The functionalisation of ruthenium(ii) and osmium(ii) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates

Article abstract of DOI:10.1039/b925536b

The complex cis-[RuCl₂(dppm)₂] reacts with the amine-terminated dithiocarbamates KS₂CN(CH₂CH ₂NEt₂)₂ and KS₂CN(CH ₂CH₂CH₂NMe₂)₂ to form the compounds [Ru{S₂CN(CH₂CH₂NEt₂) ₂}(dppm)₂]⁺ and [Ru{S₂CN(CH ₂CH₂CH₂NMe₂)₂}(dppm) ₂]⁺, respectively. The methoxy-terminated dithiocarbamate compound [Ru{S₂CN(CH₂CH₂OMe) ₂}(dppm)₂]⁺ was also prepared from the same precursor using KS₂CN(CH₂CH₂OMe)₂. The alkenyl complexes [RuRCl(CO)(BTD)(PPh₃)₂] (R = CHCHBu^t, CHCHC₆H₄Me-4, CHCHCPh₂OH), [Ru(C(CCBu^t)CHBu^t)Cl(CO)(PPh₃)₂] and [Os(CHCHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃) ₂] also react cleanly with KS₂CN(CH₂CH ₂CH₂NMe₂)₂ and KS ₂CN(CH₂CH₂NEt₂)₂ to yield [MR{S₂CN(CH₂CH₂CH₂NMe ₂)₂}(CO)(PPh₃)₂] and [MR{S ₂CN(CH₂CH₂NEt₂)₂}(CO) (PPh₃)₂], respectively. In a similar fashion, the compounds [RuR{S₂CN(CH₂CH₂OMe₂) ₂}(CO)(PPh₃)₂] (R = CHCHBu^t, CHCHC₆H₄Me-4, C(CCBu^t)CHBu^t) were also prepared. Treatment of [Ru(CHCHBu^t){S₂CN(CH ₂CH₂CH₂NMe₂)₂}(CO) (PPh₃)₂] and [Ru{S₂CN(CH₂CH ₂NEt₂)₂}(dppm)₂]⁺ with trifluoroacetic acid affords the ammonium complexes [Ru(CHCHBu ^t){S₂CN(CH₂CH₂CH ₂NHMe₂)₂}(CO)(PPh₃) ₂]²⁺ and [Ru{S₂CN(CH₂CH ₂NHEt₂)₂}(dppm)₂]²⁺, while the same reagent generates the tricationic vinylcarbene complex [Ru(CHCHCPh₂){S₂CN(CH₂CH₂CH ₂NHMe₂)₂}(CO)(PPh₃) ₂]³⁺ through loss of water from [Ru(CHCHCPh ₂OH){S₂CN(CH₂CH₂CH ₂NMe₂)₂}(CO)(PPh₃)₂]. The structures of [Ru{S₂CN(CH₂CH₂OMe) ₂}(dppm)₂]PF₆ and [Ru(CHCHC₆H ₄Me-4){S₂CN(CH₂CH₂OMe) ₂}(CO)(PPh₃)₂] were determined crystallographically.

Full text of DOI:10.1039/b925536b

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The functionalisation of ruthenium(II) and osmium(II) alkenyl complexes with
amine- and alkoxy-terminated dithiocarbamates†
Saira Naeem,a Eleanor Ogilvie,a Andrew J. P. White,a Graeme Hogarthb and James D. E. T. Wilton-Ely*a
Received 3rd December 2009, Accepted 22nd January 2010
First published as an Advance Article on the web 11th March 2010
DOI: 10.1039/b925536b
The complex cis-[RuCl2(dppm)2] reacts with the amine-terminated dithiocarbamates
KS2CN(CH2CH2NEt2)2 and KS2CN(CH2CH2CH2NMe2)2 to form the compounds
[Ru{S2CN(CH2CH2NEt2)2}(dppm)2]+ and [Ru{S2CN(CH2CH2CH2NMe2)2}(dppm)2]+, respectively.
The methoxy-terminated dithiocarbamate compound [Ru{S2CN(CH2CH2OMe)2}(dppm)2]+ was also
prepared from the same precursor using KS2CN(CH2CH2OMe)2. The alkenyl complexes
t
=
=
=
[RuRCl(CO)(BTD)(PPh3)2] (R = CH CHBu , CH CHC6H4Me-4, CH CHCPh2OH),
t
t
≡
=
=
[Ru(C(C CBu ) CHBu )Cl(CO)(PPh3)2] and [Os(CH CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] also
react cleanly with KS2CN(CH2CH2CH2NMe2)2 and KS2CN(CH2CH2NEt2)2 to yield
[MR{S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2] and [MR{S2CN(CH2CH2NEt2)2}(CO)(PPh3)2],
respectively. In a similar fashion, the compounds [RuR{S2CN(CH2CH2OMe2)2}(CO)(PPh3)2] (R =
t
t
t
=
=
≡
=
CH CHBu , CH CHC6H4Me-4, C(C CBu ) CHBu ) were also prepared. Treatment of
t
=
[Ru(CH CHBu ){S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2] and [Ru{S2CN(CH2CH2NEt2)2}-
+
t
=
(dppm)2] with trifluoroacetic acid affords the ammonium complexes [Ru(CH CHBu ){S2CN-
(CH2CH2CH2NHMe2)2}(CO)(PPh3)2]2+ and [Ru{S2CN(CH2CH2NHEt2)2}(dppm)2]2+, while the same
=
=
reagent generates the tricationic vinylcarbene complex [Ru( CHCH CPh2){S2CN-
(CH2CH2CH2NHMe2)2}(CO)(PPh3)2]3+ through loss of water from [Ru(CH CHCPh2OH){S2CN-
=
(CH2CH2CH2NMe2)2}(CO)(PPh3)2]. The structures of [Ru{S2CN(CH2CH2OMe)2}(dppm)2]PF6 and
=
[Ru(CH CHC6H4Me-4){S2CN(CH2CH2OMe)2}(CO)(PPh3)2] were determined crystallographically.
