Synthesis, structure and reactivity of tetranuclear square-type complexes of rhenium and manganese bearing pyrimidine-2-thiolate (pymS) ligands: Versatile and efficient precursors for mono- and polynuclear compounds containing M(CO)3 (M = Re, M

Article abstract of DOI:10.1039/b815337j

Reactions of M₂(CO)₁₀ (M = Re, Mn) with pyrimidine-2-thiol (pymSH) in the presence of Me₃NO afford the tetranuclear square-type complexes [M₄(CO)₁₂(μ- κ³-pymS)₄] (1, M = Re; 2, M

Full text of DOI:10.1039/b815337j

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PAPER
www.rsc.org/dalton | Dalton Transactions
Synthesis, structure and reactivity of tetranuclear square-type complexes of
rhenium and manganese bearing pyrimidine-2-thiolate (pymS) ligands:
versatile and efficient precursors for mono- and polynuclear compounds
containing M(CO)3 (M = Re, Mn) fragments†
S. E. Kabir,*a J. Alam,a S. Ghosh,a K. Kundu,a G. Hogarth,*b D. A. Tocher,b G. M. G. Hossainc and
H. W. Roesky*d
Received 2nd September 2008, Accepted 17th March 2009
First published as an Advance Article on the web 14th April 2009
DOI: 10.1039/b815337j
Reactions of M2(CO)10 (M = Re, Mn) with pyrimidine-2-thiol (pymSH) in the presence of Me3NO
3
afford the tetranuclear square-type complexes [M4(CO)12(m-k -pymS)4] (1, M = Re; 2, M = Mn). Both
consist of four M(CO)3 (M = Re, Mn) units, pairs of which are joined by tridentate pyrimidine-2-
thiolate ligands. Treatment of 1–2 with a variety of donor ligands results in cleavage of the square to
afford mononuclear species with either a mono- or bidentate pyrimidine-2-thiolate ligand.
2
Triphenylphosphine reacts with 2 to give [Mn(CO)3(PPh3)(k -pymS)] (3) in which the pyrimidine-2-
2
1
thiolate coordinates in a bidentate fashion. With diamines [M(CO)3(k -L)(k -pymS)] (4–7) (M = Re,
Mn; L = 2,2¢- bipy, 1,10-phen, en) result in which the pyrimidine-2-thiolate binds in a monodentate
fashion through sulfur. With diphosphines, complexes with different stoichiometries and
pyrimidine-2-thiolate binding modes are obtained depending on the nature of the metal and
1
2
2
diphosphine. With dppm and dppe, 1 gives [Re(CO)2(k -pymS)(k -dppm)] (8) and [Re(CO)2(k -
1
2
1
pymS)(k -dppe)2] (10), respectively, whereas 2 affords [Mn(CO)2(k -pymS)(k -dppm)2] (9) and
[Mn(CO)2(k -pyS)(k -dppe)] (11) under similar conditions. Reactions of 1–2 with [Os3(CO)10(NCMe)2]
affords mixed-metal butterfly clusters [MOs3(CO)13(m3-k -pymS)] (12–13) in which the group 7 metal
2
2
2
occupies a wing-tip position and the pyrimidine-2-thiolate ligand caps a triangular Os2M face. With
Ru3(CO)12, carbon–sulfur bond cleavage occurs to give the tetranuclear clusters [MRu3(CO)14(m4-S)(m-
1
1
k :h -pym)] (14–15) bearing both the extruded sulfur and the heterocyclic ring. The molecular
structures of 1–7, 10 and 12 have been established by X-ray diffraction allowing the binding mode of
the pyrimidine-2-thiolate ligands to be probed.
those based on the more common octahedral metal building
Introduction
blocks are relatively rare.15–25 This seems somewhat unexpected
and indeed the first square-type complexes reported by Verkade
and co-workers contained the octahedral M(CO)4 (M = Cr, W)
linking units.15 More recently, Hupp and co-workers have linked
Re(CO)3Cl units together with 4,4¢-bipy and related ligands16
and Lees have made a series of related group 7 square-like
complexes.17–19
Over the past two decades self-assembly phenomena have been
utilised for the construction of highly organised metal-containing
macrocycles, becoming an attractive and fruitful pathway for
macrocyclisation, since the usual synthetic routes for the cy-
clisation of large molecules are frequently tedious and low-
yielding.1–4 Molecular square-type complexes are amongst the
most widely studied of this family of macrocycles, their synthesis
being pioneered by Stang,5–9 Fujita10–14 and their co-workers.
While over the past twenty years, a large number of square-type
complexes have been prepared, the vast majority are based on
a square-planar metal coordination geometry, and in contrast
Pyrimidine-2-thiolate is a versatile ligand known to exhibit a
variety of coordination geometries (Chart 1) and mono-, di- and
polynuclear metal complexes containing this ligand have been
shown to display a range of different structural types.26 Reactions
aDepartment of Chemistry, Jahangirnagar University, Savar, Dhaka 1342,
Bangladesh
bDepartment of Chemistry, University College London, 20 Gordon Street,
London, UK WC1H 0AJ
cDepartment of Chemistry, Dhaka University, Dhaka 1000, Bangladesh
dInstitute of Inorganic Chemistry, Georg-August University of Go¨ttingen,
Tammannstr. 4, 37077 Go¨ttingen, Germany
† CCDC reference numbers 688773 for 1, 688774 for 2, 698944 for 3,
688777 for 4, 688778 for 5, 688776 for 6, 688775 for 7, 698965 for 10 and
698966 for 12. For crystallographic data in CIF or other electronic format
see DOI: 10.1039/b815337j
Chart 1
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of M2(CO)10 (M = Re, Mn) with pyridine-2-thiol in the presence of
Me3NO afford dinuclear complexes [M2(CO)6(m-pyS)2], contain-
ing two pyridine-2-thiolate ligands, each acting as a five-electron
donor through coordination of both sulfur and nitrogen atoms.27,28
Pyrimidine-2-thiolate contains an extra nitrogen coordination site
and should be capable of binding concurrently to a number of
different atoms. This was appealing to us in our attempts to
develop systematic syntheses of multimetallic clusters and herein
we report the synthesis, structure and reactivity of fac-tricarbonyl
manganese(I)- and rhenium(I)-based self-assembled square-type
complexes containing pyrimidine-2-thiolate as the bridging ligand.
Results and discussion
(a) Synthesis and structure of tetranuclear square-type complexes
Reaction of M2(CO)10 (M = Re, Mn) with pyrimidine-2-thiol in
3
Fig. 1 ORTEP diagram of the molecular structure of [Re4(CO)12(m-k -
◦
pymS)4] (1), showing 50% probabil◦ity thermal ellipsoids. Selected inter-
presence of Me3NO at 25 C affords the tetranuclear complexes
˚
3
atomic distances (A) and angles ( ): Re(1)–N(1) 2.175(9), Re(1)–N(8)
[M4(CO)12(m-k -pymS)4] (1, M = Re, 68%; 2, M = Mn, 72%). In
2.217(9), Re(2)–N(3) 2.179(9), Re(2)–N(2) 2.246(9), Re(3)–N(5)
2.180(9), Re(3)–N(4) 2.220(9), Re(4)–N(7) 2.177(8), Re(4)–N(6)
2.239(9), Re(1)–S(1) 2.539(3), Re(2)–S(2) 2.533(3), Re(3)–S(3) 2.518(3),
Re(4)–S(4) 2.545(3), av. C–S 1.706(11), av. Re–C 1.903(14), N(1)–
Re(1)–N(8) 86.4(3), N(8)–Re(1)–S(1) 83.6(2), N(1)–Re(1)–S(1) 65.1(2),
N(3)–Re(2)–N(2) 86.9(3), N(3)–Re(2)–S(2) 65.0(2), N(2)–Re(2)–S(2)
83.6(2), N(5)–Re(3)–N(4) 86.7(3), N(4)–Re(3)–S(3) 84.7(2), N(5)–Re(3)–
S(3) 64.7(2), N(7)–Re(4)–N(6) 86.0(3), N(7)–Re(4)–S(4) 64.8(2), N(6)–
Re(4)–S(4) 82.7(2).
each, the pyrimidine-2-thiolate ligands act as five electron donors
binding through sulfur and both nitrogen atoms (Scheme 1).
