Bromination and nitration reactions of metallated (Ru and Os) multiaromatic ligands and crystal structures of selected products

Article abstract of DOI:10.1016/S0022-328X(99)00724-X

Three nitrogen-containing aromatic heterocycles, 2-(1′-naphthyl)pyridine, 2-phenylquinoline, and 2,3-diphenylquinoxaline, have been mercurated in the naphthyl or phenyl ring 2-position and then symmetrised to form the mercury compounds Ar₂Hg (Ar=Nppy (3), Phqn (1) or Dpqx (5), respectively). These reagents are suitable for trans-metallation and reaction with MHCl(CO)(PPh₃)₃ affords the complexes M(η²-C,N-Ar)Cl(CO)(PPh₃)₂, (6, M=Ru, Ar=Nppy; 7, M=Os, Ar=Nppy; 8, M=Ru, Ar=Phqn; 9, M=Os, Ar=Phqn; 10, M=Ru, Ar=Dpqx; 11, M=Os, Ar=Dpqx) in which each product features an aryl ligand that forms a strongly chelated five-membered ring through coordination of the heterocyclic N atom. The chloride ligand in each of the complexes 6-11 can be replaced by dimethyl dithiocarbamate to give ultimately the mono-triphenylphosphine complexes, M(η²-Ar)(η²-S₂CNMe ₂)(CO)(PPh₃) (12, M=Ru, Ar=Nppy; 13, M=Os, Ar=Nppy; 14, M=Ru, Ar=Phqn; 15, M=Os, Ar=Phqn; 16, M=Ru, Ar=Dpqx; 17, M=Os, Ar=Dpqx). Similarly, compound 10 when treated with Na(acac) gives Ru(η²-Dpqx)(η²-acac)(CO)(PPh₃) (18), while treatment with trifluoroacetic acid gives Ru(η²-Dpqx)(O₂CCF₃)(CO)(PPh ₃)₂ (19). Many of these complexes were found to be very robust, making them suitable for electrophilic aromatic substitution reactions under harsh conditions. In each case, the presence of the metal had both an activating and a directing effect on the aryl ring to which it was bonded. Bromination or nitration reactions, both of which are not normally possible with organometallic substrates, were carried out successfully, giving rise to monobrominated or dinitrated products, respectively. The following compounds were characterised, M(η²-Ar-4-Br)Cl(CO)(PPh₃)₂ (20, M=Ru, Ar=Phqn; 21, M=Os, Ar=Phqn; 22, M=Ru, Ar=Dpqx; 24, M=Os, Ar=Dpqx), M(η²-Dpqx-4-Br)(η²-S₂CNMe ₂)(CO)(PPh₃) (23, M=Ru; 25, M=Os), Os(η²-Ar)Cl(CO)(PPh₃)₂ (26, Ar=Nppy-6,8-(NO₂)₂; 27, Ar=Phqn-4,6-(NO₂)₂). Crystal structures of compounds 7, 12, 15, 18, 19, 21, 23 and 25 have been determined.

Full text of DOI:10.1016/S0022-328X(99)00724-X

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 598 (2000) 262–275
Bromination and nitration reactions of metallated (Ru and Os)
multiaromatic ligands and crystal structures of selected products
Alex M. Clark, Clifton E.F. Rickard, Warren R. Roper* 1, L. James Wright* 2
Department of Chemistry, The Uni6ersity of Auckland, Pri6ate Bag, 92019 Auckland, New Zealand
Received 18 October 1999; received in revised form 23 November 1999
Abstract
Three nitrogen-containing aromatic heterocycles, 2-(1%-naphthyl)pyridine, 2-phenylquinoline, and 2,3-diphenylquinoxaline, have
been mercurated in the naphthyl or phenyl ring 2-position and then symmetrised to form the mercury compounds Ar2Hg
(Ar=Nppy (3), Phqn (1) or Dpqx (5), respectively). These reagents are suitable for trans-metallation and reaction with
MHCl(CO)(PPh3)3 affords the complexes M(h2-C,NꢀAr)Cl(CO)(PPh3)2, (6, M=Ru, Ar=Nppy; 7, M=Os, Ar=Nppy; 8,
M=Ru, Ar=Phqn; 9, M=Os, Ar=Phqn; 10, M=Ru, Ar=Dpqx; 11, M=Os, Ar=Dpqx) in which each product features an
aryl ligand that forms a strongly chelated five-membered ring through coordination of the heterocyclic N atom. The chloride
ligand in each of the complexes 6–11 can be replaced by dimethyl dithiocarbamate to give ultimately the mono-triphenylphos-
phine complexes, M(h2-Ar)(h2-S2CNMe2)(CO)(PPh3) (12, M=Ru, Ar=Nppy; 13, M=Os, Ar=Nppy; 14, M=Ru, Ar=Phqn;
15, M=Os, Ar=Phqn; 16, M=Ru, Ar=Dpqx; 17, M=Os, Ar=Dpqx). Similarly, compound 10 when treated with Na(acac)
gives Ru(h2-Dpqx)(h2-acac)(CO)(PPh3) (18), while treatment with trifluoroacetic acid gives Ru(h2-Dpqx)(O2CCF3)(CO)(PPh3)2
(19). Many of these complexes were found to be very robust, making them suitable for electrophilic aromatic substitution
reactions under harsh conditions. In each case, the presence of the metal had both an activating and a directing effect on the aryl
ring to which it was bonded. Bromination or nitration reactions, both of which are not normally possible with organometallic
substrates, were carried out successfully, giving rise to monobrominated or dinitrated products, respectively. The following
compounds were characterised, M(h2-Ar-4-Br)Cl(CO)(PPh3)2 (20, M=Ru, Ar=Phqn; 21, M=Os, Ar=Phqn; 22, M=Ru,
Ar=Dpqx; 24, M=Os, Ar=Dpqx), M(h2-Dpqx-4-Br)(h2-S2CNMe2)(CO)(PPh3) (23, M=Ru; 25, M=Os), Os(h2-
Ar)Cl(CO)(PPh3)2 (26, Ar=Nppy-6,8-(NO2)2; 27, Ar=Phqn-4,6-(NO2)2). Crystal structures of compounds 7, 12, 15, 18, 19, 21,
23 and 25 have been determined. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; Osmium; ortho-Metallation; trans-Metallation; Electrophilic aromatic substitution; X-ray structures
1. Introduction
We have previously shown that by utilising the mer-
cury reagent, Phpy2Hg, which can be prepared by
ortho-mercuration of the phenyl ring of 2-
phenylpyridine followed by symmetrisation, the 2-
phenylpyridyl ligand can be readily transferred to
ruthenium and osmium complexes by reaction with the
Cyclometallated aryl ligands of platinum group metal
complexes have long been known, and many examples
exist in the literature. For example, the metallation of
2-phenylpyridine and derivatives thereof with a variety
of electrophilic metal substrates occurs in the phenyl
ring (see Scheme 1), ortho to the attached pyridyl
substituent. This results in the formation of a five-mem-
bered chelate ring, structurally similar to complexes of
the bipyridine ligand [1].
1 *Corresponding author. Tel.: +64-9-3737999; fax: +64-9-
3737422; w.roper@auckland.ac.nz
2 *Corresponding author. Tel.: +64-9-3737999; fax: +64-9-
3737422; l.j.wright@auckland.ac.nz
Scheme 1.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00724-X