between coordination and materials chemistry. The structural and
Introduction
electrochemical properties of such materials allow them to be used
for a diversity of applications, such as sensing or catalysis.
This report explores the incorporation of amine and methoxy
functionality (Scheme 1)5 into the dithiocarbamate skeleton as a
means to extend the molecule, coordinate further metal centres
and to change the physical properties of the complex as a whole.
This latter aspect can be exploited through reversible protonation
of the amine groups or using them to ‘protect’ acid-sensitive co-
ligands from the presence of mildly acidic conditions.
In the hundred years since the synthesis of the first dithiocarba-
mate complex of a transition metal by Dele´pine,1 a huge range
of derivatives has been prepared, including examples of all the
d-block metals.2 A major part of this widespread use is the ability
of this ligand class to stabilise many different oxidation states
and co-ligand sets. This first attribute is amply illustrated by the
many electrochemical investigations that have been carried out
on dithiocarbamate compounds in the intervening years.3 Most
dithiocarbamates are derived in a straightforward manner from
secondary amines. The commercially available ligands, [S2CNR2]-
(R = Me, Et), are still commonly used while the exploration
of the potential afforded by dithiocarbamates with more diverse
substituents is often neglected. This is surprising given the ease
with which metals coordinate to the ligand, permitting the facile
incorporation of additional functionality into the molecule.
Our recent research has focused on functionalised dithiocar-
bamates, with a view to coordinating a number of different
metals within the same system.4 This has provided access to
fascinating multimetallic compounds which lie at the interface
Results and discussion
Ruthenium bis(diphenylphosphino)methane complexes
The bis(dppm) compound cis-[RuCl2(dppm)2]6 has been shown
to be a versatile starting material for the addition of bidentate
ligands4,7 and, in particular, of dithiocarbamates.4,8 This is due
to the facile generation of a pair of active sites by removal
of the chloride ligands, while the robustness of the remaining
coordination sphere is maintained due to the inertness of the
dppm ligands. The ligand KS2CN(CH2CH2CH2NMe2)2 (A) was
generated in situ by treatment of a methanol solution of 3,3¢-
iminobis(N,N-dimethylpropylamine) with carbon disulfide in the
presence of KOH. Treatment of cis-[RuCl2(dppm)2] with a slight
excess of this ligand in the presence of NH4PF6 afforded the
colourless cation [Ru{S2CN(CH2CH2CH2NMe2)2}(dppm)2]PF6
(1) in 82% yield (Scheme 2). Two new pseudotriplets were observed
aDepartment of Chemistry, Imperial College London, South Kensington
Campus, London, UK SW7 2AZ. E-mail: j.wilton-ely@imperial.ac.uk
bDepartment of Chemistry, University College London, 20 Gordon Street,
London, UK WC1H 0AJ
† Electronic supplementary information (ESI) available: X-ray crystallog-
raphy. CCDC reference numbers 750274–750275. For ESI and crystallo-
graphic data in CIF or other electronic format see DOI: 10.1039/b925536b
4080 | Dalton Trans., 2010, 39, 4080–4089
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Scheme 1 The three functionalised dithiocarbamate ligands used in this work and homoleptic examples of previous complexes prepared using them
(M = Ni, Cu, Zn).5d
Scheme 2 Preparation of dithiocarbamate complexes from cis-[RuCl2(dppm)2].
in the 31P NMR spectrum at -15.5 and -2.1 ppm, showing
coupling of 34.1 Hz. Further evidence for the presence of the dppm
ligands was provided by the multiplet resonances for the methylene
(Scheme 2) with cis-[RuCl2(dppm)2] and NH4PF6 to yield the com-
pound [Ru{S2CN(CH2CH2OMe)2}(dppm)2]PF6 (3). In contrast
to the amino-terminated dithiocarbamate ligands, no duplication
1
1
protons at 4.42 and 4.97 ppm in the H NMR spectrum. The
of resonances was observed in the H NMR spectrum. Instead,
presence of the dithiocarbamate unit was confirmed by pairs of
multiplets at 1.32, 1.40 ppm and 3.12, 3.64 ppm as well as a further
broad multiplet at 1.87 ppm, all assigned to the propylene arms of
the ligand. The methyl protons gave rise to distinct resonances at
1.95 ppm. The overall composition was supported by a molecular
ion in the electrospray mass spectrum (+ve mode) at m/z 1132 and
good agreement of elemental analysis with calculated values.
