 (m, 3H), 7.12 (m, 1H), 7.00 (m, 4H), 6.86 (m, 2H),
6.40 (m, 1H), 6.15 (m, 1H), 5.90 (m, 1H), 3.74 (m, 1H), 3.26 (m,
1H), 3.22 (m, 1H), 2.99 (m, 1H), 2.79 (m, 2H), 2.56 (m, 2H), 2.30
(m, 1H), 2.20 (m, 1H), −15.97 (ddt, J = 38.5, 11.0, 1.0 Hz, 1H).
31P{1H} NMR (CDCl3): δ 37.5 (m, 2P), −8.9 (m, 1P).
X-ray Structure Determinations. Single crystals of 3, 4, 7, 8, and
11 suitable for X-ray diffraction were obtained by recrystallization from
hexane/CH2Cl2 at 4 °C and mounted on nylon fibers with a mineral
oil, and diffraction data were collected at low temperatures on a Bruker
SMART APEX CCD diffractometer using Mo Kα radiation (λ =
Reaction of 2 with 1,2-Ethanedithiol. To a benzene solution
benzene (20 mL) of 2 (50 mg, 0.043 mmol) was added excess 1,2-
ethanedithiol (ca. 10-fold), and the mixture was heated to reflux for 15
h. The solvent was removed under reduced pressure and the residue
chromatographed by TLC on silica gel. Elution with hexane/CH2Cl2
(3/2, v/v) developed two bands. The second band afforded
Ru3(CO)3(μ-edt)2{μ-P(C4H3S)2}(μ-dppm)(μ-H) (10; 15 mg, 30%)
as orange crystals after recrystallization from hexane/CH2Cl2 at 4 °C.
Data for 10 are as follows. Anal. Calcd for C40H37O3P3Ru3S6: C, 41.63;
H, 3.20. Found: C, 41.92; H, 3.26. IR (ν(CO), CH2Cl2): 1943 s, 1922
́
0.710 73 Å). Data reduction and integration were carried out with
SAINT+, and absorption corrections were applied using the program
SADABS.40 Structures were solved by direct or Patterson 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 were linked to those of the atoms to
which they were attached (riding model). The SHELXTL PLUS V6.10
program package was used for structure solution and refinement.41 For
3 there are two independent clusters and also two molecules of
dichloromethane in the asymmetric unit. The metal-bound hydride
was not located. Crystals of 4 rapidly desolvated. Consequently the
dichloromethane solvate was refined only isotropically. One carbon
atom, C(8), of a thienyl ring was also only refined isotropically. The
metal-bound hydride was located in a difference map and refined
isotropically. Crystals of 7 contained one molecule of dichloromethane
in the asymmetric unit and were only weakly diffracting. The metal-
bound hydride was not located. Crystals of 8 contained one molecule
of dichloromethane in the asymmetric unit, which was refined
anisotropically. In one ring there was a disorder of sulfur S(5) and
carbon C(11) over two sites. This was modeled with occupancies of 60
and 40%, respectively. Due to this, no hydrogen atoms were generated
attached to C(11)−C(13). The metal-bound hydride was not located.
Crystals of 11 contained two independent clusters in the asymmetric
unit along with four molecules of toluene. Only the heavy atoms Ru, P,
and Se were refined anisotropically. Diffraction data were collected on
a small orange crystal of 12·3H2O. The following monoclinic cell
1
m cm−1. H NMR (CDCl3): δ 7.38 (m, 7H), 7.28 (m, 7H), 7.16 (m,
3H), 7.02 (m, 2H), 6.94 (m, 3H), 6.83 (m, 3H), 6.64 (m, 1H), 3.66
(m, 1H), 3.23 (m, 1H), 3.08 (m, 2H), 2.79 (m, 2H), 2.55 (m, 2H),
2.39 (m, 1H), 2.27 (m, 1H), −16.05 (m, 1H). 31P{1H} NMR
(CDCl3): δ 36.0 (m, 2P), 4.9 (m, 1P).