Both 1 and 2 have been characterised by a combination of
spectroscopic data and single-crystal X-ray crystallography. Each
shows two strong carbonyl absorptions in the IR spectra, and
1H NMR spectra are consistent with the presence of single
type of pyrimidine-2-thiolate ligand. However, on this basis the
stoichiometry of the complexes could not be determined. In the
FAB mass spectra, peaks at m/z 1526 for 1 and m/z 1000 for
2 were suggestive of tetranuclear clusters. However, the precise
attachment of the ligands could only be obtained by X-ray
diffraction studies, the results of which are summarised in Fig. 1
and 2.
Scheme 1
3
Fig. 2 ORTEP diagram of the molecular structure of [Mn4(CO)12(m-k -
The solid-state structures show that the molecules are indeed
tetranuclear; the four separate metal tricarbonyl units are joined
by pyrimidine-2-thiolate ligands. These bridge via coordination
of a single nitrogen atom to one metal atom and a chelating
interaction to another via the second nitrogen and sulfur atom.
The result is an overall square-like arrangement. The overall
coordination geometry of each metal is best described as a
distorted octahedron with a cis-arrangement of the pyrimidine-2-
thiolate ligands. Each metal is bound to three facially arranged
pymS)4] (2), showing 50% probability thermal ellipsoids. Selected
interatomic distances (A) and angles (◦): Mn(1)–N(1) 2.037(2),
˚
Mn(1)–N(8) 2.101(2), Mn(2)–N(3) 2.056(3), Mn(2)–N(2) 2.109(2),
Mn(3)–N(5) 2.034(3), Mn(3)–N(4) 2.123(2), Mn(4)–N(7) 2.022(2),
Mn(4)–N(6) 2.101(3), Mn(1)–S(1) 2.4130(9), Mn(2)–S(2) 2.4032(9),
Mn(3)–S(3) 2.4232(9), Mn(4)–S(4) 2.4370(9), av. C–S 1.714(3), av. Mn–C
1.803(3), N(1)–Mn(1)–N(8) 87.52(9), N(8)–Mn(1)–S(1) 87.00(7), N(1)–
Mn(1)–S(1) 68.71(7), N(3)–Mn(2)–N(2) 87.80(10), N(3)–Mn(2)–S(2)
68.52(7), N(2)–Mn(2)–S(2) 86.69(7), N(5)–Mn(3)–N(4) 87.68(10),
N(4)–Mn(3)–S(3) 86.61(7), N(5)–Mn(3)–S(3) 68.39(8), N(7)–Mn(4)–N(6)
86.78(10), N(7)–Mn(4)–S(4) 68.53(7), N(6)–Mn(4)–S(4) 86.34(7).
˚
carbonyls, the average metal–carbon distance (1.903(14) A in
˚
1; 1.803(3) A in 2) being similar to those observed in related
complexes.27–33 Two of the pyrimidine-2-thiolate ligands lie above
(2.178(9) A in 1; 2.037(2) A in 2) but both being within the
range reported for related compounds.27–36 The average N–M–S
chelate angles (64.9(2)◦ in 1; 68.54(7)◦ in 2) are similar to those
found in related dinuclear complexes [Re2(CO)6(m-MepyS)2]27
˚
˚
and two below the M4 plane, being slightly tilted with respect
˚
to one another. The M–Nbri distances (av. 2.231(9) A in 1; av.
˚
2.109(2) A in 2) are somewhat longer than the M–Nche distances
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(av. 65.7(3)◦) and [Mn2(CO)6(m-pyS)2]28 (av. 69.27(8)◦) and the
˚
˚
average M–S distances (2.534(3) A in 1; 2.4191(9) A in 2) are
in agreement with those in the literature.27,28,33,36–38 The diagonal
˚
M–M contacts are 8.1768(17) and 8.309(3) A in 1 and 7.8688(10)
˚
and 7.9362(10) A in 2. Each pyrimidine-2-thiolate ligand serves as
five-electron donor and hence each metal achieves an 18-electron
configuration without any metal–metal interaction. To the best of
our knowledge, the tetranuclear square-type skeletal geometry of
1 and 2 containing heterocyclic ligands and fac-M(CO)3 fragments
has not previously been detailed.
(b) Reactivity of 1 and 2 toward various mono- and
bidentate ligands
Treatment of either 1 or 2 with various mono- and bidentate
group 15 ligands resulted in breakdown of the square to give
mononuclear species within which the coordination geometry of
the pyrimidine-2-thiolate ligand varies. Reaction of 2 with PPh3
2
gives mononuclear [Mn(CO)3(PPh3)(k -pymS)] (3) in 55% yield
(Scheme 2). Now three strong carbonyl absorptions are seen in
the IR spectrum and the 31P{ H} NMR shows a simple singlet at
1
d 58.3 ppm. An ORTEP diagram of the molecular structure of
3 is depicted in Fig. 3, and selected bond lengths and angles are
listed in the caption. The molecule contains a single manganese
atom with three carbonyl groups, a triphenylphosphine ligand
and a chelating pyrimidine-2-thiolate ligand. The coordination
geometry around the manganese atom is a distorted octahedron
with three carbonyl groups arranged in a facial fashion. The
distortion from octahedral coordination geometry is evident from
the short N–Mn–S chelate angle (68.73(4)◦) of the heterocyclic
ligand which is similar to that observed in 2. The best equatorial
plane is defined by the nitrogen and sulfur atoms of the chelating
ligands and the carbon atoms of two carbonyl groups (C(1) and
C(2)). The triphenylphosphine ligand occupies an axial site with
Fig. 3 ORTEP diagram of the molecular structure of [Mn(CO)3-
2
(PPh3)(k -pymS)] (3), showing 35% probability thermal ellipsoids.
Selected interatomic distances (A) and angles (◦): Mn(1)–C(1)
˚
1.7993(19), Mn(1)–C(2) 1.8027(18), Mn(1)–C(3) 1.8291(19), Mn(1)–N(1)
2.0376(15), Mn(1)–P(1) 2.3612(5), Mn(1)–S(1) 2.4133(5), C(4)–S(1)
1.7237(17), C(1)–Mn(1)–C(2) 94.72(8), C(1)–Mn(1)–C(3) 86.12(8),
N(1)–Mn(1)–S(1) 68.73(4), C(2)–Mn(1)–C(3) 90.58(8), P(1)–Mn(1)–C(3)
176.75(6), P(1)–Mn(1)–N(1) 91.95(4), P(1)–Mn(1)–S(1) 91.883(17),
C(2)–Mn(1)–N(1) 98.66(7), C(1)–Mn(1)–S(1) 97.95(6), C(4)–S(1)–Mn(1)
78.89(6).
respect to this plane and the manganese-phosphorus distance is
somewhat larger than those normally found in the literature.39
Other bond distances are similar to those found in 2.
Reactions of 1 with 2,2¢-bipyridine (bipy) and 1,10-phenan-
2
1
throline (phen) afford [Re(CO)3(k -bipy)(k -pymS)] (4) and [Re-
2
1
(CO)3(k -phen)(k -pymS)] (5) in 62 and 66% yields, respectively.