The ligand KS2CN(CH2CH2NEt2)2 (B) shares many features
with A but has shorter and less flexible pendant arms. In a
similar manner to A, ligand B was generated in situ and then
allowed to react with cis-[RuCl2(dppm)2] and NH4PF6 to yield
[Ru{S2CN(CH2CH2NEt2)2}(dppm)2]PF6 (2). The shorter ethylene
bridge in the dithiocarbamate ligand gave rise to multiplets at
2.40, 3.28 and 3.81 ppm, while the ethyl substituents displayed
resonances at 1.05 and 2.57 ppm, showing mutual JHH coupling of
7.1 Hz. Again, a molecular ion at m/z 1160 Hz, was observed in
100% abundance in the mass spectrum (ES +ve).
a singlet at 3.38 ppm was present for the methyl protons while
a multiplet was seen at 3.51 ppm for the methylene protons
adjacent to the methoxy group and another at 3.79 ppm for the
remaining methylene protons. Single crystals of 3 were grown by
slow diffusion of ethanol into a dichloromethane solution of 3 and
the structure was determined by X-ray diffraction (Fig. 1).
The structural study reveals a distorted octahedral geom-
etry with cis-interligand angles in the range 71.444(19) to
◦
˚
103.630(19) . The Ru–S distances of 2.4237(5) and 2.4351(5) A
are comparable to those found in the bimetallic com-
plex [{(dppm)2Ru}2(S2CNC4H8NCS2)]2+, which range between
◦
2.426(2) and 2.452(2) A.4a The S(1)–C(2)–S(3) angle of 112.03(12)
˚
is also akin to those observed for the literature complex [112.3(5)
and 113.1(4)◦], while the S(1)–Ru–S(3) angle of 71.444(19)◦ is very
similar to one of its counterparts in the literature species. The C–S
and C(2)–N(4) distances are all indicative of considerable multiple
bond character and, in the latter case, can be identified as the
origin of the observed planarity of the RuS2CNR2 unit (the Ru,
S(1), C(2), S(3), N(4), C(5) and C(9) atoms are coplanar to within
A further related dithiocarbamate ligand with pendant func-
tional groups has been reported recently - the methoxy-terminated
ligand, KS2CN(CH2CH2OMe)2 (C).9 This reacted smoothly
˚
ca. 0.12 A).
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gave rise to a singlet resonance at 206.1 ppm in the 13C
NMR spectrum, while the carbons of the (CH2)3 units were
observed as pairs of resonances in the region 57.1 – 24.9 ppm.
The methyl carbons resonated at 45.5 ppm, slightly downfield
of the carbons of the tert-butyl unit. Infrared data displayed
features typical of dithiocarbamate (nCN at 1457 cm-1) and
triphenylphosphine ligands as well as an intense absorption at
1905 cm-1 due to the carbonyl ligand. The overall formulation of
t
=
[Ru(CH CHBu ){S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2] (4)
was confirmed by an abundant molecular ion in the electrospray
(+ve ion) mass spectrum at m/z 1000 and good agreement of
elemental analysis with calculated values (Scheme 3).
Two further ruthenium examples with ligand A, [Ru-
=
(CH CHC6H4Me-4){S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2]
=
(5) and [Ru(CH CHCPh2OH){S2CN(CH2CH2CH2NMe2)2}-
(CO)(PPh3)2] (6), were prepared bearing aromatic and g-hydroxy-
substituted alkenyl ligands. These were found to exhibit similar
spectroscopic features to 4. The disubstituted alkenyl derivative
t
t
≡
=
[Ru{C(C CBu ) CHBu }{S2CN(CH2CH2CH2NMe2)2}(CO)-
Fig. 1 The molecular structure of the cation in 3. Selected bond lengths
◦
˚
(A) and angles ( ); Ru–S(1) 2.4237(5), Ru–S(3) 2.4351(5), Ru–P(13)
2.3541(5), Ru–P(15) 2.3344(5), Ru–P(40) 2.3207(5), Ru–P(42) 2.3233(5),
S(1)–C(2) 1.704(2), C(2)–S(3) 1.717(2), C(2)–N(4) 1.340(3), S(1)–Ru–S(3)
71.444(19), S(1)–C(2)–S(3) 112.03(12). Protons and the hexafluorophos-
phate counteranion have been omitted for clarity.
(PPh3)2] (7) was also synthesised in the same manner from
t
t
≡
=
pentacoordinate [Ru{C(C CBu ) CHBu }Cl(CO)(PPh3)2]. The
multiplets attributed to the amine arms of the dithiocarbamate
1
ligand were found to be more closely spaced in the H NMR
spectrum of this compound than found in the other examples.