Reaction of 1 with PhSeH. A benzene solution (15 mL) of 1 (50
mg, 0.045 mmol) and PhSeH (ca. 5 fold) was boiled under reflux for
15 h. The solvent was removed under vacuum and the residue
chromatographed by TLC on silica gel. Elution with hexane/CH2Cl2
(7/3, v/v) developed five bands. The first band was unreacted 1 (12
mg). The third and second bands afforded Ru3(CO)4(κ1-SePh)(μ-
SePh)3{μ-P(C4H3O)2}(μ-dppm)(μ-H) (11; 14 mg, 20%) as green
crystals and Ru3(CO)3(μ-SePh)4(μ-P(C4H3O)2}(μ-dppm)(μ-H) (12;
19 mg, 27%) as orange crystals after recrystallization from hexane/
CH2Cl2 at 4 °C. The contents of the other two bands were too small
for characterization. Data for 11 are as follows. Anal. Calcd for
C61H49O6P3Ru3Se4: C, 46.09; H, 3.11. Found: C, 46.43; H, 3.16. IR
(ν(CO), CH2Cl2): 2036 s, 1979 m, 1947 m cm−1. 1H NMR (CDCl3):
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Article
Table 1
3
4
7
8
11
empirical formula
fw
C
102H82Cl4O14P6Ru6S4
C51H41Cl2O5P3Ru3S4
1329.10
C43H42Cl2O5P3Ru3S4
1234.03
C43H43Cl2O3P3Ru3S6
1267.15
C150H130O12P6Ru6Se8
3548.46
2593.96
temp (K)
wavelength (Å)
cryst syst
space group
a (Å)
150(2)
150(2)
123(2)
150(2)
150(2)
0.71073
0.71073
0.71073
0.71073
0.71073
monoclinic
P21/c
monoclinic,
P21/c
monoclinic
P21/c
monoclinic
P21/c
orthorhombic
P212121
21.585(3)
21.581(3)
21.924(3)
90
20.046(3)
12.570(2)
21.113(4)
90
16.510(1)
15.184(1)
18.735(1)
90
16.842(2)
15.214(2)
18.792(2)
90
14.635(3)
18.585(3)
50.286(9)
90
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
93.659(2)
90
112.080(2)
90
102.050(1)
90
101.997(2)
90
90
90
10 192(2)
4
4930(1)
4593.1(5)
4
4710(1)
13 678(4)
4
Z
4
4
Dcalcd (Mg m−3
)
1.690
1.791
1.785
1.787
1.723
μ(Mo Kα) (mm−1
)
1.210
1.331
1.421
1.471
2.906
F(000)
5168
2648
2460
2528
7008
cryst size (mm)
θ range (deg)
limiting indices
0.14 × 0.04 × 0.03
1.34−28.44
−28 ≤ h ≥ 28
−27 ≤ k ≥ 28
−29 ≤ l ≥ 28
87 844
0.26 × 0.24 × 0.14
1.93−28.33
−26 ≤ h ≥ 25
−16 ≤ k ≥ 16
−28 ≤ l ≥ 27
38 641
0.12 × 0.10 × 0.06
2.68−28.32
−21 ≤ h ≥ 21
−19 ≤ k ≥ 19
−24 ≤ l ≥ 24
38 721
0.135× 0.15 × 0.05
2.26−28.31
−22 ≤ h ≥ 22
−19 ≤ k ≥ 19
−24 ≤ l ≥ 24
39 430
0.40 × 0.22 × 0.04
1.17−28.29
−19 ≤ h ≥ 19
−24 ≤ k ≥ 24
− 67 ≤ l ≥ 66
118 372
no. of rflns collected
no. of indep rflns (Rint)
max, min transmissn
no. of data/restraints/params
goodness of fit on F2
final R indices (I > 2σ(I))
R1
24 236 (0.1287)
0.9646, 0.8498
24 236/0/1225
0.956
11 455 (0.0473)
0.8355, 0.7234
11 455/0/585
1.114
10 695 (0.1541)
0.9196, 0.8480
10 695/0/541
0.936
10 942 (0.0345)
0.9301, 0.6271
10 942/0/540
1.107
32 910 (0.0605)
0.8926, 0.3894
32 910/0/829
1.060
0.0780
0.1596
0.0727
0.2024
0.0632
0.0889
0.0275
0.0711
0.0503
0.1023
wR2
R indices (all data)
R1
0.1661
0.0961
0.1398
0.0344
0.0741
wR2
0.1912
0.2209
0.1113
0.0724
0.1116
largest diff in peak and hole (e Å−3
)
3.008 and −1.384
3.376 and −1.539
1.114 and −1.052
1.229 and −0.978
0.883 and −0.847
parameters were found; a = 14.648(3) Å, b = 20.880(5) Å, c =
19.271(6) Å, β = 110.137(25)°, V = 5533.60(2.49) Å3. A solution was
found in P21/c, and all atoms were refined anisotropically. The best
refinement was at ca. 10% and showed five to six large peaks in the
difference map that could not be accounted for. Further details of the
data collection and structure refinement for 3, 4, 7, 8, and 11 are given
in Table 1.