Similarly, upon treatment with phen or ethylenediamine (en) 2
2
1
2
1
gives [Mn(CO)3(k -phen)(k -pymS)] (6) and [Mn(CO)3(k -en)(k -
pymS)] (7) in 62 and 68% yields (Scheme 2). The IR spectra all
show three carbonyl bands indicative of a fac-M(CO)3 centre.
NMR spectra are generally not particularly informative; in
addition to aromatic resonances the 1H NMR spectrum of 7 shows
two multiplets at d 4.92 and 2.95 ppm assigned to the amine and
methylene protons, respectively, of the ethylenediamine ligand.
The mass spectrum of all of them exhibits the parent molecular
ion peak and peaks due to stepwise loss of three carbonyls. The
molecular structures of 4–7 are shown in Fig. 4–7. All have the
same overall structure consisting of a single metal atom with
three carbonyl groups arranged in a facial fashion, a chelating
diamine ligand and monodentate pyrimidine-2-thiolate ligand.
The metal atom is a distorted octahedron, the main distortion
being due to t◦he small bite-angle of the bidentate ligand (74.4(1)◦
in 4; 75.5(2) in 5; 79.19(7)◦ in 6; and 80.95(7)◦ in 7). In all,
the donor atoms of the bidentate ligand and the carbons of
two of the carbonyls constitute the best equatorial plane around
the metal centre with only small deviations from planarity and
the metal atom is practically in this plane. The M–C, M–N,
Scheme 2
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Fig. 6 ORTEP diagram of the molecular structure of [Mn(CO)3-
Fig. 4 ORTEP diagram of the molecular structure of [Re(CO)3-
2
1
2
1
(k -phen)(k -pymS)] (6), showing 50% probability ◦thermal ellip-
(k -bipy)(k -pymS)] (4), showing 50% probability thermal ellip-
◦
˚
˚
soids. Selected interatomic distances (A) and angles ( ): Mn(1)–C(1)
soids. Selected interatomic distances (A) and angles ( ): Re(1)–C(1)
1.800(3), Mn(1)–C(2) 1.806(3), Mn(1)–C(3) 1.801(2), Mn(1)–N(3)
2.0531(18), Mn(1)–N(4) 2.0556(17), Mn(1)–S(1) 2.3788(6), C(4)–S(1)
1.738(2), C(1)–Mn(1)–S(1) 174.07(8), N(3)–Mn(1)–N(4) 79.19(7),
N(4)–Mn(1)–S(1) 86.11(5), N(3)–Mn(1)–S(1) 82.16(5), C(4)–S(1)–Mn(1)
113.61(7), C(3)–Mn(1)–C(2) 88.47(11), C(2)–Mn(1)–N(3) 97.41(9),
C(2)–Mn(1)–N(4) 174.96(9).
1.914(5), Re(1)–C(2) 1.914(5), Re(1)–C(3) 1.927(5), Re(1)–N(1) 2.182(4),
Re(1)–N(2) 2.167(4), Re(1)–S(1) 2.5012(13), C(14)–S(1) 1.739(5),
C(3)–Re(1)–S(1) 178.52(15), N(2)–Re(1)–N(1) 74.43(14), N(2)–Re(1)–S(1)
86.10(10), N(1)–Re(1)–S(1) 80.46(11), C(14)–S(1)–Re(1) 110.32(16),
C(2)–Re(1)–C(1) 88.4(2), C(2)–Re(1)–N(1) 97.78(18), C(2)–Re(1)–N(2)
172.12(18).
Fig. 7 ORTEP diagram of the molecular structure of [Mn(CO)3-
2
1
(k -en)(k -pymS)] (7), showing 50% probability thermal ellipsoids. Se-
◦
˚
lected interatomic distances (A) and angles ( ): Mn(1)–C(1) 1.786(2),
Mn(1)–C(2) 1.798(2), Mn(1)–C(3) 1.800(2), Mn(1)–N(1) 2.0752(17),
Mn(1)–N(2) 2.0828(17), Mn(1)–S(2) 2.4067(6), C(6)–S(2) 1.740(2),
C(2)–Mn(1)–N(1) 92.01(9), C(1)–Mn(1)–N(2) 94.67(9), N(2)–Mn(1)–S(2)
86.94(5), N(1)–Mn(1)–N(2) 80.95(7), C(2)–Mn(1)–S(2) 176.74(8),
N(1)–Mn(1)–S(2) 91.21(5), C(6)–S(2)–Mn(1) 114.51(7), C(1)–Mn(1)–C(3)
89.05(10), C(1)–Mn(1)–N(1) 175.59(9).
Fig. 5 ORTEP diagram of the molecular structure of [Re(CO)3-
2
1
(k -phen)(k -pymS)] (5), showing 50% probability thermal ellip-
◦
˚
soids. Selected interatomic distances (A) and angles ( ): Re(1)–C(1)
1.916(8), Re(1)–C(2) 1.900(8), Re(1)–C(3) 1.899(10), Re(1)–N(1)
2.182(6), Re(1)–N(2) 2.171(5), Re(1)–S(1) 2.506(2), C(16)–S(1) 1.753(8),
C(3)–Re(1)–S(1) 174.3(2), N(2)–Re(1)–N(1) 75.5(2), N(2)–Re(1)–S(1)
86.29(17), N(1)–Re(1)–S(1) 84.48(17), C(16)–S(1)–Re(1) 110.6(3),
C(2)–Re(1)–C(1) 90.3(3), C(2)–Re(1)–N(1) 98.7(3), C(2)–Re(1)–N(2)
171.6(3).
of the phosphorus atoms. In contrast, reaction of 2 with dppm gave
2
1
the bis(diphosphine) complex [Mn(CO)2(k -pymS)(k -dppm)2] (9)
in 26% yield (Scheme 2). This was characterised by a comparison
2
1
of spectroscopic data with those of [Mn(CO)2(k -MepyS)(k -
2
1
and M–S distances are similar to those observed in the parent
complexes.
dppm)2]28a and [Mn(CO)2(k -pyS)(k -dppm)2].28b The IR spectrum
shows two strong carbonyl bands and the FAB mass spectrum gave
1
In contrast to the behaviour with diamines, reactions of 1
and 2 with diphosphines give different products depending on
both the backbone of the diphosphine and the size of the
metal. Reaction of 1 with bis(diphenylphosphino)methane (dppm)
a molecular ion at m/z 990. Most informative was the 31P{ H}
NMR spectrum which displays a singlet at d 64.8 ppm (broad
and unresolved, coordinated P atom) and a sextet at d -23.8 ppm
(J ca. 31.4 within each ligand, J ca. 56.7 Hz between two ligands
and across the manganese atom, non-coordinated P atom) like
2
1
affords [Re(CO)2(k -dppm)(k -pymS)] (8) in 42% yield, which is
structurally akin to the diamine complexes. The IR spectrum
shows three strong carbonyl absorption bands and in the 1H
NMR spectrum, in addition to the aromatic resonances, two
equal intensity multiplets at d 3.28 and 3.76 ppm were observed.
2
1
[Mn(CO)2(k -MepyS)(k -dppm)2].28 The sextet consists of four
closely spaced central lines of almost equal intensity and two
outer lines of small intensity at comparatively large distance for the
uncoordinated phosphorus atoms while the broad and unresolved
resonance appeared due to the coordinated phosphorus atoms.28b
The differing reactivity of 1 and 2 towards dppm is somewhat
1
The 31P{ H} NMR spectrum exhibits two doublets at d 13.7 and
23.4 ppm (JPP = 88.4 Hz) indicating the expected non-equivalence
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surprising but may reflect the stronger manganese–nitrogen versus
rhenium–nitrogen interactions, and also the known propensity
of the small bite-angle diphosphine to more readily form chelate
complexes with the heavier (larger) transition metals.
d 98.9 and 77.6 ppm due to the non-equivalent phosphorus nuclei.