=
An osmium example, [Os(CH CHC6H4Me-4){S2CN-
(CH2CH2CH2NMe2)2}(CO)(PPh3)2] (8), was prepared from
Ruthenium and osmium alkenyl complexes
=
[Os(CH CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] to confirm that
Having demonstrated the coordination chemistry of the three lig-
ands A-C with the Ru(dppm)2 unit, the focus of the research shifted
to the use of the ligands with group 8 alkenyl complexes.10 These
compounds have enjoyed great interest, principally stemming from
an analogous reaction ensued between the dithiocarbamate ligand
and a representative alkenyl complex of the heaviest congener of
group 8. Spectroscopic data were found to be similar to those for
5, apart from the characteristically lower frequency of the nCO
absorption at 1894 cm-1 in the solid state infrared spectrum.
1
2
=
the preparation of the complexes [Ru(CR CHR )Cl(CO)L2]
(L = PPri3,11 PPh312) in the 1980s. The rich reactivity of these
compounds, both in terms of transformation of the alkenyl group
as well as coordination chemistry at the metal centre, makes
them ideal choices for exploring new mono-, bi- and tridentate
In an analogous fashion, the diethylamino variant, KS2CN-
t
=
(CH2CH2NEt2)2 (B), was used to prepare [Ru(CH CHBu )-
{S2CN(CH2CH2NEt2)2}(CO)(PPh3)2]
(9)
Features
from
[Ru-
associated
t
=
(CH CHBu )Cl(CO)(BTD)(PPh3)2].
ligands.11-20 The compounds [Ru(CR CHR )Cl(CO)(PPh3)2]
with the alkenyl, phosphine and carbonyl ligands were found
to be similar to those observed for 4. Pairs of multiplets
were again seen in the 1H NMR spectrum at 1.93, 2.21
and 2.83, 3.28 ppm for the ethylene units with overlapping
multiplets identified for the diethylamino substituents at 0.95 and
2.43 ppm. Mass spectrometry and elemental analysis data were
in good agreement with the above formulation. The complexes
1
2
12
=
1
2
=
and [Ru(CR CHR )Cl(CO)(BTD)(PPh3)2] (BTD
=
2,1,3-
benzothiadiazole - a labile ligand)17c are the most convenient
triphenylphosphine-stabilised alkenyl complexes to use as starting
points for this chemistry. Although many ruthenium (and to a
lesser extent osmium) dithiocarbamates are known, no example
has been reported with the amine- or methoxy-terminated ligands
used here.
=
[Ru (CH CHC6H4Me - 4) {S2CN (CH2CH2NEt2)2} (CO) (PPh3)2]
=
(10), [Ru(CH CHCPh2OH){S2CN(CH2CH2NEt2)2}(CO)(PPh3)2]
t t
Addition of a slight excess of KS2CN(CH2CH2CH2NMe2)2
(A) to an orange dichloromethane solution of [Ru(CH CHBu )-
t
=
≡
=
(11), [Ru{C(C C Bu) CH Bu}{S2CN(CH2CH2NEt2)2}(CO)-
=
Cl(CO)(BTD)(PPh3)2] led to a rapid decolourisation and forma-
tion of a pale yellow solution. Work up yielded a pale yellow
microcrystalline material, which gave rise to a new singlet in the
31P NMR spectrum at 39.5 ppm. Evidence for the retention of
the alkenyl ligand was provided by a singlet at 0.40 ppm (tBu)
(PPh3)2] (12) and [Os(CH CHC6H4Me-4){S2CN(CH2CH2-
NEt2)2}(CO)(PPh3)2] (13) were also prepared to confirm
the generality of the coordination chemistry shown by
[S2CN(CH2CH2NEt2)2]- with the alkenyl precursors and to
increase the options for structural determination through X-ray
diffraction (Scheme 3).
1
in the H NMR spectrum and alkenyl resonances at 4.60 and
6.30 ppm showing mutual coupling of 16.4 Hz. The downfield
alkenyl signal was found to display coupling to the mutually
trans phosphine ligands (JHP = 2.7 Hz) and was assigned as
Ha. In addition, singlets at 2.12 and 2.14 ppm were observed
for the methyl protons of the terminal NMe2 units along with
pairs of multiplets for the propylene chain in the region 1.09
to 3.19 ppm. The CS2 nucleus of the dithiocarbamate ligand
The ligand, KS2CN(CH2CH2OMe)2 (C), was prepared as
a methanol solution and added to the alkenyl complexes
[Ru(alkenyl)Cl(CO)(BTD)(PPh3)2], however, these reactions
did not lead to a single product but rather to an inseparable
mixture which gave rise to two closely spaced resonances in
the 31P NMR spectrum in each case. The presence of two
compounds was further supported by two sets of alkenyl
4082 | Dalton Trans., 2010, 39, 4080–4089
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Scheme 3 Preparation of alkenyl dithiocarbamate complexes.
resonances in the 1H NMR spectrum. A partially successful
crystallographic investigation revealed a complex with the
methyl xanthate ligand, [S2COMe]-, presumably formed by
deprotonation of methanol and reaction with carbon disulfide.
data were obtained for 14 - 16 (Scheme 3). Single crystals of
=
[Ru(CH CHC6H4Me-4){S2CN(CH2CH2OMe)2}(CO)(PPh3)2]
(15) were grown and the molecular structure determined by X-ray
diffraction (Fig. 2).