Road, Cambridge CB2 1FZ, U.K.; fax +44-1223-336033; e-mail
deposit@ccdc.cam.ac.uk).
AUTHOR INFORMATION
■
Notes
The authors declare no competing financial interest.
Computational Details. Calculations were performed on all
derivatives with the Gaussian 03 (G03) program package42 employing
the DFT method with the Becke three-parameter hybrid functional43
and Lee−Yang−Parr’s gradient-corrected correlation functional44
(B3LYP). The LanL2DZ basis set45 and effective core potential
were used for the Ru, P, and S atoms, and the split-valence 3-21G**
basis set46 was applied for all other atoms. The geometry of the
clusters and the electronic structures were calculated in the gas phase.
Normal mode analysis was employed to confirm the stationary point
nature of the geometry calculated.
ACKNOWLEDGMENTS
■
This research has been sponsored by the Ministry of Science
and Information & Communication Technology, Government
of the People’s Republic of Bangladesh. M.I.H. thanks the
Bangladesh Academy of Sciences for a fellowship. We thank Dr.
Michael Morris (University of Sheffield) for reading a draft of
this work and passing on many helpful comments.
REFERENCES
■
ASSOCIATED CONTENT
■
(1) (a) 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. (b) Ansari, M. A.; Ibers, J. A. Coord.
Chem. Rev. 1990, 100, 223. (c) Roof, L. C.; Kolis, J. W. Chem. Rev.
1993, 93, 1037. (d) Kanatzidis, M. G.; Huang, S. P. Coord. Chem. Rev.
1994, 130, 223. (e) Mathur. Adv. Organomet. Chem. 1997, 41, 243.
(f) Degroot, M. W.; Corrigan, J. F. Ed. McCleverty, J. A.; Meyer, T. J.
Compr. Coord. Chem. II 2004, 7, 57. (g) Corrigan, J. F.; DeGroot, M.
W.; Rao, C. N. R.; Mueller, A.; Cheetham, A. K. Chem. Nanomater.
S
* Supporting Information
Text, tables and cif files giving details of the X-ray
crystallographic structure determinations of 3, 4, 7, 8, and 11.
This material is available free of charge via the Internet at
http://pubs.acs.org. Crystal data are also available from http://
www.ccdc.cam.ac.uk/conts/retrieving.html as supplementary
publications CCDC Nos. 864698−864702 (CCDC, 12 Union
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Article
2004, 2, 418. (h) Hogarth, G.; Kabir, S. E.; Nordlander, E. Dalton
Trans. 2010, 39, 6153.
(2) (a) Hunter, C. A. Chem. Soc. Rev. 1994, 101. (b) Johnson, B. F.
G.; Lewis, J.; Lodge, P. G.; Raithby, P. R.; Henrick, K; McPartlin, M. J.
Chem. Soc., Chem. Commun. 1979, 719.
Azam, K. A.; Hursthouse, M. B.; Kabir, S. E.; Malik, K. M. A.; Mottalib,
M. A.; Rosenberg, E. J. Cluster Sci. 2001, 12, 5.
(13) Uddin, M. N.; Begum, N.; Hassan, M. R.; Hogarth, G.; Kabir, S.