These data are similar to those found for the related manganese
2
2
complex [Mn(CO)2(k -S2NC7H4)(k -dppe)].42
(c) Formation of mixed-metal clusters
Treatment of 1 with bis(diphenylphosphino)ethane (dppe) fur-
2
1
nishes [Re(CO)2(k -pymS)(k -dppe)2] (10) in 30% yield, which
is structurally analogous to 9. The IR spectrum exhibits two
strong carbonyl bands, while the FAB mass spectrum shows a
molecular ion at m/z 1150 together with peaks for successive
loss of both carbonyls. In addition to the usual resonances for
the phenyl and pyrimidyl protons, the 1H NMR spectrum shows
four equal intensity multiplets at d 2.10, 2.30, 2.50, and 3.05 ppm
for the methylene protons of the diphosphine ligands, while the
We recently reported the synthesis of a series of mixed-metal
clusters [MM¢3(CO)13(m-SN2C4H5)] (M = Mn, Re; M¢ = Ru,
Os) obtained from reactions between [M2(CO)6(m-SN2C4H5)2] and
[M¢3(CO)10L2] (L = CO, MeCN). In these, the facile metal–sulfur
bond cleavage of dimeric [M2(CO)6(m-N2C4H5)2] is believed to gen-
erate reactive mononuclear intermediates, [M(CO)3(SN2C4H5)]
(M = Mn, Re), which react further with [Os3(CO)10(NCMe)2] and
Ru3(CO)12.43 In an attempt to prepare further tetranuclear mixed-
metal clusters of this type, we have investigated the reactions of
1 and 2 with [Os3(CO)10(NCMe)2] and Ru3(CO)12. Reactions of
1 and 2 with [Os3(CO)10(NCMe)2] in refluxing benzene afforded
1
31P{ H} NMR spectrum displays two singlets at d 35.0 and
47.6 ppm. The molecular structure of 10 was confirmed by an
X-ray crystallographic study, the results of which are summarised
in Fig. 8. The molecule contains a single rhenium atom with two
carbonyl ligands, two monodentate dppe ligands and a chelating
pyrimidine-2-thiolate ligand, the latter being bonded to rhenium
through the sulfur and one nitrogen atom. The coordination
geometry at the rhenium atom is a highly distorted octahedron, the
small chelate angle of the pyrimidine-2-thiolate ligand (65.20(14)◦)
being similar to that in 1. The molecule contains a crystallographic
plane of symmetry containing the two carbonyls and pyrimidine-
2-thiolate ligand and the pendent diphosphine ligands lie trans
to one another, presumably to minimise steric congestion. The
2
the mixed-metal clusters [ReOs3(CO)13(m3-k -pymS)] (12) and
2
[MnOs3(CO)13(m3-k -pymS)] (13) in 40 and 31% yields, respectively
(Scheme 3).
˚
Re–P bond length, Re(1)–P(1), of 2.3988(9) A is within the range
found in the literature30,40,41 while other bond distances are similar
to those observed in 1. The reaction of dppe with 2 again differs
2
2
from that of 1 affording [Mn(CO)2(k -pymS)(k -dppe)] (11) in
38% yield (Scheme 2). The IR spectrum exhibits carbonyl bands
at 1937 and 1858 cm-1, while the FAB mass spectrum shows a
molecular ion at m/z 620. In the 1H NMR spectrum, in addition
to the aromatic resonances, a series of multiplets between d 2.01–
3.36 ppm are assigned to the methylene protons of the diphosphine
Scheme 3
The molecular structure of 12 is depicted in Fig. 9, and
selected bond angles and distances are listed in the caption. The
cluster consists of four metal atoms in a butterfly array with the
rhenium atom occupying a wing-tip position. The triply bridging
1
ligand, while the 31P{ H} NMR spectrum shows two singlets at
Fig. 9 ORTEP diagram of the molecular structure of [ReOs3(CO)13-
2
Fig. 8 ORTEP diagram of the molecular structure of [Re(CO)2-
(m3-k -pymS)] (12), showing 50% probability thermal ellipsoids. Selected
interatomic distances (A) and angles (◦): Os(1)–Os(2) 2.8626(8),
˚
2
1
(k -pymS)(k -dppe)2] (10), showing 35% probability thermal ellipsoids.
◦
˚
Selected interatomic distances (A) and angles ( ): Re(1)–C(1) 1.894(6),
Re(1)–C(2) 1.895(7), Re(1)–N(1) 2.172(5), Re(1)–P(1) 2.3988(9),
Re(1)–P(1¢) 2.3988(9), Re(1)–S(1) 2.5426(15), C(3)–S(1) 1.743(7),
C(1)–Re(1)–C(2) 93.1(3), P(1)–Re(1)–P(1¢) 176.25(5), N(1)–Re(1)–S(1)
65.20(14), P(1¢)–Re(1)–S(1) 88.93(2), C(3)–S(1)–Re(1) 80.75(19),
C(1)–Re(1)–N(1) 100.4(2), C(2)–Re(1)–N(1) 166.5(2), C(1)–Re(1)–P(1)
90.66(2), C(1)–Re(1)–P(1¢) 90.66(2).
Os(1)–Os(3) 2.8685(8), Os(2)–Os(3) 2.7896(8), Os(2)–Re(4) 2.9310(9),
Os(3)–Re(4) 2.9107(9), Os(2)–S(1) 2.419(4), Os(3)–S(1) 2.411(4),
Re(4)–N(1) 2.212(11), C(14)–S(1) 1.781(14), Os(2)–Os(1)–Os(3)
58.256(19), Os(3)–Os(2)–Os(1) 60.98(2), Os(2)–Os(3)–Os(1) 60.77(2),
Os(3)–Os(2)–Re(4) 61.11(2), Os(1)–Os(2)–Re(4) 118.03(3), Os(2)–Os(3)–
Re(4) 61.84(2), Os(1)–Os(3)–Re(4) 118.51(3), Os(3)–Re(4)–Os(2)
57.048(19), Os(3)–S(1)–Os(2) 70.55(10).
4462 | Dalton Trans., 2009, 4458–4467
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pyrimidine-2-thiolate ligand is facially located on the convex side
of the cluster which bridges the hinge metal atoms through the
sulfur atom, but coordinates to the wing-tip rhenium atom through
a nitrogen atom. The cluster has thirteen terminal carbonyl groups,
three of which are bonded to each of the hinge metal and the wing-
tip rhenium, while four are bonded to the wing-tip osmium. The
lated or even detected, suggesting that tetrameric [M4(CO)12(m-
k -pymS)4] is the most thermodynamically stable product. Reac-
3
tivity studies of 1–2 with various mono- and bidentate ligands
have revealed that the metal-nitrogen bonds in these complexes
are relatively weak as in every case sulfur-bound mononuclear
complexes were produced. With these the pyrimidine-2-thiolate
ligand showed two types of coordination mode, namely mono-
or bidentate. Reactions of 1–2 with [Os3(CO)10(NCMe)2] leads
to the rational formation of 62-electron tetranuclear mixed-metal
butterfly clusters with the pyrimidine-2-thiolate ligand capping a
triangular face. In contrast, with Ru3(CO)12 although tetrameric
complexes were also prepared, these result from the cleavage of the
carbon-sulfur bond affording sulfido-bridged tetranuclear mixed
metal complexes.