In order to confirm the nature of the contaminant, the complex
A distorted octahedral geometry is found for the ruthenium
centre with cis-interligand angles in the range 70.346(15)
to 101.83(6)◦ while the P(1)–Ru–P(2) angle of 174.221(15)◦
approaches linearity. The Ru–S distances of 2.4661(4) and
t
=
[Ru(CH CHBu )(S2COMe)(CO)(PPh3)2] was prepared in the
same manner as the isopropyl xanthate analogue,19b and found to
account for the remaining resonances (e.g., S2COMe resonance at
around 3.20 ppm in the 1H NMR spectra) in the product mixtures
obtained initially. Elimination of methanol from both ligand
preparation and work up of the complex allowed the complexes
˚
2.4936(4) A are longer than those found in complex 3, reflecting
the greater trans influence of the carbonyl and alkenyl ligands
compared to the phosphorus donors of the dppm ligands. A
similar elongation of the Ru–S distance opposite the alkenyl
ligand over that trans to the carbonyl is also found in the complex
[Ru(alkenyl){S2CN(CH2CH2OMe)2}(CO)(PPh3)2] (alkenyl
=
t
t
t
=
=
≡
=
CH CHBu , 14; CH CHC6H4Me-4, 15; C(C CBu ) CHBu ),
16) to be prepared in high yield from an aqueous solution of C.
1H NMR analysis of complex 14 revealed two singlets for the
methoxy protons at 3.19 and 3.20 ppm as well as triplets for the
protons of the pendant arms at 2.85, 3.07, 3.18 and 3.48 ppm
(all showing coupling of around 6 Hz) alongside typical features
for the alkenyl ligands. Similar spectroscopic and analytical
+
4c
≡
=
[Ru(C(C CPh) CHPh)(S2CNC4H8NH2)(CO)(PPh3)2] .
The
S(1)–C(2)–S(3) angle of 113.47(10)◦ in 15 is slightly larger than
that of 112.03(12)◦ observed for the same ligand in complex
3, while the S(3)–Ru–S(1) angle of 70.346(15)◦ is smaller than
in 3 [71.444(19)◦]. These changes are associated with a longer
˚
Ru ◊ ◊ ◊ C(2) separation in 15 [2.9628(18) A] cf. that seen in 3
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=
The parent alkenyl complexes, [Ru(CR CHR)Cl(CO)-
(BTD)(PPh3)2] are susceptible to cleavage of the organic lig-
and by acids such as HCl so it was not assumed that re-
action with acid would be limited to straightforward pro-
tonation of the amine functionality. Again, addition of two
t
=
equivalents of trifluoroacetic acid to [Ru(CH CHBu ){S2CN-
(CH2CH2CH2NMe2)2}(CO)(PPh3)2] (4) did not appear to cause
any colour change and little difference was observed in the
chemical shift of the 31P NMR resonance. However, significant
shifts in the resonances for the methyl (2.66 and 2.72 ppm) and
propylene (1.42–3.51 ppm) protons with respect to the values
for 4 clearly indicated that protonation had occurred. Negligible
difference in the alkenyl and phosphine resonances in the same
spectrum showed that the co-ligands had been unaffected by
this transformation. The IR spectrum displayed a new peak
at 1674 cm-1 attributed to the trifluoroacetate counteranions
alongside the nCO absorption at 1915 cm-1. The formulation of
t
=
[Ru(CH CH Bu){S2CN(CH2CH2CH2NHMe2)2}(CO)(PPh3)2]-
(OSO2CF3)2 (18) was further supported by mass spectrometry and
elemental analysis (Scheme 4). This protonation was found to be
reversible on addition of DBU, which regenerated 4.
˚
Fig. 2 The molecular structure of 15. Selected bond lengths (A) and an-
gles (◦); Ru–S(1) 2.4936(4), Ru–S(3) 2.4661(4), Ru–P(1) 2.3684(4), Ru–P(2)
2.3680(4), Ru–C(13) 2.0851(18), Ru–C(22) 1.860(2), S(1)–C(2) 1.7105(19),
C(2)–S(3) 1.7066(19), C(2)–N(4) 1.337(2), C(13)–C(14) 1.328(3),
S(1)–Ru–S(3) 70.346(15), P(1)–Ru–P(2) 174.221(15), S(1)–C(2)–S(3)
113.47(10), Ru–C(13)–C(14) 127.45(15).