E.; Miah, M. A.; Nordlander, E.; Tocher, D. A. Dalton Trans. 2008,
6219.
(14) Ghosh, S.; Hogarth, G.; Kabir, S. E.; Nordlander, E.; Salassa, L.;
Tocher, D. A. J. Organomet. Chem. 2011, 696, 1982.
(15) Hogarth, G.; O’Brien, M.; Tocher, D. A. J. Organomet. Chem.
2003, 672, 29.
(3) (a) Hogarth, G.; Taylor, N. J.; Carty, A. J.; Meyer, A. J. Chem.
Soc., Chem. Commun. 1988, 834. (b) Humphrey, M. G.; Lockhart-
Gillett, B.; Samoc, M.; Skelton, B. W.; Tolhurst, V.-A.; White, A. H.;
Wilson, A. J.; Yates, B. F. J. Organomet. Chem. 2005, 690, 1487.
(c) Graiff, C.; Predieri, G.; Tiripicchio, A. Eur. J. Inorg. Chem. 2003,
1659. (d) Baistrocchi, P.; Careri, M.; Cauzzi, D.; Graiff, C.; Lanfranchi,
M.; Manini, P.; Predieri, G.; Tiripicchio, A. Inorg. Chim. Acta 1996,
252, 367.
(4) (a) Broadhurst, P. V.; Johnson, B. F. G.; Lewis, J. J. Chem. Soc.,
Dalton Trans. 1982, 1881. (b) Arce, A. J.; Arrojo, P.; Sanctis, Y.; De.;
Deeming, A. J.; West, D. J. Polyhedron 1992, 11, 1013. (c) Arce, A. J.;
Arrojo, P.; De Sanctis, Y.; Deeming, A. J. J. Chem. Soc, Chem. Commun.
1991, 1491. (d) Zhang, J.; Leong, W. K. Dalton Trans. 2000, 1279.
(5) (a) Fomperyrine, P.; Lavigne, G.; Bonnet, J. J. J. Chem. Soc.,
Dalton Trans. 1987, 91. (b) Hodge, S. R.; Johnson, B. F. G.; Lewis., J.;
Raithby, P. R. J. Chem. Soc., Dalton Trans. 1987, 931. (c) Bryan, E. G.;
Johnson, B. F. G.; Lewis, J. J. Chem. Soc., Dalton Trans. 1977, 1328.
(d) Kiel, G. Y.; Takats, J. Organometallics 1989, 8, 839. (e) Adams, R.
D. Polyhedron 1985, 4, 2003. (f) Adams, R. D.; Horvath, I. T. Prog.
Inorg. Chem. 1985, 33, 127. (g) Adams, R. D.; Horvath, I. T. Prog.
Inorg. Synth. 1989, 26, 303.
(16) (a) Ju, T. D.; Lang, R. F.; Roper, G. C.; Hoff, C. D. J. Am. Chem.
Soc. 1996, 118, 5328. (b) Zhao, X.; Hsiao, Y.-M.; Lai, C.-H.;
Reibenspies, J. H.; Darensbourg, M. Y. Inorg. Chem. 2002, 41, 699.
(c) Jennings, M. C.; Puddephatt, R. J. Inorg. Chem. 1988, 27, 4280.
(17) (a) Georgakaki, I. P.; Thomson, L. M.; Lyon, E. J.; Hall, M. B.;
Darensbourg, M. Y. Coord. Chem. Rev. 2003, 238−239, 255. (b) Evans,
D. J.; Pickett, C. J. Chem. Soc. Rev. 2003, 32, 268. (c) Rauchfuss, T. B.
Inorg. Chem. 2004, 43, 14. (d) Sun, L.; Åkermark, B.; Ott, S. Coord.
Chem. Rev. 2005, 249, 1653. (e) Liu, X.; Ibrahim, S. K.; Tard, C.;
Pickett, C. J. Coord. Chem. Rev. 2005, 249, 1641. (f) Adam, F. I.;
Hogarth, G.; Richards, I. J. Organomet. Chem. 2007, 692, 3957.