A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
263
Electrophilic substitution of organometallic ligands is
currently a very uncommon method of introducing
functional groups. Although there are numerous exam-
ples of substituted s-aryl complexes of transition
metals, the functionality is almost invariably introduced
to the organic fragment prior to its attachment to a
metal. We are interested in extending our studies on the
electrophilic substitution reactions of organometallic
ligands to include more complicated aromatic systems,
as well as applying new techniques for introducing
functional groups.
Scheme 2.
substrates MHCl(CO)(PPh3)3 (M=Ru, Os) [2] to form
the corresponding cyclometallated products shown in
Scheme 2. Similar trans-metallation reactions using
mercury reagents of the form Ar2Hg have been used to
deliver a wide variety of s-bound aryl fragments,
chelating or non-chelating, to these ruthenium and
osmium substrates. In each case the same stoichiometry
is observed, with the deposition of elemental mercury,
loss of one triphenylphosphine ligand and the forma-
tion of one equivalent of the unmetallated ligand, ArH
[3].
It was found that complexes with chelating
organometallic ligands, especially M(h2-Phpy)Cl(CO)-
(PPh3)2, were very robust, and seemingly resistant to a
variety of reaction conditions that few organometallic
compounds are able to withstand without suffering
metal–carbon bond cleavage. This is thought to be due
mainly to the favourable five-membered chelate ring.
Because of this robustness, it was possible to take
advantage of a specific activating and directing effect
associated with these metal-ligand fragments. For both
the ruthenium and osmium complexes, the s-bound
phenyl group of the Phpy ligand was found to be highly
activated toward electrophilic aromatic substitution
reactions, and both nitration and bromination reactions
were able to be conducted under relatively mild con-
ditions with excellent selectivity, and no discernible
decomposition due to loss of the metal–carbon s-
bond.
2. Results and discussion
2.1. Mercuration
The aryl rings of the three organic compounds shown
in Scheme 3, 2-(1%-naphthyl)pyridine, 2-phenylquinoline
and 2,3-diphenylquinoxaline have each been directly
mercurated in the position ortho to the nitrogen-con-
taining attached side-arm. As shown in Scheme 3, the
ortho-metallated forms of these ligands are denoted as
Nppy, Phqn and Dpqx, respectively. The new com-
pounds ArHgCl (2, Ar=Nppy; 4, Ar=Dpqx), have
been characterised. Upon symmetrisation, the
organomercury chlorides, ArHgCl, yield Ar2Hg (1,
Ar=Phqn; 3, Ar=Nppy; 5, Ar=Dpqx). In the case
of 2,3-diphenylquinoxaline, both phenyl rings could, in
principle, undergo mercuration. Although in the related
palladation reaction of this compound both rings are
cyclopalladated [4], in this study mercuration was ob-
served to occur in one position only, as indicated.
2.2. Trans-metallation
The reaction of MHCl(CO)(PPh3)3 (M=Ru, Os)
with Ar2Hg gives rise to M(h2-Ar)Cl(CO)(PPh3)2 (6,
M=Ru, Ar=Nppy; 7, M=Os, Ar=Nppy; 8, M=
Ru, Ar=Phqn; 9, M=Os, Ar=Phqn; 10, M=Ru,
Ar=Dpqx; 11, M=Os, Ar=Dpqx) as shown in
Scheme 4 (IR data for all new complexes are given in
Scheme 3.

264
A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
Scheme 4.
Table 1). The yields are good, although not as satisfac-
tory as for some of the analogous trans-metallation
reactions involving smaller, simpler aryl ligands. Com-
plexes of the Phpy and Nppy ligands are yellow or pale
orange, colours typical of related coordinatively satu-
rated ruthenium(II) and osmium(II) compounds. Com-
plexes of the Dpqx ligand are very intensely coloured,
being deep red (ruthenium) or dark purple (osmium).
The strong coloration is probably due to a charge-
transfer transition, rather than coordinative unsatura-
tion at the metal centre since the coordination face of
this ligand is structurally very similar to Phqn.
iodide as solvent did not result in methylation at nitro-
gen. Recrystallisation of Ru(h2-Dpqx)Cl(CO)(PPh3)2
(10) in the presence of trifluoroacetic acid produced the
compound Ru(h2-Dpqx)(h1-O2CCF3)(CO)(PPh3)2 (19),
in which the labile chloride ligand was replaced by
monodentate trifluoroacetate. This product has been
structurally characterised by X-ray crystallography (see
below).
2.3. Metal-centred deri6atisation
The
reactivity
of
the
complexes
M(h2-
All of the resultant complexes were found to be very
robust and easy to handle, being stable in air and not
decomposed by conditions such as recrystallisation in
the presence of mineral acids. The uncoordinated nitro-
gen atom in each of the complexes 10 and 11 was not
very basic, and in fact was quite unreactive. Recrystalli-
sation of either the ruthenium or osmium compound in
the presence of dilute HCl gave rise to unchanged
starting material, and heating under reflux in methyl
Ar)Cl(CO)(PPh3)2 (6–11) largely parallels that of the
previously reported complexes, M(h2-Phpy)Cl(CO)-
(PPh3)2 [2]. One method of derivatisation that was
applied to all of the complexes 6–11 involved removal
of the chloride ligand from each using AgSbF6, fol-
lowed by treatment of the resulting cation with sodium
dimethyldithiocarbamate. The intermediate compound,
in which the dithiocarbamate ligand was bound in a
monodentate fashion, was in some cases observed by
Table 1
Infrared data for ruthenium and osmium complexes
Complex
w(CO) (cm−1
)
Other bands
Ru(h2-Nppy)Cl(CO)(PPh3)2 (6)
1915 s
1898 s
1927 s
1910 s
1939 s
1920 s
1923 s
1908 s
1935 s
1917 s
1938 s
1921 s
1933 s
1949 s
1929 s
1907 s
1955 s
1949 s
1922 s
1931 s
1916 s
1943 s
Os(h2-Nppy)Cl(CO)(PPh3)2 (7)
Ru(h2-Phqn)Cl(CO)(PPh3)2 (8)
Os(h2-Phqn)Cl(CO)(PPh3)2 (9)
Ru(h2-Dpqx)Cl(CO)(PPh3)2 (10)
Os(h2-Dpqx)Cl(CO)(PPh3)2 (11)
Ru(h2-Nppy)(h2-S2CNMe2)(CO)(PPh3) (12)
Os(h2-Nppy)(h2-S2CNMe2)(CO)(PPh3) (13)
Ru(h2-Phqn)(h2-S2CNMe2)(CO)(PPh3) (14)
Os(h2-Phqn)(h2-S2CNMe2)(CO)(PPh3) (15)
Ru(h2-Dpqx)(h2-S2CNMe2)(CO)(PPh3) (16)
Os(h2-Dpqx)(h2-S2CNMe2)(CO)(PPh3) (17)
Ru(h2-Dpqx)(h2-acac)(CO)(PPh3) (18)
Ru(h2-Dpqx)(O2CCF3)(CO)(PPh3)2 (19)
Ru(h2-Phqn-4-Br)Cl(CO)(PPh3)2 (20)
Os(h2-Phqn-4-Br)Cl(CO)(PPh3)2 (21)
Ru(h2-Dpqx-4-Br)Cl(CO)(PPh3)2 (22)
Ru(h2-Dpqx-4-Br)(h2-S2CNMe2)(CO)(PPh3)(23)
Os(h2-Dpqx-4-Br)Cl(CO)(PPh3)2 (24)
Os(h2-Dpqx-4-Br)(h2-S2CNMe2)(CO)(PPh3) (25)
Os(h2-Nppy-6,8-(NO2)2)Cl(CO)(PPh3)2 (26)
Os(h2-Phqn-4,6-(NO2)2)Cl(CO)(PPh3)2 (27)
1503 m (dithiocarbamate)
1531 m (dithiocarbamate)
1513 m (dithiocarbamate)
1515 m (dithiocarbamate)
1519 m (dithiocarbamate)
1515 m (dithiocarbamate)
1515 m (acetylacetonate)
1682 m (trifluoroacetate)
1504 m (dithiocarbamate)
1505 m (dithiocarbamate)
1538, 1531 m (nitro)
1520, 1504 m (nitro)

A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
265
Scheme 5.
1H-NMR spectroscopy. These intermediates rapidly
lost one triphenylphosphine ligand in solution to give
the complexes in which the dithiocarbamate ligand is
bound to the metal in a bidentate manner. The com-
pounds 12–17 were formed in this way (see Scheme 5).
Qualitatively, it was observed that the loss of the
triphenylphosphine ligand proceeded more rapidly
when the metal was ruthenium than when it was os-
mium, and also more rapidly for the two ligands, Phqn
and Dpqx, than for Nppy. These latter observations
could possibly be a consequence of steric effects since
Nppy must bring considerably less steric bulk to the
metal coordination sphere than the other two ligands.
It was also found that Ru(h2-Dpqx)Cl(CO)(PPh3)2
(10) reacted with sodium acetylacetonate in a manner
similar to the reactions with dimethyldithiocarbamate,
to form Ru(h2-Dpqx)(h2-acac)(CO)(PPh3) (18).
each case, a high yield of the product was obtained in
which a bromo substituent had been introduced in the
4-position of the phenyl ring, directly para to the
metal–carbon bond.
Although it would be expected that the 2-position,
ortho to the metal–carbon bond, would also be elec-
tronically activated, in none of the bromination reac-
tions was substitution observed in this position. Similar
results have been observed for bromination of the
analogous compounds containing the smaller Phpy [2]
or 8-quinolyl [5] ligands. In these cases, the position
para to the metal–aryl bond was substituted, and under
no conditions was substitution on the heterocyclic ring
observed.
It is interesting to note that for the ligands Phqn and
Dpqx, no substitution occurs in the aromatic rings
which are not activated by the coordinated metal. This
supports the supposition that it is the activating and
directing effect of the metal substituent which makes
such electrophilic aromatic substitution reactions possi-
ble under conditions which would be considered mild
for similar non-metallated substrates.
2.4. Electrophilic aromatic substitution reactions
The cyclometallated ligands in the complexes 6–11
were found to be suitable substrates for electrophilic
aromatic substitution reactions.
The complexes 22 and 24, which contain the bromi-
nated h2-Dpqx ligand, both react with dimethyldithio-
2.4.1. Bromination
Reaction of organometallic compounds with molecu-
lar bromine usually results in cleavage of any metal–
carbon s-bonds that are present, although in some
cases where suitable higher oxidation states of the metal
are accessible (e.g. PtII), oxidative addition at the metal
centre may be observed without metal–carbon bond
cleavage. However, we have previously demonstrated
that it is possible to brominate s-bonded aryl ligands at
specific positions on the aromatic ring without metal–
carbon bond cleavage, provided the metal–aryl bonds
are very robust [2,5].
It was found that bromination of the cyclometallated
ligands in the complexes 8, 9, 10, and 11, did occur
smoothly and cleanly as shown in Scheme 6. One
equivalent of bromine was delivered in the form of
[pyridineH]Br3, a conveniently stable solid. A catalytic
quantity of iron powder was also added, without which
the reaction did not proceed at room temperature. In
Scheme 6.