Following the successful protonation of the tert-butyl
alkenyl complex 4, the g-hydroxy alkenyl complex [Ru-
=
(CH CHCPh2OH) {S2CN (CH2CH2CH2NMe2)2} (CO) (PPh3)2]
(6) was treated with excess trifluoroacetic acid causing an instant
colour change from colourless to intense red. Since protonation
of 4 had involved no discernible colour change, it was clear
that a new chromophore had been generated in the molecule. A
singlet was observed in the 31P NMR spectrum of the compound
at 32.0 ppm, shifted significantly from the value found for the
˚
[2.928(2) A]. As noted in 3, the RuS2CNR2 unit is again flat, the
Ru, S(1), C(2), S(3), N(4), C(5) and C(9) atoms being coplanar to
˚
within ca. 0.09 A.
1
precursor 6 (39.9 ppm). The H NMR spectrum displayed two
Protonation studies
new downfield doublets at 8.10 and 14.68 ppm, showing a mutual
coupling of 14.0 Hz, the latter typical of the chemical shift of
a carbene proton. The signals due to the protons of the methyl
substituents of the dithiocarbamate ligand were shifted from
2.11 and 2.15 ppm in 6 to 2.80 and 2.83 ppm in this complex,
suggesting protonation had occurred also at the nitrogen lone
pairs. The other protons of this ligand were apparent only as
two broad multiplets centred at 1.41 and 2.98 ppm. The shift in
frequency of the nCO absorption from 1913 cm-1 in 6 to 1952 cm-1
in 19 indicated a decrease in electron density at the metal centre,
consistent with formation of a cation. On the basis of these
data in conjunction with 13C NMR spectroscopy (310.5 ppm,
RuCH, JCP = 8.6 Hz) mass spectrometry (molecular ion at m/z
1108 and peak for fragmentation of the vinylcarbene unit at
m/z 916) and elemental analysis, the product was formulated
With the amine functionality now introduced into the complexes
through the dithiocarbamate ligand, the reactivity of the pendant
groups was probed. Given the sustained interest in solubility
of metal complexes in aqueous media,21 the first investigation
attempted was the treatment of the complexes with acid to form
ammonium functionalised metal compounds.
Due to the robustness of the dppm co-ligands, the complex
[Ru{S2CN(CH2CH2NEt2)2}(dppm)2]PF6 (1) was chosen for the
first protonation attempt. Two equivalents of trifluoroacetic acid
were added but little change was observed to the colour of the
1
solution. After work up, H NMR analysis revealed a shift and
significant broadening in the chemical shift of the resonances
of the ethyl substituents of the dithiocarbamate ligand. The
multiplet resonances for the ethylene units were also displaced.
A new, intense band was observed in the solid state infrared
spectrum at 1670 cm-1 for the trifluoroacetate counteranions as
well as a nPF absorption at 833 cm-1 for the hexafluorophos-
phate anion. These data led to the formulation of the product
as [Ru{S2CN(CH2CH2NHEt2)2}(dppm)2](PF6)(O2CCF3)2 (17), as
= =
as
[Ru( CHCH CPh2){S2CN(CH2CH2CH2NHMe2)2}(CO)-
(PPh3)2](O2CCF3)3 (19), formed through elimination of water
after protonation (Scheme 4).
The formation of 18 and 19 bodes well for the use of these
ligands in the construction of systems in which protection of acid-
sensitive functionality is necessary. Thus, attack of small amounts
of acid may occur preferentially at the amine functionality rather
than elsewhere in the molecule. This was demonstrated in the
reaction of 6 with one equivalent of trifluoroacetic acid. Initially,
a slight red colouration was observed, however, 1H NMR analysis
revealed protonation of the amine groups rather than formation
of the vinylcarbene compound. Formation of 19 only occurs on
addition of more than two equivalents of F3CCO2H.
-
shown in Scheme 2. The retention of the PF6 counteranion
suggested a relatively strong interaction with the ammonium units.
Attempts to obtain NMR data for this material in D2O were
unsuccessful, however, treatment of 1 with two equivalents of dry
HCl afforded 17 as the chloride salt, which showed modest water
solubility. Aqueous solubility will undoubtedly be improved if
more than one dithiocarbamate unit can be attached to the metal
centre.
4084 | Dalton Trans., 2010, 39, 4080–4089
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Scheme 4 Protonation reactions of alkenyl complexes 4 (R = But) and 6 (R = CPh2OH).
spectrometry data were obtained using a Micromass LCT Premier
instrument and infrared data were measured using a Perkin Elmer
Spectrum 100 FT-IR spectrometer. Characteristic phosphine-
associated infrared data have been omitted. NMR spectroscopy
was performed at 25 ◦C using a Bruker AV400 spectrometer in
CDCl3 unless otherwise indicated. All couplings are in Hertz
and 31P NMR spectra are proton decoupled. Resonances for the
hexafluorophosphate anion are not reported. Elemental analysis
data were obtained from London Metropolitan University.
The procedures given provide materials of sufficient purity for
synthetic and spectroscopic purposes. Samples were recrystallised
from a mixture of dichloromethane and ethanol for elemental
analysis. Solvates were confirmed by integration of the 1H NMR
spectrum.