(g) Ezzaher, S.; Capon, J.-F.; Gloaguen, F.; Petillon, F. Y.;
Schollhammer, P.; Talarmin, J. Inorg. Chem. 2007, 46, 9863.
(h) Adam, F. I.; Hogarth, G.; Richards, I.; Sanchez, B. E. Dalton
Trans. 2007, 2485.
(18) Ghosh, S.; Hogarth, G.; Holt, K. B.; Kabir, S. E.; Rahaman, A.;
Unwin, D. G. Chem. Commun. 2011, 47, 11222.
(19) (a) Hogarth, G.; Phillips, J. A.; Van Gastel, F.; Taylor, N. J.;
Marder, T. B.; Carty, A. J. J. Chem. Soc., Chem.Commun. 1988, 1570.
(b) Corrigan, J. F.; Dinardo, M.; Doherty, S.; Hogarth, G.; Sun, Y.;
Taylor, N. J.; Carty, A. J. Organometallics 1994, 13, 3572.
(20) Mealli, C.; Proserpio, D. M. J. Am. Chem. Soc. 1990, 112, 5484.
(21) (a) Cabeza, J. A.; Matinez-Garcia, M. A.; Riera, V.; Ardura, D.;
Garcia-Granda, S. Organometallics 1998, 17, 1471. (b) Hanif, K. M.;
Kabir, S. E.; Mottalib, M. A.; Hursthouse, M. B.; Malik, K. M. A.;
Rosenberg, E. Polyhedron 2000, 19, 1073. (c) Hossain, G. M. G.;
Hyder, M. I.; Kabir, S. E.; Malik, K. M. A.; Miah, M. A.; Siddiquee, T.
A. Polyhedron 2003, 22, 633.
(22) Kabir, S. E.; Hogarth, G. Coord. Chem. Rev. 2009, 253, 1285.
(23) (a) Adams, R. D.; Chen, L.; Yamamoto, J. H. Inorg. Chim. Acta
1995, 229, 47. (b) Adams, R. D.; Yamamoto, J. H. Organometallics
1995, 14, 3704. (c) Adams, R. D.; Yamamoto, J. H. J. Cluster Sci 1996,
7, 643.
(24) Kabir, S. E.; Malik, K. M. A.; Rosenberg, E.; Siddiquee, T. A.
Inorg. Chem. Commun. 2000, 3, 140.
́
(25) Adams, R. D.; Horvath, I. T. Inorg. Chem. 1984, 23, 4718.
(26) Begum, N.; Hassan, M.; Kabir, S. E. Indian J. Chem., Sect. A
2005, 44A, 490.
(27) Schermer, E. D.; Baddley, W. H. J. Organomet. Chem. 1971, 30,
67.
(28) Begum, N; Hyder, M. I.; Hassan, M. R.; Kabir, S. E.; Bennett, D.
W.; Haworth, D. T.; Siddiquee, T. A.; Rokhsana, D.; Sharmin, A.;
Rosenberg, E. Organometallics 2008, 27, 1550.
(6) Hieber, W.; Spacu, P Z. Anorg. Chem. 1937, 233, 353.
(7) Kettle, S. F. A.; Orgel, L. E. J. Chem. Soc. A 1960, 3890.
(8) Osbourne, A. G.; Stone, F. G. A. J. Chem. Soc., Chem. Commun.
1965, 361.
(9) (a) Bryan, E. G.; Johnson, B. F. G.; Lewis, J. J. Chem. Soc., Dalton
Trans. 1977, 1328. (b) Allen, V. F.; Mason, R.; Hitchcock, J. J.
Organomet. Chem. 1977, 140, 297. (c) Leadbeater, N. E. J. Organomet.
Chem. 1999, 573, 211. (d) Crooks, G. R.; Johnson, B. F. G.; Lewis, J.;
Williams, I. G. J. Chem. Soc. A 1969, 797. (e) Evans, J.; Gracey, B. P. J.
Chem. Res. Synop. 1986, 42. (f) Evans, J.; Gracey, B. P. J. Chem. Soc.,
Dalton Trans. 1982, 1123.