266
A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
moiety is transmitted through the naphthyl ring, and the
6- and 8-positions are activated.
2.5. Crystal-structure determinations
Crystallographic details for the structure determina-
tions of compounds 7, 12, 15, 18, 19, 21, 23, and 25 are
presented in Table 2, and molecular structures are
presented in Figs. 1–8. The remaining crystallographic
data has been deposited with the Cambridge Crystallo-
graphic Data Centre.
The principal value of the structural data lies in
confirmation of the position of substitution of the
aromatic ring. However, some useful conclusions can
also be drawn, and for the purposes of comparison a
summary of the MꢀC and MꢀN bond distances and
CꢀMꢀN angles is given in Table 3. The metalꢀaryl
bond distances vary only slightly depending on the
organometallic ligand and the arrangement of the ancil-
liary ligands. The four ruthenium complexes struc-
turally characterised have an average metalꢀaryl bond
Scheme 7.
carbamate in the same way as the corresponding non-
functionalised complexes and the resultant mono-tri-
phenylphosphine products, M(h2-Dpqx-4-Br)(h2-S2-
CNMe2)(CO)(PPh3) (23, M=Ru; 25, M=Os), are
formed. Both 23 and 25 have been structurally
characterised by X-ray crystallography (see below).
,
,
distance of 2.04 A, the osmium complexes 2.05 A. A
search of the Cambridge Crystallographic Structural
Database revealed 196 ruthenium–aryl complexes, with
,
an average bond distance of 2.108(6) A, and for os-
mium, 106 complexes, with an average bond distance of
2.4.2. Nitration
Unlike bromination, we have in the past been success-
ful at nitrating compounds with metal–aryl linkages
that are more fragile than those in compounds 6–11,
albeit in low yields and often with numerous byproducts
[6]. The reaction is much more straightforward,
however, when robust substrates with chelated aryl
ligands are used. Reasonably high yields and a single
major product are typical in these cases [5].
,
2.13(10) A. Therefore, the complexes of the ligands
Nppy, Phqn and Dpqx possess shorter than average
metal–aryl bonds, no doubt attributable to the pres-
ence of the five-membered chelate ring.
The structurally characterised complexes given in
Table 3 exhibit averaged metalꢀnitrogen bond distances
of 2.16 (RuꢀN), and 2.19 A (OsꢀN). A CCSD search
,
for compounds with five-membered chelate rings featur-
ing one or two pyridyl nitrogen donors (mostly com-
plexes of 2,2%-bipyridine) revealed average bond
distances of 2.05(6) (RuꢀN, 644 compounds) and
Nitration of the substrates Os(h2-Nppy)Cl(CO)-
(PPh3)2 (7) and Os(h2-Phqn)Cl(CO)(PPh3)2 (9) was
undertaken, using an adaptation of the Menke con-
ditions, which involve stirring the substrate in a slurry
of Cu(NO3)2 in acetic anhydride [7] (see Scheme 7). For
compound 9, two nitro groups were introduced, in the
2- and 4-positions, that is ortho and para to the metal–
carbon bond. We have previously observed similar
substitution patterns for simple phenyl complexes
[6,8].
,
2.06(8) A (OsꢀN, 51 compounds). Therefore, the MꢀN
distances observed in this work are longer than average.
It can be seen in Table 3 that the CꢀMꢀN bond
angles are very closely similar for all eight structures.
2.6. Conclusions
Os(h2-Nppy)Cl(CO)(PPh3)2 (7) differs significantly
from 9 in that the most activated and available site for
substitution, the position para to the metal, is at an
aromatic ring junction, and is thus not available for
functionalisation. However, it was ascertained by
1H-NMR spectroscopy that two nitrations had
occurred. Although crystals of sufficient quality for
X-ray structural analysis were not able to be grown, the
substitution pattern of the Nppy ligand was determined
by COSY, HSQC and HMBC NMR techniques, and it
was found that the two sites substituted were the 6- and
8-positions. The implications of this result are that the
electronic activating effect of the electron-rich metal
The work described herein reinforces and extends our
previous conclusions regarding the electrophilic substi-
tution reactions undergone by metallated arenes. In
particular we have found: (1) in more complicated
chelated ring systems substitution still occurs preferen-
tially para to the metal substituent, (2) the bromination
of 10 and 11 shows that substitution occurs preferen-
tially in the metallated phenyl ring rather than the
non-metallated phenyl ring, (3) in one instance (nitra-
tion of 7) the activating and directing effect of the metal
substituent is transmitted through a fused naphthyl ring
system so that substitution occurs in the non-metallated
ring.

A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
267
Table 2
Data collection and processing parameters
7
12
15
18
Formula
C52H40ClNOOsP2
982.44
Monoclinic
P21/n
C
731.80
Monoclinic
P21/n
37H31N2O2PruS2
C37H31N2OOsPS2
804.93
Orthorhombic
Pna21
C44H35N2O4PRu
787.78
Monoclinic
P21/c
Molecular weight
Crystal system
Space group
,
a (A)
11.6650(1)
28.9526(1)
12.6381(2)
9.7032(1)
21.4602(1)
16.6156(2)
17.3375(2)
16.3242(2)
11.2616(1)
21.7287(2)
10.6347(1)
17.5246(1)
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
102.73(1)
101.705(1)
107.49(1)
3
,
V (A )
Z
4163.39(8)
4
1.576
1960
3.24
3387.96(6)
4
1.435
1496
0.67
3187.27(6)
4
1.677
1592
4.22
3862.45
4
1.355
1616
0.49
Dcalc (g cm−3
F(000)
)
v (mm−1
)
q (min–max) (°)
Reflections collected/unique
Rint
1.8–27.5
23681/9179
0.0451
1.6–27.3
32629/7429
0.0246
1.7–27.5
18065/5814
0.0456
2.0–26.0
23234/7551
0.0240
No. observed reflections I\2|(I)
Crystal size (mm)
A (min-max)
6911
6672
4430
6396
0.20×0.14×0.14
0.563, 0.659
1.084
0.65×0.34×0.22
0.670, 0.887
1.107
0.34×0.09×0.07
0.328, 0.756
1.056
0.38×0.16×0.07
0.835, 0.966
1.076
Goodness of fit on F2
R (observed data)
0.0436
0.0376
0.0425
0.416
WR2 (all data)
Difference map (min–max) e A
0.0809
+1.57, −0.73
0.1129
+1.51, −0.76
0.0908
+0.69, −1.01
0.1320
+1.73, −0.71
−3
,
19
21
23
25
Formula
C59H34F3N2O3P2Ru
C53H41BrCl3NOOsP2
C43H35BrCl2N3OPRuS2
C42H33BrN3O4OsPS2
Molecular weight
Crystal system
Space group
1047.96
Monoclinic
P21/c
12.1376(1)
23.6920(4)
17.9721(3)
1146.27
Triclinic
956.71
Orthorhombic
Pbca
12.2938(2)
17.5246(2)
39.0487(7)
1008.91
Triclinic
(
(
P1
P1
,
a (A)
9.8350(1)
11.6149(1)
22.1280(1)
86.829(1)
84.068(1)
65.132(1)
2280.84(3)
2
11.6579(2)
16.8450(3)
13.9706(3)
72.212(1)
86.956(1)
79.675(1)
2112.34(7)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
105.984(1)
3
,
V (A )
4968.3(1)
4
1.401
2177
0.44
8412.8(2)
8
1.511
3856
1.63
Z
Dcalc (g cm−3
F(000)
)
1.669
1132
3.96
1.586
992
4.14
v (mm−1
)
2q (min–max) (°)
Reflections collected/unique
Rint
1.5–27.5
29775/10870
0.0704
1.8–27.5
22206/9827
0.0242
1.0–25.0
45139/7414
0.0887
1.5–27.5
20176/9138
0.0248
No. observed reflections I\2|(I)
Crystal size (mm)
A (min–max)
7535
8942
5369
8417
0.38×0.18×0.14
0.851, 0.941
1.034
0.0641
0.2117
0.38×0.07×0.07
0.314, 0.769
1.099
0.0375
0.0957
0.30×0.25×0.13
0.641, 0.816
1.132
0.0732
0.1556
0.45×0.20×0.15
0.257, 0.575
1.041
0.342
0.1074
Goodness of fit on F2
R (observed data)
wR2 (all data)
−3
,
Difference map (min–max) (e A
)
+1.29, −0.75
+2.13, −2.55
+2.06, −0.91
+2.86, −1.27
R=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ
wR2={S[w(F2o−F2c)2]/S[w(Fo2)2]}1/2
3. Experimental
specified, solvents were degassed using three freeze–
thaw–degas cycles, in Schlenk tubes, and the reactions
carried out under oxygen-free nitrogen. Infrared spectra
were recorded as Nujol mulls between KBr plates on
a Perkin–Elmer Paragon 1000 spectrometer. NMR
3.1. General
Most reactions were undertaken under atmospheric
conditions using standard reagents and solvents. Where