Conclusion
Using bis(dppm) and s-alkenyl compounds as model com-
plexes, the first examples of ruthenium and osmium with
the amine- or methoxy-terminated ‘smart’ dithiocarbamate lig-
ands, [S2CN(CH2CH2CH2NMe2)2]-, [S2CN(CH2CH2NEt2)2]- and
[S2CN(CH2CH2OMe)2]- have been prepared. They have been
shown to yield coordinatively saturated complexes which can then
be used as a starting point for further chemistry. Protonation
of the amine-terminated compounds leads to clean formation
of ammonium units rendering them moderately water soluble
whereas, in the case of the g-hydroxyalkenyl complex, a vinylcar-
bene ligand is also generated. The ammonium complexes discussed
here have modest water solubility (the precursors are completely
insoluble) due to the presence of only one dithiocarbamate unit.
However, the commercial availability and low cost of the amines
HN(CH2CH2NEt2)2 and HN(CH2CH2CH2NMe2)2 and the simple
preparation of the corresponding dithiocarbamates could make
these ligands an attractive alternative to more complicated or
expensive water solubilising ligands such as sulfonated phosphines.
Furthermore, the amine units can also be employed to protect acid-
sensitive co-ligands from cleavage or unwanted reaction during
transformations in the presence of acid.
Reactions with cis-[RuCl2(dppm)2]
A solution of cis-[RuCl2(dppm)2] (80 mg, 0.085 mmol) in
dichloromethane (20 mL) was treated with two equivalents of
the dithiocarbamate ligand and NH4PF6 (28 mg, 0.172 mmol)
in methanol (10 mL) and stirred for 30 min. All solvent was
removed and the residue dissolved in the minimum volume of
dichloromethane and filtered through diatomaceous earth (celite).
Ethanol (10 mL) was added and the solvent volume reduced
(rotary evaporation) until precipitation was complete. The product
was washed with ethanol (10 mL) and petroleum ether (10 mL).
The product was dried under vacuum.
Experimental
General comments
Reactions of alkenyl complexes with KS2CN(CH2CH2CH2NMe2)2
All experiments were carried out under aerobic conditions
and the majority of the complexes appear indefinitely stable
towards the atmosphere in solution or in the solid state.
A solution of KS2CN(CH2CH2CH2NMe2)2 in water was prepared
by a literature procedure5d and 0.129 mmol was added to a
dichloromethane–methanol (10 mL:10 mL) solution of the metal
alkenyl complex. The reaction was stirred for one hour. Reduction
in solvent volume (rotary evaporator) led to precipitation of the
product. This was washed with water (5 mL), ethanol (10 mL) and
petroleum ether (10 mL). The product was dried under vacuum.
Solvents were used as received from commercial sources.
t
=
The complexes [Ru(CH CHBu )Cl(CO)(BTD)(PPh3)2], [Ru-
=
=
(CH CHC6H4Me-4)Cl(BTD)(CO)(PPh3)2] and [Ru(CH CH-
CPh2OH)Cl(BTD)(CO)(PPh3)2] were prepared using the literature
route,17c substituting 2,1,3-benzoselanadiazole (BSD) for the for
the commercially available 2,1,3-benzothiadiazole (BTD)
=
ligand. The compounds [Os(CH CHC6H4Me-4)Cl(BTD)-
Reactions of alkenyl complexes with KS2CN(CH2CH2NEt2)2
t
t
22
(CO)(PPh3)2],17h
[Ru{C(C CBu ) CHBu }Cl(CO)(PPh3)2],
≡
=
and cis-[RuCl2(dppm)2]15b were synthesised as described in the
indicated reports. Solutions (4.0 mmol) of the ligands, KS2CN-
(CH2CH2CH2NMe2)2 (methanol),5 KS2CN(CH2CH2NEt2)2,5
KS2CN(CH2CH2OMe)2.9b were prepared in water unless
otherwise stated, by literature methods. Electrospray mass
A solution of KS2CN(CH2CH2NEt2)2 in methanol was prepared
by a literature procedure5d and 0.132 mmol was added to a
dichloromethane–methanol (10 mL:10 mL) solution of the metal
alkenyl complex. The reaction was stirred for one hour. Reduction
in solvent volume (rotary evaporator) led to precipitation of the
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product. This was washed with water (5 mL), ethanol (10 mL) and
petroleum ether (10 mL). The product was dried under vacuum.
1905(nCO), 1572, 1457 (nCN), 1369, 1354, 1257, 1211, 1174, 1034,
981, 937 cm-1. 31P NMR (CDCl3): 39.5 (s, PPh3) ppm. 13C NMR
(CD2Cl2): 207.3 (t, CO, JCP = 15.9 Hz); 206.1 (s, CS2); 141.9 (t,
Cb, JCP = 3.5 Hz); 135.0 (tv, o/m-C6H5, JCP = 5.2 Hz); 134.7 (tv,
ipso-C6H5, JCP = 20.9 Hz); 134.2 (t, Ca, JCP = 12.5 Hz); 129.2 (s, p-
C6H5); 127.6 (tv, o/m-C6H5, JCP = 4.5 Hz); 57.1, 56.9 (s ¥ 2, NCH2);
48.3, 47.5 (s ¥ 2, NCH2), 45.5 (s, NMe2); 35.7 (s, CMe3); 29.7 (s,
tBu-Me); 25.2, 24.9 (s ¥ 2, CCH2C) ppm. 1H NMR (CDCl3): 0.40
Reactions of alkenyl complexes with KS2CN(CH2CH2OMe)2
A solution of KS2CN(CH2CH2OMe)2 in water was prepared by
a literature procedure9b and 0.132 mmol was added to an acetone
solution (20 mL) of the metal alkenyl complex. The reaction was
stirred for one hour. All solvent was removed and diethyl ether
(20 mL) added and the crude product triturated ultrasonically.