(10) (a) Kabir, S. E.; Johns, C. A.; Malik, K. M. A.; Mottalib, M. A.;
Rosenberg, E. J. Organomet. Chem. 2001, 625, 112. (b) Azam, K. A.;
Kabir, S. E.; Miah, A.; Day, M. W. J. Organomet. Chem. 1992, 435, 157.
(c) Fomperyrine, P.; Lavigne, G.; Bonnet, J. J. J. Chem. Soc., Dalton
Trans. 1987, 91. (d) Hodge, S. R.; Johanson, B. F. G.; Lewis., J.;
Raithby, P. R. J. Chem. Soc., Dalton Trans. 1987, 931. (e) Kiel, G. Y.;
Takats, J. Organometallics 1989, 8, 839. (f) Ahmad, J. U.; Kabir, S. E.;
Miah, M. A. J. Banglad. Chem. Soc. 1991, 4, 61. (g) Adams, R. D.;
Babin, J. E.; Tasi, M. Inorg. Chem. 1986, 25, 4514.
(11) (a) Johnson, B. F. G.; Johnston, R. D.; Josty, P. L.; Lewis, J.;
Williams, I. G. Nature 1967, 213, 901. (b) Schermer, E. D.; Baddley,
W. H. J. Organomet. Chem. 1971, 30, 67. (c) Chan, L.-F. S.; Low, K.-
H.; So, G. K.-M.; Chui, S. S.-Y.; Che, C.-M. Chem. Commun. 2011, 47,
8808.
(12) (a) Begum, N.; Hyder, M. I.; Kabir, S. E.; Kundu, K. Indian J.
Chem. 2005, 44A, 521. (b) Kabir, S. E.; Pervin, S.; Sarker, N. C.;
Yesmin, A.; Sharmin, A.; Siddiquee, T. A.; Haworth, D. T.; Bennett, D.
W.; Malik, K. M. A. J. Organomet. Chem. 2003, 681, 237. (c) Akter, T.;
Begum, N.; Yesmin, A.; Haworth, D. T.; Bennett, D. W.; Kabir, S. E.;
Miah, Md. A.; Sarker, N. C.; Siddiquee, T. A.; Rosenberg, E. J.
Organomet. Chem. 2004, 689, 237. (d) Ahmed, S. J.; Hyder, Md. I.;
Kabir, S. E.; Miah, Md. A.; Deeming, A. J.; Nordlander, E. J.
Organomet. Chem. 2006, 691, 309. (e) Akter, H.; Deeming, A. J.;
Hossain, G. M. G.; Kabir, S. E.; Mondol, D. N.; Nordlander, E.;
Sharmin, A.; Tocher, D. A. J. Organomet. Chem. 2005, 690, 4628.
(f) Hyder, Md. I.; Hossain, G. M. G.; Kabir, S. E.; Miak, Md. A.
Polyhedron 2005, 24, 872. (g) Kabir, S. E.; Begum, N.; Hassan, Md.
M.; Hyder, Md. I.; Nur, H.; Bennett, D. W.; Siddiquee, T. A.;
Haworth, D. T.; Rosenberg, E. J. Organomet. Chem. 2004, 689, 1569.
(h) Kabir, S. E.; Saha, M. S.; Tocher, D. A.; Hossain, G. M. G.;
Rosenberg, E. J. Organomet. Chem. 2006, 691, 97. (i) Abedin, S. M. T.;
(29) (a) Song, L.-C.; Yan, C.-G.; Hu, Q.-M.; Wang, R.-J.; Wang, H.-
G. Huaxue Xuebao 1995, 53, 402. (b) Song, L.-C.; Sun, Y.; Hu, Q.-M.;
Lin, Y J. Organomet. Chem. 2003, 676, 80. (c) Song, L.-C.; Lu, G.-L.;
Hu, Q.-M.; Fan, H.-T.; Chen, J.-B.; Sun, J.; Huang, X.-Y. J. Organomet.
Chem. 2001, 627, 255.
(30) Arce, A. J.; Arrojo, P.; Deeming, A. J.; De Sanctis, Y. J. Chem.
Soc., Chem. Commun. 1991, 1491.