268
A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
Fig. 1. Molecular structure of 7. Hydrogen atoms have been omitted
for clarity.
Fig. 3. Molecular structure of 15. Hydrogen atoms have been omitted
for clarity.
bardment technique with a Varian VG 70-SE mass
spectrometer. The following starting materials were
prepared according to literature procedures: RuH-
Cl(CO)(PPh3)3 [9], OsHCl(CO)(PPh3)3 [10], 2-
phenylquinoline [11], 2-(1%-naphthyl)pyridine [12], and
2,3-diphenylquinoxaline [13]. Infrared data are shown
in Table 1, and other characterisation data are given
following the preparative details for each new
compound.
spectra were obtained on a Bruker DRX 400 at 25°C in
CDCl3 solution, and referenced with tetramethylsilane.
Multiplicity and coupling data is given as experimen-
tally observed, and apparent triplets (atoms coupling to
two similar but non-identical vicinal atoms) are written
as triplets, with coupling data listed for both vicinal
nuclei as an average. Where necessary, assignment of
the 1H spectra was made by possible by running a
COSY spectrum. Where 13C-NMR data are given, as-
signments were made by also performing HSQC and
HMBC experiments to correlate carbon chemical shifts
with the corresponding protons. The numbering scheme
used in all the NMR assignments is given in Scheme 3.
Mass spectra were recorded using the fast atom bom-
3.2. Preparation of Phqn2Hg (1)
Mercuration of 2-phenylquinoline was carried out
using a method very similar to that described in the
literature [11]. PhqnHgCl (1.5 g) was added to a solu-
tion of sodium thiosulfate (5 g) in water (100 ml) and
Fig. 2. Molecular structure of 12. Hydrogen atoms have been omitted
Fig. 4. Molecular structure of 18. Hydrogen atoms have been omitted
for clarity.
for clarity.

A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
269
Fig. 5. Molecular structure of 19. Hydrogen atoms have been omitted
for clarity.
Fig. 7. Molecular structure of 23. Hydrogen atoms have been omitted
for clarity.
the mixture thoroughly stirred. After 1 h, the substrate
had largely dissolved and a milky precipitate had be-
gun to form. The flask was left to stand overnight at
0°C, and then the white solid was removed by filtra-
tion. The filtrate was extracted with dichloromethane,
and the organic phase then used to dissolve the solid
product. The resulting solution was filtered through
filter paper, heptane added, and the volume reduced in
vacuo until precipitation was complete. The pure,
cream-coloured 1 was obtained by filtration (680 mg,
66%). 1H-NMR: l 7.99 (d, JH4=7.68 Hz, 2H, H3),
7.40 (dt, JH6=1.26, JH3+H5=7.56 Hz, 2H, H4), 7.55
(dt, JH3=1.08, JH4+H6=7.12 Hz, 2H, H5), 7.85 (dd,
JH5%=1.42, JH6%+H8%=6.86 Hz, 2H, H7%), 7.42 (d,
JH7%=8.20 Hz, 2H, H8%) ppm. 13C{1H}-NMR: l 168.53
(s, C1), 146.88 (s, C2), 128.22 (s, C3), 126.92 (s, C4),
128.97 (s, C5), 139.64 (s, C6), 160.21 (s, C2%), 119.77
(s, C3%), 135.97 (s, C4%), 126.39 (s, C10%), 126.85 (s, C5%),
125.60 (s, C6%), 129.18 (s, C7%), 128.97 (s, C8%), 146.58
(s, C9%) ppm. MS, m/z: 407 [MI−Hg−H], 610
[MI]. Anal. Calc. for C30H20HgN2·(1/3)CH2Cl2: C,
57.16; H, 3.27; N, 4.40. Found: C, 56.87; H, 3.02; N,
4.38%.
3.3. Preparation of NppyHgCl (2)
JH4=1.02, JH5=7.10 Hz, 2H, H6), 7.58 (d, JH4=8.68
Hz, 2H, H3%), 7.70 (d, JH3%=8.64 Hz, 2H, H4%), 7.46
(dd, JH7%=1.36, JH6=8.16 Hz, 2H, H5%), 7.24 (dt,
JH8%=1.36, JH5%+H7%=7.36 Hz, 2H, H6%), 7.19 (dt,
2-(1%-Naphthyl)pyridine [12] (7 g) was added to a
solution of mercuric acetate (11 g) in ethanol (60 ml),
and the mixture heated under reflux for 2 h. A solution
of lithium chloride (3 g) in methanol (100 ml) was
Fig. 6. Molecular structure of 21. Hydrogen atoms have been omitted
for clarity.
Fig. 8. Molecular structure of 25. Hydrogen atoms have been omitted
for clarity.