˚
average metal–metal distance in 12 (2.8725(9) A) is similar to that
of the 2-mercapto-1-methylimidazolate complex [ReOs3(CO)13(m3-
2
k -SN2C4H5)]43 (2.8762(4) A). The molecule contains a non-
˚
crystallographic mirror plane of symmetry passing through the
plane of the heterocyclic ring and also containing the wing-tip
metals of the butterfly. Assuming that the pyrimidine-2-thiolate
ligand serves as a five electron donor, then 12 is electronically
saturated with a total electron count of 62. The solid-state structure
1
of 12 is supported by the solution spectroscopic data. The H
NMR spectrum displays a triplet at d 7.31 ppm (J = 5.6 Hz)
and two doublets of doublets at d 8.80 ppm (J = 2.4, 5.6 Hz)
and 9.66 ppm (J = 2.4, 5.6 Hz) assigned to the ring protons
of the pyrimidine-2-thiolate ligands. The infrared spectrum of
Experimental
Methods and materials
2
12 is similar to that of [ReOs3(CO)13(m3-k -SN2C4H5)],43 while
Metal carbonyls (Strem) and pyrimidine-2-thiol (Aldrich) were
used as received. All reactions were carried out under a nitrogen
atmosphere unless otherwise stated. Reagent grade solvents were
freshly distilled from appropriate drying agents prior to use.
Infrared spectra were recorded on a Shimadzu FTIR 8101
spectrophotometer. NMR spectra were recorded on a Bruker
DPX 400 instrument. Mass spectra were recorded on a Varian
Mat 312 mass spectrometer. Elemental analyses were performed
by the microanalytical laboratories, University College London.
The cluster [Os3(CO)10(NCMe)2]46 was prepared according to a
published procedure.
the FAB mass spectrum shows a molecular ion at m/z 1234.
In view of the similarity of the IR spectra of 13 to those
2
2
of 12, [ReOs3(CO)13(m3-k -SN2C4H5)]43 and [MnOs3(CO)13(m3-k -
SN2C4H5)],43 it is reasonable to suggest that they are isostructural.
The 1H NMR spectrum of 13 displays three broad singlets in the
aromatic region with a relative intensity of 1 : 1 : 1 and the FAB
mass spectrum shows a molecular ion at m/z 1102 together with
peaks due to sequential loss of all thirteen carbonyls.
Heating 1 and 2 with Ru3(CO)12 affords the sulfido-bridged
1
1
tetranuclear clusters [MRu3(CO)14(m4-S)(m-k :h -pym)] (14–15) in
moderate yields. Both are characterised by comparison of their
1
1
spectroscopic data with those of [ReRu3(CO)14(m4-S)(m-k :h -
thpym)] (thpymH = tetrahydropyrimidine) which, on the basis of
an X-ray diffraction study, consists of an Re(CO)3(thpym) moiety
coupled with one Ru(CO)4 and two Ru(CO)3 units and is electron
precise with two metal–metal bonds reported by Deeming et al.44,45
The carbonyl regions of the IR spectra of 14 and 15 are very
Syntheses
Reaction of Re2(CO)10 with pymSH. A CH2Cl2 solution
(50 mL) of Re2(CO)10 (400 mg, 0.613 mmol), Me3NO (92 mg,
1.23 mmol) and pyrimidine-2-thiol (137 mg, 1.22 mmol) was
stirred at room temperature for 48 h during which time the colour
of the reaction mixture changed from pale yellow to orange. The
solution was then filtered through a short silica column (4 cm) to
remove excess Me3NO. The solvent was removed under reduced
pressure and the residue recrystallised from acetone–ethanol at
1
1
similar to that of [ReRu3(CO)14(m4-S)(m-k :h -thpym)] indicating
1
that the three are isostructural. The H NMR spectra of both
display two sets of resonances in the aromatic region attributed
to the presence of two isomers in solution relating to the relative
positions of the pyrimidinate and group 7 carbonyl centres,44 and
the FAB mass spectra show a parent molecular ion at 993 (14)
and 863 (15) together with fragmentation peaks due to successive
loss of fourteen carbonyl ligands which are consistent with our
proposed structures. The cleavage of the carbon–sulfur bond at
the ruthenium centre reflects the facile nature of the oxidative
addition at this metal.
◦
3
4 C to give [Re4(CO)12(m-k -pymS)4] (1) (318 mg, 68%) as orange
crystals. Anal. calcd for C28H12N8O12Re4S4: C 22.04, H 0.79, N
7.35. Found (%): C 22.36, H 0.87, N 7.43. IR (nCO, CH2Cl2): 2028
(vs), 1923 (s, br) cm-1. H NMR (CDCl3): d 7.44 (t, J = 5.6 Hz,
1
4H), 8.82 (dd, J = 2.0, 5.6 Hz, 4H), 8.97 (dd, J = 2.0, 5.6 Hz, 4H).
FAB MS: m/z 1526 (M+).
Reaction of Mn2(CO)10 with pymSH. A solution of Mn2(CO)10
(400 mg, 1.03 mmol), Me3NO (154 mg, 2.05 mmol) and
pyrimidine-2-thiol (230 mg, 2.05 mmol) in CH2Cl2 (50 mL) was
stirred at room temperature for 48 h during which time the colour
of the reaction mixture changed from pale yellow to yellow. The
solution was then filtered through a short silica column (4 cm) to
remove excess Me3NO. The solvent was removed under reduced
pressure and recrystallisation of the residue from acetone–hexane
Conclusions
Herein, we have documented the synthesis, structure, and re-
activity of tetranuclear square-type complexes of rhenium and
manganese. These macrocyclic supramolecules can be prepared,
in a predictable way, by assembling suitable polydentate bridging
ligand (e.g. pyrimidine-2-thiolate) and fac-M(CO)3 corners. The
self-assembly process possibly proceeds through the formation
◦
3
at 4 C afforded [Mn4(CO)12(m-k -pymS)4] (2) (366 mg, 72%) as
yellow crystals. Anal. calcd for C28H12Mn4N8O12: C 33.61, H 1.21,
N 11.20. Found (%): C 33.98, H 1.33, N 11.31. IR (nCO, CH2Cl2):
2
of the intermediate dimeric, [M2(CO)6(m-k -pymS)2] and trimeric
2
[M3(CO)9(m-k -pymS)3], although in no instance were these iso-
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2027 (vs), 1934 (s, br) cm-1. 1H NMR (CDCl3): d 6.63 (s, 4H), 8.46
(s, 4H), 8.61 (s, 4H). FAB MS: m/z 1000 (M+).
Reaction of 2 with en. To a CH2Cl2 solution (40 mL) of 2
(161 mg, 0.161 mmol) was added a large excess of ethylenediamine
(10 equiv.) and the mixture heated to reflux for 48 h. The solvent
was removed under vacuum and the residue chromatographed
by TLC on silica gel. Elution with hexane–acetone (3 : 2, v/v)
developed one band, which gave [Mn(CO)3(k -en)(k -pymS)] (7)
(136 mg, 68%) as yellow crystals after recrystallisation from
hexane–CH2Cl2 at 4 ◦C. Anal. calcd for C9H11MnN4O3S: C 34.85,
H 3.57, N 18.06. Found (%): C 35.12, H 3.69, N 18.17%. IR
(nCO, CH2Cl2): 2021 (vs), 1923 (s, br), 1902 (s, br) cm-1. 1H NMR
(CDCl3): d 8.25 (m, 2H), 6.84 (m, 1H), 4.92 (m, 4H), 2.95 (m, 4H).
FAB MS: m/z 310 (M+).
Reaction of 2 with PPh3. To a CH2Cl2 solution (40 mL) of
2 (100 mg, 0.100 mmol) was added PPh3 (105 mg, 0.401 mmol)
and the mixture was then stirred for 72 h at room temperature.
The solvent was removed by rotary evaporation and the residue
chromatographed by TLC on silica gel. Elution with hexane–
CH2Cl2 (3 : 7, v/v) developed two bands. The major band gave
2
1
2
[Mn(CO)3(PPh3)(k -pymS)] (3) (113 mg, 55%) as yellow crystals
after recrystallisation from hexane–CH2Cl2 at 4 ◦C while the
content of the minor band was too small for characterization.