(31) Adams, H.; Bailey, N. A.; Gay, S. R.; Gill, L. J.; Hamilton, T.;
Morris, M. J. J. Chem. Soc., Dalton Trans. 1996, 2403.
(32) Adams, Morris, M. J.; Mountford, P.; Patel, R.; Spey, S. E. J.
Chem. Soc., Dalton Trans. 2001, 2601.
(33) Adams, H.; Bailey, N. A.; Gay, S. R.; Hamilton, T.; Morris, M. J.
J. Organomet. Chem. 1995, 493, C25.
(34) Adams, H.; Biebricher, A.; Gay, S. R.; Hamilton, T.; McHugh, P.
E.; Morris, M. J.; Mays, M. J. J. Chem. Soc., Dalton Trans. 2000, 2983.
́
(35) (a) Schollhammer, P.; Petillon, F. Y.; Poder-Guillou, S.;
Talarmin, J.; Muir, K. W.; Yufit, D. S. J. Organomet. Chem. 1996, 513,
2557
dx.doi.org/10.1021/om201052u | Organometallics 2012, 31, 2546−2558

Organometallics
Article
́
181. (b) Petillon, F. Y.; Schollhammer, P.; Talarmin, J.; Muir, K. W.
Coord. Chem. Rev. 1998, 178−180, 203.
(36) (a) Benson, I. B.; Killops, S. D.; Knox, S. A. R.; Welch, A. J. J.
Chem. Soc., Chem. Commun. 1980, 1137. (b) Shaver, A.; Soo Lum, B.;
Bird, P.; Livingstone, E.; Schweitzer, M. Inorg. Chem. 1990, 29, 1832.
(37) (a) Anwar, M. K.; Hogarth, G.; Senturk, O. S.; Clegg, W.;
Elsegood, M. R. J.; Doherty, S. J. Chem. Soc., Dalton Trans. 2001, 341.
(b) Doherty, S.; Hogarth, G. Chem. Commun. 1998, 1815.
(38) (a) Rivomanana, S.; Lavigne, G.; Lugan, N.; Bonnet, J.-J. Inorg.
Chem. 1991, 30, 4110. (b) Rivomanana, S.; Mongin, C.; Lavigne, G.
Inorg. Chem. 1996, 35, 1195.
(39) (a) Adams, R. D.; Boswell, E. M.; Captain, B.; Patel, M. A. Inorg.
Chem. 2007, 46, 533. (b) Adams, R. D.; Captain, B.; Fu, W.; Smith, M.
D. Inorg. Chem. 2002, 41, 5593. (c) Adams, R. D.; Captain, B.; Fu, W.;
Smith, M. D. Inorg. Chem. 2002, 41, 2302. (d) Adams, R. D.; Captain,
B.; Smith, J. L. Jr.; Hall, M. B.; Beddie, C. L.; Webster, C. E. Inorg.
Chem. 2004, 43, 7576. (e) Adams, R. D.; Captain, B.; Fu, W. Inorg.
Chem. 2003, 42, 1328. (f) Adams, R. D.; Captain, B.; Smith, J. L Jr.
Inorg. Chem. 2005, 44, 1413. (g) Adams, R. D.; Smith, J. L. Jr. Inorg.
Chem. 2005, 44, 4276.
(40) SMART and SAINT+ software for CCDC diffractometers, version
6.1; Bruker AXS, Madison, WI, 2000.
(41) Sheldrick, G. M. SHELXTL PLUS, version 6.1; Bruker AXS,
Madison, WI, 2000.
(42) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.; Vreven, T.;
Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.;
Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.;
Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,
O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J.
B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,
O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J.; Ayala, P. Y.;
Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.;
Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Forestman,
J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.;
Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.;
Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
W.; Wong, M. W.; Gonzales, C.; Pople, J. A. Gaussian 03. (revision
D.01); Gaussian Inc., Wallingford, CT, 2004.
(43) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
(44) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter
1988, 37, 785.
(45) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270.
(46) Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980,
102, 939.
2558
dx.doi.org/10.1021/om201052u | Organometallics 2012, 31, 2546−2558