270
A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
Table 3
,
Summary of MꢀC and MꢀN bond lengths (A) and CꢀMꢀN angles (°) for 7, 12, 15, 18, 19, 21, 23, 25
d(MꢀC)
d(MꢀN)
Ú(CꢀMꢀN)
Os(h2-Nppy)Cl(CO)(PPh3)2 (7)
2.057(5)
2.068(3)
2.030(9)
2.017(3)
2.036(4)
2.050(5)
2.042(7)
2.047(4)
2.151(4)
2.145(2)
2.217(6)
2.159(3)
2.205(4)
2.268(4)
2.146(6)
2.166(4)
77.47(17)
77.53(11)
77.3(4)
78.87(11)
77.71(17)
76.59(18)
78.6(3)
Ru(h2-Nppy)(h2-S2CNMe2)(CO)(PPh3) (12)
Os(h2-Phqn)(h2-S2CNMe2)(CO)(PPh3) (15)
Ru(h2-Dpqx)(h2-acac)(CO)(PPh3) (18)
Ru(h2-Dpqx)(h1-O2CCF3)(CO)(PPh3)2 (19)
Os(h2-Phqn-4-Br)Cl(CO)(PPh3)2 (21)
Ru(h2-Dpqx-4-Br)(h2-S2CNMe2)(CO)(PPh3) (23)
Os(h2-Dpqx-4-Br)(h2-S2CNMe2)(CO)(PPh3) (25)
77.60(17)
added to the hot solution, and the mixture permitted to
cool to room temperature. The solution was filtered
and the solid extracted with several portions of
dichloromethane (total ca. 50 ml). Crystallisation was
induced by adding heptane and reducing the solvent
volume in vacuo. The pure, cream 2 that formed was
obtained by filtration (3.6 g, 24%). H-NMR: l 7.46–
8.81 (m, 10H, ArH) ppm. MS, m/z: 204 [MIꢀHgꢀCl],
440 [MIꢀH].
3.6. Preparation of Dpqx2Hg (5)
4 (6.5 g) was added to a solution of sodium thiosul-
fate (5 g) in water (100 ml) as described in Section 3.1.
The solid was filtered from aqueous solution and ex-
tracted with several portions of dichloromethane (total
ca. 50 ml). Heptane was added and the solvent volume
reduced in vacuo to induce crystallisation. The cream-
coloured, pure 4 was then collected by filtration (2.75 g,
29%). 1H-NMR: l 7.33 (d, JH4=8.24 Hz, 2H, H3),
1
3.4. Preparation of Nppy2Hg (3)
7.41 (t, JH3+H5=7.28 Hz, 2H, H4), 7.00 (t, JH4+H6=
7.62 Hz, 2H, H5), 7.20 (d, JH5=7.52 Hz, 2H, H6), 7.75
(d, JH6%=8.24 Hz, 2H, H5%), 7.60 (s, 2H, H6%), 7.54 (s,
2H, H7%), 7.93 (d, JH7%=8.12 Hz, 2H, H8%), 7.67 (s,
4H, H2¦), 7.35 (s, 4H, H3¦), 7.33 (s, 2H, H4¦) ppm.
MS, m/z: 765 [MI+H]. Anal. Calc. for C40H26HgN4·
(2/3)CH2Cl2: C, 59.58; H, 3.36; N, 6.83. Found: C,
59.20; H, 3.71; N, 6.71%.
2 (2.5 g) was added to a solution of sodium thiosul-
fate (5 g) in water (100 ml) as described in Section 3.1.
The solid was filtered from the aqueous solution, dis-
solved in dichloromethane, placed on a short column
(5×3 cm) of silica gel and eluted using dichloro-
methane. The pale yellow, motile band was collected
and crystallisation induced by adding heptane and
reducing the volume in vacuo. Pure 3 was collected
3.7. Preparation of Ru(p2-Nppy)Cl(CO)(PPh3)2 (6)
1
as a pale yellow solid by filtration (400 mg, 23%). H-
NMR: l 7.28–8.81 (m, 20H, ArH) ppm. MS, m/z:
611 [MI+H], 204 [MIꢀHgꢀNppy]. Anal. Calc. for
C30H20HgN2.CH2Cl2: C, 53.65; H, 3.19; N, 4.04.
Found: C, 53.55; H, 2.79; N, 4.08%.
RuHCl(CO)(PPh3)3 (100 mg) and Nppy2Hg (90 mg)
were added to deoxygenated toluene (10 ml) and the
mixture heated under reflux under a nitrogen atmo-
sphere for 2 h. After this time the solution was dis-
tinctly yellow and deposition of elemental mercury was
observed. The toluene solution was placed on a short
column (10×3 cm) of silica gel. The column was eluted
with hexane to expel the soluble byproducts. The eluant
was changed to dichloromethane and the yellow band
that eluted from the column was collected. Ethanol was
added, the solvent volume reduced in vacuo and the
pure crystals of 6 that formed were collected by filtra-
tion (87 mg, 85%). 1H-NMR: l 6.98–7.31 (m, 31H,
3.5. Preparation of DpqxHgCl (4)
2,3-Diphenylquinoxaline [13] (5 g) was added to a
solution of mercuric acetate (7.6 g) in ethanol (50 ml)
and heated under reflux for 30 h. A solution of lithium
chloride (2.5 g) in methanol (40 ml) was added to the
hot solution, and the voluminous precipitate that
formed was filtered whilst the solution was still warm.
The solid product was added to a flask of ethanol,
which was heated to boiling for several minutes to
dissolve any soluble impurities, and the hot solution
was filtered to obtain a white solid (4.6 g, 50%). The
analytical sample of 4 was obtained by recrystallisation
ArH), 8.75 (d, JH5%=5.60 Hz, 1H, H6%), 8.08 (d, JH7
=
8.52 Hz, 1H, H8), 7.92 (d, JH4%=8.00 Hz, 1H, H3%),
7.52 (d, JH6=7.92 Hz, 1H, H5), 7.35 (t, JH6+H8=7.70
Hz, 1H, H7), 7.20 (t, JH3%+H5%=7.40 Hz, 1H, H4%), 6.86
(d, JH4=8.36 Hz, 1H, H3), 6.54 (d, JH3=8.40 Hz, 1H,
H4), 6.21 (t, JH4%+H6%=6.52 Hz, 1H, H5%) ppm. MS,
m/z: 893 [MI], 858 [MIꢀCl]. Anal. Calc. for
C52H40ClNOP2Ru: C, 69.91; H, 4.51; N, 1.57. Found:
C, 69.94; H, 4.61; N, 1.70%.
1
from dichloromethane–heptane. H-NMR: l 7.00–8.31
(m, 13H, ArH) ppm. MS, m/z: 518 [MI]. Anal. Calc.
for C20H13ClHgN2·1/3CH2Cl2: C, 57.16; H, 3.27; N,
4.40. Found: C, 56.87; H, 3.02; N, 4.38%.

A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
271
3.8. Preparation of Os(p2-Nppy)Cl(CO)(PPh3)2 (7)
vacuo. The orange crystals of pure 9 were collected by
filtration (160 mg, 68%). 1H-NMR: l 6.87–7.25 (m,
30H, ArH), 7.35 (d, JH4=7.72 Hz, 1H, H3), 6.58 (t,
OsHCl(CO)(PPh3)3 (100 mg) and Nppy2Hg (90 mg)
were added to deoxygenated toluene (10 ml) and the
mixture heated under reflux under nitrogen for 4 h,
after which time the solution was distinctly yellow and
deposition of elemental mercury was observed. The
product was purified and isolated as described above in
3.6 to give deep yellow microcrystals of pure 7, (72 mg,
J
H3+H5=7.40 Hz, 1H, H4), 6.21 (t, JH4+H6=6.80 Hz,
1H, H5), ꢀ6.85 (s, 1H, H6), 7.54 (d, JH4%=8.84 Hz,
1H, H3%), 7.69 (d, JH3%=8.72 Hz, 1H, H4%), 7.30 (d,
JH6%=7.30 Hz, 1H, H5%), ꢀ7.15 (s, 1H, H6%), ꢀ7.15
(s, 1H, H7%), 9.51 (d, JH7%=8.60 Hz, 1H, H8%) ppm.
13C{1H}-NMR: l 185.94 (t, JP=10.0 Hz, CO), 133.84
(t, JP=5.0 Hz, PPh3 ortho), 132.23 (t, JP=24.5 Hz,
PPh3 ipso), 128.76 (s, PPh3 para), 127.07 (t, JP=4.5
Hz, PPh3 meta), 141.10 (s, C6), 137.57 (s, C4%), 130.74
(s, C8%), 129.86 (s, C5), 126.34 (s, C5%), 125.38 (s, C3),
119.34 (s, C4), 116.28 (s, C3%) ppm. Anal. Calc. for
C52H40ClNOOsP2·(2/3)CH2Cl2: C, 60.88; H, 4.01; N,
1.35. Found: C, 60.80; H, 3.73; N, 1.48%.
1
76%). H-NMR: l 7.03–7.28 (m, 30H, ArH), 6.58 (d,
J
H3=8.36 Hz, 1H, H4), 7.00 (d, JH4=8.44 Hz, 1H,
H3), 7.56 (d, JH6=7.88 Hz, 1H, H5), 7.20 (s, 1H, H6),
7.38 (t, JH6+H8=7.62 Hz, 1H, H7), 8.10 (d, JH7=8.64
Hz, 1H, H8), 7.98 (d, JH4%=8.56 Hz, 1H, H3%), ꢀ7.25
(s, 1H, H4%), 6.17 (t, JH4%+H6%=6.42 Hz, 1H, H5%), 8.60
(d, JH5%=5.56 Hz, 1H, H6%) ppm. MS, m/z: 983 [MI],
948 [MI]. Anal. Calc. for C52H40ClNOOsP2: C, 63.57;
H, 4.10; N, 1.43. Found: C, 63.43; H, 3.80; N, 1.32%.
3.11. Preparation of Ru(p2-Dpqx)Cl(CO)(PPh3)2 (10)
3.9. Preparation of Ru(p2-Phqn)Cl(CO)(PPh3)2 (8)
RuHCl(CO)(PPh3)3 (200 mg) and Dpqx2Hg (200 mg)
were added to deoxygenated toluene (20 ml). The solu-
tion was heated under reflux under nitrogen for 24 h,
after which time solution had become deep red in
colour and elemental mercury had deposited. The solu-
tion was placed on a short column (10×3 cm) of silica
gel. The rapidly moving orange band was eluted with
dichloromethane and discarded. The eluant was then
changed to dichloromethane containing acetone (ca.
10%). The bright red band that eluted was collected,
heptane was added and the solvent volume reduced in
vacuo. The red crystals of pure 10 were collected by
filtration (140 mg, 69%). 1H-NMR: l 6.95–7.97 (m,
35H, ArH), 9.64 (d, JH7%=8.60 Hz, 1H, H8%), 7.78 (d,
JH6%=8.16 Hz, 1H, H5%), ꢀ7.3 (s, 1H, H6%), ꢀ7.2 (s,
1H, H3), ꢀ7.1 (s, 1H, H7%), 6.79 (d, JH5=7.96 Hz,
1H, H6), 6.30 (t, 1H, H5), 6.26 (t, 1H, H4) ppm. MS,
m/z: 935 [MIꢀCl]. Anal. Calc. for C57H43ClN2OP2Ru·
(1/2)CH2Cl2: C, 68.18; H, 4.38; N, 2.77. Found: C,
68.15; H, 4.67; N, 3.01%.
RuHCl(CO)(PPh3)3 (300 mg) and Phqn2Hg (250 mg)
were added to deoxygenated toluene (30 ml). The solu-
tion was heated under reflux under nitrogen for 16 h,
after which time a deep brown–red solution was ob-
served, as well as deposition of elemental mercury. The
solution was placed on a short column (10×3 cm) of
silica gel and eluted with dichloromethane. The strongly
coloured band that eluted first was discarded. The
eluant was then changed to dichloromethane containing
acetone (ca. 10%) and the intense red band that then
eluted was collected. Heptane was added and on reduc-
ing the solvent volume in vacuo yellow crystals of pure
8 formed and these were collected by filtration (140 mg,
1
50%). H-NMR: l 6.87–7.24 (m, 33H, ArH), 7.36 (d,
JH4:6 Hz, 1H, H3), 6.63 (t, JH3+H5=7.38 Hz, 1H,
H4), 6.29 (t, JH4+H6=7.22 Hz, 1H, H5), 7.65 (d,
JH4%=9.56 Hz, 1H, H3%), 7.75 (d, JH3%=8.64 Hz, 1H,
H4%), 7.31 (d, JH6%=7.88 Hz, 1H, H5%), 9.68 (d, JH7%:8
Hz, 1H, H8%) ppm. MS, m/z: 858 [MIꢀCl]. Anal. Calc.
for C52H40ClNOP2Ru·(1/3)CH2Cl2: C, 68.20; H, 4.45;
N, 1.52. Found: C, 68.13; H, 4.40; N, 1.65%.
3.12. Preparation of Os(p2-Dpqx)Cl(CO)(PPh3)2 (11)
OsHCl(CO)(PPh3)3 (500 mg) and Dpqx2Hg (400 mg)
were added to deoxygenated toluene (30 ml). The solu-
tion was heated under reflux under nitrogen for 24 h,
after which time the solution had become deep purple
and elemental mercury had deposited. Hydrochloric
acid (30%, 1 ml) was added to the solution to decom-
pose any residual Dpqx2Hg, and after several minutes
of stirring the resulting mixture, the organic phase was
separated and washed with water. The toluene solution
was placed on a column (15×3 cm) of silica gel, and
eluted with toluene. The eluant was then changed to
dichloromethane, and the fast-moving green band dis-
carded. The purple band that eluted next was collected,
3.10. Preparation of Os(p2-Phqn)Cl(CO)(PPh3)2 (9)
OsHCl(CO)(PPh3)3 (250 mg) and Phqn2Hg (180 mg)
were added to deoxygenated toluene (30 ml). The solu-
tion was heated under reflux under nitrogen for 16 h,
after which time the solution had turned deep orange in
colour and elemental mercury had deposited. The solu-
tion was placed on a short column (10×3 cm) of silica
gel and eluted with dichloromethane. The fastest mov-
ing band was deep red, and was discarded. The deep
orange band that subsequently eluted was collected,
heptane added and the solvent volume reduced in