Anal. calcd for C25H18MnN2O3PS: C 58.60, H 3.54, N 5.47. Found
(%): C 58.92, H 3.57, N 5.52. IR (nCO, CH2Cl2): 2026 (vs), 1944 (s,
br), 1913 (s, br) cm-1. 1H NMR (CDCl3): d 7.93 (s, 1H), 7.82–7.40
Reaction of 1 with dppm. A toluene solution (40 mL) of 1
(100 mg, 0.066 mmol) and dppm (100 mg, 0.260 mmol) was heated
to reflux for 7 h. The solvent was removed under vacuum and
the residue chromatographed by TLC on silica gel. Elution with
hexane–acetone (4 : 1, v/v) developed one major and several minor
1
(m, 16H), 6.37 (s, 1H). 31P{ H} NMR (CDCl3): d 58.3 (s). FAB
MS: m/z 512 (M+).
1
2
bands. The major band gave [Re(CO)3(k -pymS)(k -dppm)] (8)
(85 mg, 42%) as pale yellow crystals after recrystallisation from
hexane–CH2Cl2 at 4 ◦C while the content of the minor bands were
too small for characterization. Anal. calcd for C32H25N2O3P2ReS:
C 50.19, H 3.29, N 3.66. Found (%): C 50.52, H 3.42, N 3.42.
Reaction of 1 with bipy. A CH2Cl2 solution (40 mL) of 1
(100 mg, 0.066 mmol) and 2,2¢-bipyridine (42 mg, 0.269 mmol)
was heated to reflux for 24 h. The solvent was removed under
reduced pressure and the residue chromatographed by TLC on
silica gel. Elution with hexane–acetone (4 : 1, v/v) developed
two bands. The first band gave [Re(CO)3(k -bipy)(k -pymS)] (4)
(87 mg, 62%) as red crystals after recrystallisation from hexane–
acetone at 4 ◦C while the content of the second band was too small
for characterization. Anal. calcd for C17H11N4O3ReS: C 37.98, H
2.06, N 10.42. Found (%): C 38.29, H 2.15, N 10.53. IR (nCO,
CH2Cl2): 2018 (vs), 1919 (s, br), 1898 (s, br) cm-1. 1H NMR
(CDCl3): d 6.61 (t, J = 4.8 Hz, 1H), 7.45 (t, J = 5.6 Hz, 2H),
8.00 (t, J = 5.6 Hz, 2H), 8.15 (d, J = 5.6 Hz, 2H), 8.20 (d, J =
5.6 Hz, 2H), 9.18 (d, J = 4.8 Hz, 2H). FAB MS: m/z 538 (M+).
1
IR (nCO, CH2Cl2): 2027 (vs), 1934 (s, br), 1902 (s, br) cm-1. H
2
1
NMR (CDCl3): d 8.05 (m, 1H), 7.22 (m, 1H), 7.11–7.31 (m, 20H),
1
6.23 (m, 1H), 3.76 (m, 1H), 3.28 (m, 1H). 31P{ H} NMR (CDCl3):
d 13.7 (d, J = 88.4 Hz), 23.4 (d, J = 88.4 Hz). FAB MS: m/z
766 (M+).
Reaction of 2 with dppm. A cyclohexane solution (40 mL) of
2 (230 mg, 0.230 mmol) and dppm (340 mg, 0.885 mmol) was
heated to reflux for 48 h. The solvent was removed under reduced
pressure and the residue chromatographed by TLC on silica gel.
Elutionwithhexane–acetone(6 :4, v/v) developedone band which
2
1
Reaction of 1 with phen. A CH2Cl2 solution (40 mL) of
1 (100 mg, 0.066 mmol) and 1,10-phenanthroline (48 mg,
0.267 mmol) was heated to reflux for 24 h. The solvent was removed
under vacuum and the residue chromatographed by TLC on silica
gel. Elution with hexane gave one major and several minor bands.
The major band gave [Re(CO)3(k -phen)(k -pymS)] (5) (97 mg,
66%) as red crystals after recrystallisation from hexane–CH2Cl2
at 4 ◦C while the contents of the minor bands were too small for
characterization. Anal. calcd for C19H11N4O3ReS: C 40.64, H 1.97,
N 9.98. Found (%): C 40.98, H 2.09, N 10.06. IR (nCO, CH2Cl2):
2017 (vs), 1919 (s, br), 1898 (s, br) cm-1. 1H NMR (CDCl3): d 7.07
(t, J = 5.2 Hz, 1H), 7.87 (m, 2H), 8.02 (s, 2H), 8.56 (m, 4H), 9.40
(d, J = 5.02 Hz, 2H). FAB MS: m/z 562 (M+).
gave [Mn(CO)2(k -pymS)(k -dppm)2] (9) (241 mg, 26%) as orange
crystals after recrystallisation from hexane–acetone at 4 ◦C. Anal.
calcd for C56H47MnN2O2P4S: C 61.94, H 4.39, N 4.51. Found (%):
C 62.19, H 4.47, N 4.55. IR (nCO, CH2Cl2): 1923 (vs), 1848 (vs) cm-1.
1H NMR (CDCl3): d 3.42 (m, 2H), 3.64 (m, 2H), 6.52 (m, 1H),
2
1
1
7.00–7.39 (m, 41), 7.55 (m, 1H). 31P{ H} NMR (CDCl3): d 64.8
(br. s), 23.8 (sextet, J = 31.4, 56.7 Hz). FAB MS: m/z 990 (M+).
Reaction of 1 with dppe. A toluene solution (40 mL) of 1
(100 mg, 0.066 mmol) and dppe (105 mg, 0.264 mmol) was heated
to reflux for 24 h. The solvent was removed by rotary evaporation
and the residue chromatographed by TLC on silica gel. Elution
with hexane–acetone (7 : 3, v/v) developed two bands. The faster
2
1
moving band gave [Re(CO)2(k -pymS)(k -dppe)2] (10) (90 mg,
30%) as yellow crystals after recrystallisation from hexane–CH2Cl2
at 4 ◦C while the content of the second band was too small for
characterization. Anal. calcd for C58H51N2O2P4ReS: C 60.56, H
4.47, N 2.44. Found (%): C 60.92, H 4.60, N 2.47. IR (nCO, CH2Cl2):
1919 (vs), 1844 (vs), cm-1. 1H NMR (CDCl3): d 2.10 (m, 2H), 2.30
(m, 2H), 2.50 (m, 2H), 3.05 (m, 2H), 5.40 (t, J = 5.0 Hz, 1H), 6.25
Reaction of 2 with phen. 1,10-Phenanthroline (116 mg,
0.644 mmol) was added to a CH2Cl2 solution (40 mL) of 2 (161 mg,
0.161 mmol) and the mixture heated to reflux for 48 h. The solvent
was removed under vacuum and the residue chromatographed
by TLC on silica gel. Elution with hexane–acetone (3 : 2, v/v)
2
1
developed one band, which gave [Mn(CO)3(k -phen)(k -pymS)]
(6) (172 mg, 62%) as red crystals after recrystallisation from
hexane–CH2Cl2 at 4 ◦C. Anal. calcd for C19H11MnN4O3S: C 53.03,
H 2.58, N 13.02. Found (%): C 53.41, H 2.67, N 13.11%. IR
(nCO, CH2Cl2): 2020 (vs), 1933 (s, br), 1918 (s, br) cm-1. 1H NMR
(CDCl3): d 9.53 (m, 2H), 8.38 (m, 2H), 8.16 (m, 2H), 7.91 (m, 2H),
7.75 (m, 2H), 6.59 (m, 1H). FAB MS: m/z 430 (M+).
1
(d, J = 5.0 Hz, 2H), 7.10–7.60 (m, 40H). 31P{ H} NMR (CDCl3):
d 35.0 (s), 47.6 (s). FAB MS: m/z 1150 (M+).
Reaction of 2 with dppe. A toluene solution (40 mL) of 2
(200 mg, 0.200 mmol) and dppe (325 mg, 0.817 mmol) was heated
to reflux for 24 h. The solvent was removed by rotary evaporation
and the residue chromatographed by TLC on silica gel. Elution
4464 | Dalton Trans., 2009, 4458–4467
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This journal is
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Dalton Trans., 2009, 4458–4467 | 4465
©

View Article Online
with hexane–acetone (3 : 2, v/v) developed one band which
of the third band was too small for characterization. Anal. calcd
for C18H3MnN2O14Ru3S: C 25.10, H 0.35, N 3.25. Found (%): C
25.37, H 0.38, N 3.29. IR (nCO, CH2Cl2): 2118 (w), 2081 (m), 2058
2
2
gave [Mn(CO)2(k -pymS)(k -dppe)] (11) (189 mg, 38%) as orange
crystals after recrystallisation from hexane–acetone at 4 ◦C. Anal.
calcd for C32H27MnN2O2P2S: C 67.88, H 4.78, N 2.83. Found (%):
C 68.22, H 4.90, N 2.89. IR (nCO, CH2Cl2): 1937 (vs), 1858 (vs)
cm-1. 1H NMR (CDCl3): d 2.01–3.36 (m, 4H), 6.48 (m, 1H), 7.02–
1
(vs), 2046 (s), 2006 (m), 1979 (m), 1961 (m), 1940 (m) cm-1. H
NMR (CDCl3) for major isomer: d 6.95 (s, 1H), 7.86 (s, 1H), 9.51
(s, 1H). FAB MS: m/z 863 (M+).
1
7.88 (m, 21H), 8.19 (m, 1H). 31P{ H} NMR (CDCl3): d 98.9 (s),
77.6 (s). FAB MS: m/z 620 (M+).
Crystallography
Reaction of 1 with [Os3(CO)10(NCMe)2]. A benzene solution
(40 mL) of [Os3(CO)10(NCMe)2] (250 mg, 0.268 mmol) and 1
(100 mg, 0.066 mmol) was heated to reflux for 3 h. The solvent was
removed by rotary evaporation and the residue chromatographed
by TLC on silica gel. Elution with hexane–acetone (4 : 1, v/v)
gave one major and several minor bands. The major band afforded
Single crystals were mounted on fibres and diffraction data
collected at low temperature (see Table 1) on Enraf Nonius
CAD4 (1, 2, 4, 10), Nonius Kappa CCD (5, 6, 7, 12) and
Bruker AXS SMART APEX CCD (3) diffractometers using
˚
MoKa radiation (l = 0.71073 A). Data collection, indexing and
initial cell refinements were all done using SMART47 software.
Data reduction was accomplished with SAINT48 software and the
DIFABS49 and SADABS50 program was used to apply empirical
absorption corrections. The structures were solved by direct
methods51 and refined by full matrix least-squares.52 All non-
hydrogen atoms were refined anisotropically and hydrogen atoms
were included using a riding model. Scattering factors were taken
from International Tables for X-ray Crystallography.53 Additional
details of data collection and structure refinement are given in
Table 1.
2
[ReOs3(CO)13(m3-k -pymS)] (12) (130 mg, 40%) as red crystals from
hexane–CH2Cl2 at 4 ◦C while the content of the second band was
too small for characterization. Anal. calcd for C17H3N2O13Os3ReS:
C 16.57, H 0.25, N 2.27. Found (%): C 16.74, H 0.28, N 2.33. IR
(nCO, CH2Cl2): 2112 (m), 2044 (vs), 2029 (m), 2013 (m), 1985 (w),
1965 (m, br) cm-1. 1H NMR (CDCl3): d 7.31 (t, J = 5.6 Hz, 1H),
8.80 (dd, J = 2.4, 5.6 Hz, 1H), 9.66 (dd, J = 2.4, 5.6 Hz, 1H). FAB
MS: m/z 1234 (M+).
Reaction of 2 with [Os3(CO)10(NCMe)2]. A benzene solution
(40 mL) of [Os3(CO)10(NCMe)2] (380 mg, 0.407 mmol) and 2
(100 mg, 0.100 mmol) was heated to reflux for 3 h. The solvent was
removed under reduced pressure and the residue chromatographed
by TLC on silica gel. Elution with hexane–acetone (4 : 1, v/v)
gave one major and several minor bands. The major band
Acknowledgements
Part of this work was carried out by S. E. K. at the University of
Go¨ttingen. S. E. K. gratefully acknowledges the von Humboldt
Foundation for a Fellowship to spend time at the University of
Go¨ttingen.
2
afforded [MnOs3(CO)13(m3-k -pymS)] (13) (136 mg, 31%) as red
crystals from hexane–CH2Cl2 at 4 ◦C while the content of the
second band was too small for characterization. Anal. calcd for
C17H3MnN2O13Os3S: C 18.55, H 0.27, N 2.54. Found (%): C 18.79,
H 0.31, N 2.58. IR (nCO, CH2Cl2): 2110 (m), 2042 (vs), 2027 (m),
2002 (m), 1981 (w), 1961 (m, br) cm-1. 1H NMR (CDCl3): d 7.20 (s,
br, 1H), 8.80 (s, br, 1H), 10.20 (s, br, 1H). FAB MS: m/z 1102 (M+).
References
1 S. Leininger, B. Olenyuk and P. J. Stang, Chem. Rev., 2000, 100, 853.
2 B. J. Holliday and C. A. Mirkin, Angew. Chem., Int. Ed., 2001, 40, 2022.
3 N. C. Gianneschi, M. S. Masar III and C. A. Mirkin, Acc. Chem. Res.,
2005, 38, 825.
Reaction of 1 with Ru3(CO)12. A toluene solution (40 mL) of
Ru3(CO)12 (256 mg, 0.400 mmol) and 1 (154 mg, 0.101 mmol)
was heated to reflux for 1 h. The solvent was removed in vacuo
and the residue chromatographed by TLC on silica gel. Elution
with hexane–acetone (4 : 1, v/v) developed three bands. The
first band was unreacted Ru3(CO)12 (trace). The second band
4 M. Fujita, Acc. Chem. Res., 1999, 32, 53.
5 P. J. Stang and D. Cao, J. Am. Chem. Soc., 1994, 116, 4981.
6 P. J. Stang, D. H. Cao, S. Saito and A. M. Arif, J. Am. Chem. Soc.,
1995, 117, 6273.
7 P. J. Stang and B. Olenyuk, Angew. Chem., Int. Ed. Engl., 1996, 35, 732.
8 P. J. Stang, B. Olenyuk, J. Fan and A. M. Arif, Organometallics, 1996,
15, 904.
9 P. J. Stang and J. A. Whiteford, Organometallics, 1994, 13, 3776.
10 M. Fujita, S. Nagao, M. Iida, K. Ogata and K. Ogura, J. Am. Chem.
Soc., 1993, 115, 1574.
11 M. Fujita, J. Yazaki and K. Ogura, J. Am. Chem. Soc., 1990, 112, 5645.
12 M. Fujita, K. Umemoto, M. Yoshizawa, N. Fujita, T. Kusukawa and
K. Biradha, Chem. Commun., 2001, 509.
13 M. Fujita, S. Nagao, M. Iida, K. Ogata and K. Ogura, J. Am. Chem.
Soc., 1993, 115, 1574.