272
A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
3.15. Preparation of
heptane added and the solvent volume reduced in
vacuo to give pure, purple crystals of 11 which were
collected by filtration (320 mg, 63%). 1H-NMR: l
6.89–7.33 (m, 35H, ArH), ꢀ7.10 (s, 1H, H3), 6.13 (t,
Ru(p2-Phqn)(p2-S2CNMe2)(CO)(PPh3) (14)
Ru(h2-Phqn)Cl(CO)(PPh3)2 (40 mg) was treated in
the same manner as in Section 3.12, giving rise to
yellow crystals of pure 14 (30 mg, 94%). H-NMR: l
7.00–7.50 (m, 18H, ArH), 8.69 (d, JH7%= ꢀ8 Hz, 1H,
JH3+H5=7.28 Hz, 1H, H4), 6.21 (t, JH4+H6=7.64 Hz,
1
1H, H5), 6.77 (t, JH5=7.96 Hz, 1H, H6), 7.66 (d,
JH6%=8.12 Hz, 1H, H5%), ꢀ7.30 (s, 1H, H6%), ꢀ7.05
(s, 1H, H7%), 9.47 (d, JH7%=8.84 Hz, 1H, H8%) ppm.
MS, m/z: 1060 [MI], 1025 [MI–Cl]. Anal. Calc. for
C57H43ClN2OOsP2·C6H5CH3: C, 66.74; H, 4.46; N,
2.43. Found: C, 66.40; H, 4.43; N, 3.07%.
H8%), 7.96 (d, JH3%=8.96 Hz, 1H, H4%), 7.93 (d, JH4%
=
8.88 Hz, 1H, H3%), 7.80 (d, JH5=7.28 Hz, 1H, H6),
7.57 (d, JH4=7.56 Hz, 1H, H3), 6.88 (t, JH4+H6=6.96
Hz, 1H, H5), 6.77 (t, JH3+H5=7.28 Hz, 1H, H4), 3.21
(s, 3H, NꢀMe), 2.99 (s, 3H, NꢀMe) ppm. Anal. Calc.
for C37H31N2OPRuS2·(1/3)CH2Cl2: C, 60.26; H, 4.29;
N, 3.76. Found: C, 60.50; H, 4.58; N, 3.55%.
3.13. Preparation of
Ru(p2-Nppy)(p2-S2CNMe2)(CO)(PPh3) (12)
3.16. Preparation of
Ru(h2-Nppy)Cl(CO)(PPh3)2 (30 mg) was dissolved in
dichloromethane (10 ml), to which was added AgSbF6
(20 mg) in water (2 ml) and ethanol (5 ml). The
resulting solution was stirred for 10 minutes, after
which time excess water was added and the organic
layer collected. NaS2CNMe2 (15 mg) in water (2 ml)
and ethanol (5 ml) was added, and the solution stirred
for 10 min. Excess water was then added and once
again the organic layer was separated, then filtered. The
resulting solution was heated under reflux for 10 min,
then heptane was added and the solvent volume re-
duced in vacuo to give pure, deep yellow crystals of
12which were collected by filtration (20 mg, 82%).
Os(p2-Phqn)(p2-S2CNMe2)(CO)(PPh3) (15)
Os(h2-Phqn)Cl(CO)(PPh3)2 (25 mg) was treated in
the same manner as described in Section 3.13, to give
light orange crystals of pure 15 (38 mg, 93%). 1H-
NMR: l 7.01–7.40 (m, 15H, ArH), 8.52 (d, JH7%=8.48
Hz, 1H, H8%), 7.98 (d, JH3%=8.84 Hz, 1H, H4%), 7.94 (d,
JH4%=8.92 Hz, 1H, H3%), 7.80 (d, JH5=7.76 Hz, 1H,
H6), 7.51 (d, JH4=7.44 Hz, 1H, H3), 7.45 (d, JH6%
7.84 Hz, 1H, H5%), ꢀ7.15 (s, 1H, H6%), ꢀ7.10 (s, 1H,
H7%), 6.85 (t, JH4+H6=7.44 Hz, 1H, H5), 6.74 (t,
=
J
H3+H5=7.32 Hz, 1H, H4), 3.12 (s, 3H, NꢀMe), 2.88
(s, 3H, NꢀMe) ppm. MS, m/z: 806 [MI], 778 [MIꢀCO].
Anal. Calc. for C37H31N2OOsPS2: C, 55.21; H, 3.88; N,
3.48. Found: C, 55.38; H, 3.62; N, 3.37%.
1H-NMR: l 7.06–7.40 (m, 15H, ArH), 7.71 (d, JH4
7.92 Hz, 1H, H3), ꢀ7.3 (s, 1H, H4), 8.06 (d, JH6
=
=
8.12 Hz, 1H, H5), ꢀ7.3 (s, 1H, H6), ꢀ7.4 (s, 1H,
H7), 8.16 (d, JH7=8.56 Hz, 1H, H8), 8.07 (d, JH4%
3.17. Preparation of
=
Ru(p2-Dpqx)(p2-S2CNMe2)(CO)(PPh3) (16)
8.08 Hz, 1H, H3%), 7.50 (t, JH3%+H5%=7.27 Hz, 1H,
H4%), 6.67 (t, JH4%+H5%=5.96 Hz, 1H, H5%), 8.80 (d,
JH5%=8.80 Hz, 1H, H6%), 3.34 (s, 3H, NꢀMe), 3.13 (s,
3H, NꢀMe) ppm. Anal. Calc. for C37H31N2OPRuS2·
(1/6)CH2Cl2: C, 61.15; H, 4.33; N, 3.84. Found: C,
61.29; H, 4.67; N, 3.53%.
Ru(h2-Dpqx)Cl(CO)(PPh3)2 (30 mg) was treated in
the same manner as described in Section 3.13, to give
dark pink crystals of pure 16 (20 mg, 82%). H-NMR:
l 6.98–7.78 (m, 24H, ArH), 8.46 (d, JH7%=8.68 Hz,
1
1H, H8%), 7.92 (d, JH6%=7.80 Hz, 1H, H5%), 6.52 (t,
J
H4+H6=6.78 Hz, 1H, H5), 6.46 (t, JH3+H5=7.28 Hz,
3.14. Preparation of
1H, H4), 3.22 (s, 3H, NꢀMe), 3.04 (s, 3H, NꢀMe) ppm.
Anal. Calc. for C42H34N3OPRuS2·(3/4)CH2Cl2: C,
59.94; H, 4.18; N, 4.91. Found: C, 59.61; H, 3.56; N,
5.36%.
Os(p2-Nppy)(p2-S2CNMe2)(CO)(PPh3) (13)
Os(h2-Nppy)Cl(CO)(PPh3)2 (30 mg) was treated in
the same manner as described in Section 3.13, giving
rise to deep yellow crystals of pure 13 (20 mg, 80%).
3.18. Preparation of
1H-NMR: l 6.99–7.29 (m, 17H, ArH), 8.67 (d, JH5%
=
Os(p2-Dpqx)(p2-S2CNMe2)(CO)(PPh3) (17)
5.32 Hz, 1H, H6%), 8.19 (d, JH7=8.44 Hz, 1H, H8),
8.14 (d, JH4%=8.24 Hz, 1H, H3%), 8.10 (d, JH6=8.20
Hz, 1H, H5), 7.70 (d, JH4=8.24 Hz, 1H, H3), 7.47 (t,
JH3%+H5%=7.68 Hz, 1H, H4%), 7.36 (t, JH6+H8=7.50
Hz, 1H, H7), 6.60 (t, JH4%+H6%=6.60 Hz, 1H, H5%), 3.26
(s, 3H, NꢀMe), 3.02 (s, 3H, NꢀMe) ppm. Anal. Calc.
for C37H31N2OOsPS2·(1/4)C7H16: C, 56.07; H, 4.25; N,
3.38. Found: C, 56.34; H, 3.99; N, 3.29%.
Os(h2-Dpqx)Cl(CO)(PPh3)2 (30 mg) was treated in
the same manner as described in Section 3.13, to give
1
purple crystals of pure 17 (15 mg, 60%). H-NMR: l
7.02–7.45 (m, 24H, ArH), 8.29 (d, JH7%=8.44 Hz, 1H,
H8%), 7.75 (d, JH6%=8.24 Hz, 1H, H5%), 6.47 (t,
H4+H6=7.12 Hz, 1H, H5), 6.43 (t, JH3+H5=7.20 Hz,
1H, H4), 3.13 (s, 3H, NꢀMe), 2.94 (s, 3H, NꢀMe) ppm.
J

A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
273
MS, m/z: 883 [MI], 855 [MIꢀCO]. Anal. Calc. for
C42H34N3OOsPS2·(1/4)CH2Cl2: C, 56.18; H, 3.85; N,
4.65. Found: C, 56.13; H, 3.74; N, 4.28%.
large excess of sodium chloride (0.5 g) in water (20 ml)
was added. The resulting solution was stirred for a
further 10 min. The organic layer was separated,
filtered through filter paper, concentrated in volume
under reduced pressure, and then placed on a 10×3 cm
column of silica gel. The column was eluted with
dichloromethane, and the slow-moving orange band
was collected, heptane added, and the solvent volume
reduced in vacuo to induce crystallisation of pure,
orange crystals of 20. These were collected by filtration
3.19. Preparation of Ru(p2-Dpqx)(p2-acac)(CO)(PPh3)
(18)
Ru(h2-Dpqx)Cl(CO)(PPh3)2 (100 mg) was added to a
solution of methanol (20 ml), acetylacetone (1 ml) and
sodium metal (ca. 50 mg). The suspension was stirred
overnight (16 h), after which time dichloromethane (5
ml) was added, and stirring continued for 1 h. Excess
water was added, the organic layer separated, and the
solvent volume reduced in vacuo. The remaining solu-
tion was then placed on a short column (10×3 cm) of
silica gel, and eluted with excess hexane to remove
impurities such as acetylacetone. The eluant was then
changed to dichloromethane and the bright red band
that eluted from the column was collected. Ethanol and
a little water were added to this red solution and the
solvent volume reduced in vacuo to induce the crystalli-
sation of pure 18, which was collected by filtration (35
1
(107 mg, 49%). H-NMR: l 6.89–7.24 (m, 33H, ArH),
9.71 (m, 1H, H8%), 7.82 (d, JH3%=8.72 Hz, 1H, H4%),
7.50 (d, JH4%=8.80 Hz, 1H, H3%), 7.39 (d, JH4=2.00
Hz, 1H, H3), 6.75 (d, JH5=8.28 Hz, 1H, H6), 6.34 (dd,
JH3=2.02 Hz, JH4=8.26 Hz, 1H, H5) ppm. Anal.
Calc. for C52H39BrClNOP2Ru·(1/4)CH2Cl2: C, 63.17;
H, 4.01; N, 1.41. Found: C, 63.40; H, 3.82; N, 1.60%.
3.22. Preparation of Os(p2-Phqn-4-Br)Cl(CO)(PPh3)2
(21)
Os(h2-Phqn)Cl(CO)(PPh3)2 (140 mg) was dissolved in
dichloromethane (10 ml) to which was added
pyridine·HBr3 (50 mg) in methanol (5 ml). The mixture
was treated as in Section 3.21. The bright orange band
was eluted from the column, heptane added and the
solvent volume reduced in vacuo to give orange micro-
1
mg, 44%). H-NMR: l 6.42 (t, JH3+H5=7.14 Hz, 1H,
H4), 7.03–7.86 (m, 25H, ArH), 6.88 (d, JH5=7.44 Hz,
1H, H6), 6.50 (t, JH4+H6=7.44 Hz, 1H, H5), 4.86 (s,
1H, CH[acac]), 1.93 (s, 3H, CH3[acac]), 1.57 (s, 3H,
CH3[acac]) ppm. Anal. Calc. for C44H35N2O3PRu·
(1/3)CH2Cl2: C, 66.55; H, 4.49; N, 3.50. Found: C,
66.45; H, 4.81; N, 3.48%.
1
crystals of pure 21 (140 mg, 92%). H-NMR: l 6.88–
7.24 (m, 32H, ArH), 9.55 (d, JH7%=8.60 Hz, 1H, H8%),
7.76 (d, JH3%=8.64 Hz, 1H, H4%), 7.50 (d, JH4%=8.76
Hz, 1H, H3%), 7.44 (d, JH5=1.60 Hz, 1H, H3), 7.35 (d,
JH6%=7.08 Hz, 1H, H5%), 6.67 (d, JH5=8.28 Hz, 1H,
H6), 6.26 (dd, JH3=1.72 Hz, JH6=8.24 Hz, 1H, H5)
ppm. MS, m/z: 1026 [MIꢀCl]. Anal. Calc. for
C52H39BrClNOOsP2: C, 58.84; H, 3.70; N, 1.32. Found:
C, 58.64; H, 3.54; N, 1.51%.
3.20. Preparation of Ru(p2-Dpqx)(O2CCF3)(CO)(PPh3)2
(19)
Ru(h2-Dpqx)Cl(CO)(PPh3)2 was recrystallised from
dichloromethane, ethanol and a little water containing
a single drop of trifluoroacetic acid. The pure 19 thus
1
formed was collected by filtration. H-NMR: l 6.94–
7.56 (m, 36H, ArH), 9.48 (d, JH7%=8.76 Hz, 1H, H8%),
3.23. Preparation of Ru(p2-Dpqx-4-Br)Cl(CO)(PPh3)2
(22)
7.92 (d, JH6%=7.72 Hz, 1H, H5%), 7.76 (t, JH5%+H7%
=
8.12 Hz, 1H, H6%), 7.20 (d, JH4%=7.92 Hz, 1H, H3),
7.71 (d, JH5=8.08 Hz, 1H, H6), 6.51 (t, JH4+H6=7.28
Hz, 1H, H5), 6.45 (t, JH3+H5=7.58 Hz, 1H, H4) ppm.
Anal. Calc. for C59H43F3N2O3P2Ru·CH2Cl2: C, 63.61;
H, 4.00; N, 2.47. Found: C, 63.26; H, 3.85; N, 3.48%.
Ru(h2-Dpqx)Cl(CO)(PPh3)2 (85 mg) was dissolved in
dichloromethane (10 ml), to which was added
pyridine·HBr3 (80 mg) in methanol (5 ml). The mixture
was treated as in Section 3.21. Heptane was added to
the eluted red band and the solvent volume reduced to
afford dark peach microcrystals of pure 22 (25 mg,
27%). 1H-NMR: l 6.07–9.60 (m, 42H, ArH) ppm.
Anal. Calc. for C57H42BrClN2OP2Ru·(1/2)CH2Cl2: C,
63.26; H, 3.97; N, 2.57. Found: C, 63.03; H, 4.34; N,
2.99%.
3.21. Preparation of Ru(p2-Phqn-4-Br)Cl(CO)(PPh3)2
(20)
Ru(h2-Phqn)Cl(CO)(PPh3)2 (200 mg) was dissolved
in dichloromethane (20 ml), to which was added
pyridine·HBr3 (100 mg) in methanol (5 ml). A small
amount of iron powder (ca. 1 mg) was added, and the
solution stirred for 1 h. The solution was washed with
water, and then AgSbF6 (120 mg) in water (5 ml) and
ethanol (5 ml) was added to the organic phase. The
resulting solution was stirred for 10 min, and then a
3.24. Preparation of
Ru(p2-Dpqx-4-Br)(p2-S2CNMe2)(CO)(PPh3) (23)
Ru(h2-Dpqx-4-Br)Cl(CO)(PPh3)2 (25 mg) was treated
as described above in Section 3.13, to give dark pink