1
1
afforded [ReRu3(CO)14(m4-S)(m2-k :h -pym)] (14) (176 mg, 44%)
as red crystals from hexane–CH2Cl2 at 4 ◦C while the content of
the third band was too small for characterization. Anal. calcd for
C18H3N2O14ReRu3S: C 21.78, H 0.30, N 2.82. Found (%): C 21.93,
H 0.31, N 2.84. IR (nCO, CH2Cl2): 2114 (w), 2080 (m), 2056 (vs),
2044 (s), 2003 (m), 1975 (m), 1955 (m) cm-1. 1H NMR (CDCl3) for
major isomer: d 7.69 (s, 1H), 7.51 (s, 1H), 7.11 (s, 1H). FAB MS:
m/z 993 (M+).
14 M. Fujita, F. Ibukuro, H. Seki, O. Kamo, M. Imanari and K. Ogura,
J. Am. Chem. Soc., 1996, 118, 899.
15 P. M. Stricklen, E. J. Volcko and J. G. Verkade, J. Am. Chem. Soc.,
1983, 105, 2494.
16 R. V. Slone, J. T. Hupp, C. L. Stern and T. E. Albrecht-Schmitt, Inorg.
Chem., 1996, 35, 4096.
17 S.-S. Sun and A. J. Lees, J. Am. Chem. Soc., 2000, 122, 8956.
18 S.-S. Sun, A. S. Silva, I. M. Brin and A. J. Lees, Inorg. Chem., 2000, 39,
1344.
19 S.-S. Sun and A. J. Lees, Inorg. Chem., 2000, 38, 4181.
20 H. Yan, G. Su¨ss-Fink, A. Neels and H. Stoeckli-Evans, J. Chem. Soc.,
Dalton Trans., 1997, 4345.
Reaction of 2 with Ru3(CO)12. A toluene solution (40 mL) of
Ru3(CO)12 (256 mg, 0.400 mmol) and 2 (100 mg, 0.100 mmol)
was heated to reflux for 30 min. The solvent was removed by
rotary evaporation and the residue chromatographed by TLC on
silica gel. Elution with hexane–acetone (4 : 1, v/v) developed three
bands. The first band was unreacted Ru3(CO)12 (trace). The second
1
1
band afforded [MnRu3(CO)14(m4-S)(m-k :h -pym)] (15) (159 mg,
46%) as red crystals from hexane–CH2Cl2 at 4 ◦C while the content
4466 | Dalton Trans., 2009, 4458–4467
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21 K. D. Benkstein, J. T. Hupp and C. L. Stern, Inorg. Chem., 1998, 37,
5404.
38 H. Egold, D. Schwarze and U. Flo¨rke, J. Chem. Soc., Dalton Trans.,
1999, 3203.
39 S. E. Kabir, F. Ahmed, S. Ghosh, M. R. Hassan, M. S. Islam, A.
Sharmin, D. A. Tocher, D. T. Haworth, S. V. Lindeman, T. A. Siddique,
D. W. Bennett and K. I. Hardcastle, J. Organomet. Chem., 2008, 693,
2657.
22 S. M. Woessner, J. B. Helms, Y. Shen and B. P. Sullivan, Inorg. Chem.,
1998, 37, 5406.
23 K. D. Benkstein, J. T. Hupp and C. L. Stern, J. Am. Chem. Soc., 1998,
120, 12982.
24 T. Kajiwara and T. Ito, J. Chem. Soc., Chem. Commun., 1994, 1773.
25 R. V. Slone, D. I. Yoon, R. M. Calhoun and J. T. Hupp, J. Am. Chem.
Soc., 1995, 117, 11813.
26 S. E. Kabir, K. M. A. Malik, E. Molla and M. A. Mottalib, J.
Organomet. Chem., 2000, 616, 157, and references therein.
27 A. J. Deeming, M. Karim, P. A. Bates and M. B. Hursthouse,
Polyhedron, 1988, 7, 1401.
28 (a) S. E. Kabir, M. M. Karim, K. Kundu, S. M. B. Ullah and K. I.
Hardcastle, J. Organomet. Chem., 1996, 517, 155; (b) M. Islam, C. A.
Johns, S. E. Kabir, K. Kundu, K. M. A. Malik and S. M. B. Ullah, J.
Chem. Crystallogr., 1999, 29, 1001.
40 D. J. Rose, K. P. Maresca, P. B. Kettler, Y. D. Chang, V. Soghomomian,
Q. Chen, M. J. Abrams, S. K. Larsen and J. Zubieta, Inorg. Chem.,
1996, 35, 3548.
41 A. K. Das, E. Bulak, B. Sarkar, F. Lissner, T. Schleid, M. Niemeyer, J.
Fiedler and W. Kaim, Organometallics, 2008, 27, 218.
42 S. E. Kabir, unpublished results.
43 S. Ghosh, S. E. Kabir, S. Pervin, A. K. Raha, G. M. G. Hossain, D. T.
Haworth, S. V. Lindeman, T. A. Siddiquee, D. W. Bennett, L. Salassa
and H. W. Roesky, Dalton Trans., 200910.1039/b819226j.
44 A. J. Deeming, M. Karim, N. I. Powell and K. I. Hardcastle, Polyhedron,
1990, 9, 623.
29 M. P. Brown, J. Buckett, M. M. Harding, R. M. Lynden-Bell, M. J.
Mays and K. W. Woulfe, J. Chem. Soc., Dalton Trans., 1991, 3097.
30 G. Albertin, S. Antoniutti, A. Bacchi, A. Celebrin, G. Pelizzi and G.
Zanardo, Dalton Trans., 2007, 661.
31 W. Liu, R. Wang, X.-H. Zhou, J.-L. Zuo and X.-Z. You,
Organometallics, 2008, 27, 126.
45 B. Cockerton, A. J. Deeming, M. Karim and K. I. Hardcastle, J. Chem.
Soc., Dalton Trans., 1991, 431.
46 B. F. G. Johnson, J. Lewis and D. A. Pippard, J. Chem. Soc., Dalton
Trans., 1981, 407.
47 SMART Version 5.628, Bruker AXS, Inc.: Madison, WI, 2003.
48 SAINT Version 6.36, Bruker AXS, Inc.: Madison, WI, 2002.
49 N. Walker and D. Stuart, Acta Crystallogr., Sect. A: Found. Crystallogr.,
1983, 39, 158.
50 G. Sheldrick, SADABS Version 2.10, University of Go¨ttingen,
2003.
32 S. Top, M. Gunn, G. Jaouen, J. Vaissermann, J.-C. Daran and M. J.
McGlinchey, Organometallics, 1992, 11, 1201.
ˆ
33 R. Garcia, A. Domingos, A. Paulo, I. Santos and R. Alberto, Inorg.
Chem., 2002, 41, 2422.
51 Program XS from SHELXTL package, V. 6.12, Bruker AXS, Inc.:
34 R. Chiozzone, R. Gonza´lez, C. Kremer, M. F. Cerda´, D. Armentano,
G. D. Munno, J. Mart´ınez-Lillo and J. Faus, Dalton Trans., 2007, 653.
35 P. O. Nubel, S. R. Wilson and T. L. Brown, Organometallics, 1983, 2,
515.
Madison, WI, 2001.
52 Program XL from SHELXTL package, V. 6.12, Bruker AXS, Inc.:
Madison, WI, 2001.
53 International Tables for X-Ray Crystallography, Volume C, ed. A. J. C.
Wilson, Kynoch, Academic Publishers: Dordrecht, 1992; Tables 6.1.1.4
(pp. 500–502) and 4.2.6.8 (pp. 219–222).
36 R. D. Adams and M. Huang, Organometallics, 1996, 15, 3644.
37 M. A. Reynolds, I. A. Guzei and R. J. Angelici, Chem. Commun., 2000,
513.
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