274
A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
microcrystals of pure 23 (15 mg, 72%). 1H-NMR: l
7.05–7.50 (m, 23H, ArH), 8.46 (d, JH7%=8.68 Hz, 1H,
H8%), 7.79 (d, JH6%=8.24 Hz, 1H, H5%), 7.38 (t, JH5%+
H7%=7.58 Hz, 1H, H6%), 6.62 (dd, JH3=2.10 Hz,
on reducing solvent volume in vacuo (95 mg, 87%).
1H-NMR: l 6.98–7.40 (m, 33H, ArH), 8.78 (d, JH5
=
2.32 Hz, 1H, H7), 8.63 (d, JH7=2.36 Hz, 1H, H5), 8.46
(d, JH3%=5.64 Hz, 1H, H2%), 6.58 (d, JH3=8.40 Hz,
1H, H4), 6.32 (t, JH2%+H4%=6.48 Hz, 1H, H3%) ppm.
Anal. Calc. for C52H38ClN3O5OsP2: C, 58.24; H, 3.57;
N, 3.92. Found: C, 57.95; H, 3.50; N, 4.04%.
JH6=8.10 Hz, 1H, H5), 3.23 (s, 3H, NꢀMe), 3.03 (s,
3H, NꢀMe) ppm. Anal. Calc. for C43H33BrN3-
OPRuS2·CH2Cl2: C, 53.98; H, 3.69; N, 4.39. Found: C,
54.21; H, 5.01; N, 5.60%.
3.28. Preparation of
Os(p2-Phqn-4,6-(NO2)2)Cl(CO)(PPh3)2 (27)
3.25. Preparation of Os(p2-Dpqx-4-Br)Cl(CO)(PPh3)2
(24)
Os(h2-Phqn)Cl(CO)(PPh3)2 (50 mg) and Cu(NO3)2
(140 mg) were added to acetic anhydride (3 ml) at room
temperature, and the slurry stirred for 1 h. To the
resulting greenish solution was added sodium acetate
(100 mg) in water (20 ml), and the mixture was stirred
until the product coagulated sufficiently for filtration.
After filtration, the resulting paste was redissolved in
dichloromethane and placed on a short column (10×3
cm) of silica gel. The product was eluted with
dichloromethane containing acetone (20%). Pure micro-
crystals of 27 were obtained by adding heptane to the
eluate and reducing the solvent volume in vacuo (20
Os(h2-Dpqx)Cl(CO)(PPh3)2 (90 mg) was dissolved in
dichloromethane (10 ml), to which was added
pyridine·HBr3 (50 mg) in methanol (5 ml). The mixture
was treated as described in Section 3.21. Heptane was
added to the eluted band and the solvent volume
reduced in vacuo, to afford blue–purple microcrystals
1
of pure 24 (50 mg, 52%). H-NMR: l 6.95–7.50 (m,
37H, ArH), 9.45 (d, JH7%=8.88 Hz, 1H, H8%), 7.70 (d,
JH6%=8.16 Hz, 1H, H5%), 6.86 (d, JH5=8.40 Hz, 1H,
H6), 6.77 (d, JH5=2.08 Hz, 1H, H3), 6.18 (dd, JH3
=
2.04 Hz, JH6=8.32 Hz, 1H, H5) ppm. MS, m/z: 1138
[MI], 1103 [MIꢀCl]. Anal. Calc. for C57H42BrClN2-
OOsP2: C, 60.14; H, 3.72; N, 2.46. Found: C, 60.11; H,
3.97; N, 2.42%.
1
mg, 37%). H-NMR: l 6.92–7.24 (m, 30H, ArH), 9.72
(d, JH7%=8.92 Hz, 1H, H8%), 8.06 (d, JH3%=8.68 Hz,
1H, H4%), 7.97 (s, 1H, H5), 7.64 (d, JH4%=8.80 Hz, 1H,
H3%), 7.58 (s, 1H, H3), 7.56 (d, JH6%=8.24 Hz, 1H,
H5%), 7.36 (t, JH6%+H8%=7.32 Hz, 1H, H7%), 7.14
(t, JH5%+H7%=7.96 Hz, 1H, H6%) ppm. MS, m/z:
1038 [MIꢀCl]. Anal. Calc. for C52H38ClN3O5OsP2·
(3/4)CH2Cl2: C, 55.76; H, 3.50; N, 3.70. Found: C,
55.65; H, 3.57; N, 3.97%.
3.26. Preparation of
Os(p2-Dpqx-4-Br)(p2-S2CNMe2)(CO)(PPh3) (25)
Os(h2-Dpqx-4-Br)Cl(CO)(PPh3)2 (30 mg) was treated
as described in Section 3.13, to give purple microcrys-
1
tals of pure 25 (20 mg, 79%). H-NMR: l 7.04–7.52
3.29. X-ray crystal structures for 7, 12, 15, 18, 19,
21, 23, 25
(m, 23H, ArH), 8.30 (d, JH7%=8.24 Hz, 1H, H8%), 7.78
(dd, JH7%=1.20 Hz, JH6%=8.28 Hz, 1H, H5%), 7.36 (t,
JH5%+H7%=7.68 Hz, 1H, H6%), 6.57 (dd, JH3=2.08 Hz,
Data were collected on a Siemens SMART diffrac-
tometer with a CCD area detector and graphite
JH8=8.24 Hz, 1H, H5), 3.13 (s, 3H, NꢀMe), 2.93 (s,
3H, NꢀMe) ppm. MS, m/z: 961 [MI], 933 [MIꢀCO].
Anal. Calc. for C42H33BrN3OOsPS2·(1/3)C6H14: C,
53.40; H, 3.84; N, 4.25. Found: C, 53.39; H, 4.05; N,
4.01%.
,
monochromated Mo–Ka radiation, u=0.71073 A.
Unit cell parameters were obtained from a least-squares
fit to all data with I\10|(I). The data were corrected
for Lorentz and polarisation effects and empirical ab-
sorption corrections applied [14]. Equivalent reflections
were averaged to give the unique data set. Details of
crystal data and data collection parameters are given in
Table 1.
3.27. Preparation of
Os(p2-Nppy-6,8-(NO2)2)Cl(CO)(PPh3)2 (26)
Os(h2-Nppy)Cl(CO)(PPh3)2 (100 mg) and Cu(NO3)2
(100 mg) were added to acetic anhydride (2.5 ml) and
the mixture stirred for 20 minutes. A solution of
sodium acetate (200 mg) in water (10 ml) was added
and the stirring continued until the product had coagu-
lated sufficiently for filtration. After filtration, the solid
was dissolved in dichloromethane and the solution
placed on a short column (10×3 cm) of silica gel. The
column was eluted with dichloromethane and the dark
red band collected. Ethanol was added to the red
eluate, and red microcrystals of pure 26 were obtained
3.30. Structure solution and refinement
The structures were solved by Patterson and Fourier
techniques using SHELXS [15] and refined by full-matrix
least squares on F2 using SHELXL [16]. All non-hydro-
gen atoms were allowed to refine anisotropically. Hy-
drogen atoms were placed geometrically and refined
with a riding model (including free rotation of methyl
groups) with Uiso fixed at 20% greater than the carrier
atom. Refinement details are given in Table 1.

A.M. Clark et al. / Journal of Organometallic Chemistry 598 (2000) 262–275
275
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4. Supplementary material
Tables of thermal and H atom parameters and com-
plete lists of bond lengths and angles have been de-
posited at the Cambridge Crystallographic Database
Centre. The deposition numbers CCDC 134378–
134385 have been allocated to the compounds 7, 12, 15,
18, 19, 21, 23, 25, respectively. Copies of this informa-
tion can be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(Fax:
+44-1223-336033;
e-mail:
deposit@ccdc.
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
[4] P.J. Steel, G.B. Caygill, J. Organomet. Chem. 395 (1990) 359.
[5] A.M. Clark, C.E.F. Rickard, W.R. Roper, L.J. Wright,
Organometallics 17 (1998) 4535.
Acknowledgements
We thank the Marsden fund for supporting this work
and for granting a PhD. scholarship to A.M.C. We also
thank A.G. Oliver for assistance with the
crystallography.
[6] G.R. Clark, C.E.L. Headford, W.R. Roper, L.J. Wright, V.P.D.
Yap, Inorg. Chim. Acta 220 (1994) 261.
[7] J.B. Menke, Recl. Trav. Chim. Pays-Bas 44 (1925) 141.
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Yap, Inorg. Chim. Acta 251 (1996) 65.
[9] P.S. Hallman, B.R. McGarvey, G. Wilkinson, J. Chem. Soc. (A)
(1968) 3143.
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