The pale yellow precipitate was filtered and washed with water
(5 mL) and diethyl ether (10 mL). The product was dried under
vacuum.
t
(s, 9H, Bu); 1.09, 1.36 (m ¥ 2, 2 ¥ 2H, NCH2CH2CH2N); 1.97
(t, 2H, CH2NMe2; JHH = 6.9 Hz); 2.07 (t, 2H, CH2NMe2; JHH
=
7.1 Hz); 2.12, 2.14 (s ¥ 2, 2 ¥ 6H, NMe2); 2.79, 3.19 (m ¥ 2, 2 ¥
2H, CH2NCS2); 4.60 (dt, 1H, Hb, JHH = 16.4 Hz; JHP = 1.8 Hz);
6.30 (dt, 1H, Ha, JHH = 16.4 Hz, JHP = 2.7 Hz); 7.27–7.31, 7.55–
7.60 (m ¥ 2, 30H, C6H5) ppm. MS (ES +ve) m/z (abundance) =
1000 (74) [M]+; 738 (85) [M - PPh3]+. Analysis: Calculated for
C54H65N3OP2RuS2 (Mw = 999.26): C 64.9%, H 6.6%, N 4.2%;
Found: C 65.0%, H 6.6%, N 4.1%.
[Ru{S2CN(CH2CH2CH2NMe2)2}(dppm)2]PF6 (1)
Reaction of two equivalents of KS2CN(CH2CH2CH2NMe2)2 with
cis-[RuCl2(dppm)2] (80 mg, 0.085 mmol) gave 88.8 mg of colourless
product (82%). IR (solid state): 1504, 1358, 1309, 1258, 1231, 878,
833 (nPF) cm-1. 31P NMR (CD2Cl2): -15.5, -2.1 (tv ¥ 2, dppm,
=
[Ru(CH CHC6H4Me-4){S2CN(CH2CH2CH2NMe2)2}(CO)-
1
(PPh3)2] (5)
=
JPP 34.1 Hz) ppm. H NMR (CD2Cl2): 1.32, 1.40 (m ¥ 2, 2 ¥ 2H,
NCH2CH2CH2N); 1.87 (m, 4H, CH2NMe2); 1.95 (s, 12H, NMe2);
3.12, 3.64 (m ¥ 2, 2 ¥ 2H, CH2NCS2); 4.42, 4.97 (m ¥ 2, 2 ¥ 2H,
PCH2P); 6.37, 6.77, 6.95, 7.07, 7.17, 7.25, 7.56 (m ¥ 7, 40H, C6H5)
ppm. MS (ES +ve) m/z (abundance) = 1132 (100) [M]+. Analysis:
Calculated for C61H68F6N3P5RuS2 (Mw = 1277.27): C 57.4%, H
5.4%, N 3.3%; Found: C 57.3%, H 5.2%, N 3.2%.
=
[Ru(CH CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
(100
mg,
0.106 mmol) gave 69 mg of pale yellow product (63%). IR
(solid state): 1905 (nCO), 1540, 1500, 1462 (nCN), 1416, 1367, 1349,
1296, 1258, 1039, 830 cm-1. 31P NMR (CDCl3): 39.2 (s, PPh3) ppm.
1H NMR (CDCl3): 1.23, 1.33 (m ¥ 2, 2 ¥ 2H, NCH2CH2CH2N);
2.05 (m, 4H, CH2NMe2); 2.12, 2.16 (s ¥ 2, 2 ¥ 6H, NMe2); 2.24
(s, 3H, CCH3); 2.94, 3.20 (m ¥ 2, 2 ¥ 2H, CH2NCS2); 5.55 (d, 1H,
Hb, JHH = 16.8 Hz); 6.39, 6.83 (AB, 4H, C6H4, JAB = 8.0 Hz);
[Ru{S2CN(CH2CH2NEt2)2}(dppm)2]PF6 (2)
7.27–7.34, 7.53–7.58 (m ¥ 2, 30H, C6H5); 7.72 (dt, 1H, Ha, JHH
=
Reaction of two equivalents of KS2CN(CH2CH2NEt2)2 with cis-
[RuCl2(dppm)2] (80 mg, 0.085 mmol) gave 70 mg of colourless
product (63%). IR (solid state): 1454 (nCN), 1382, 1356, 1311,
1246, 1173, 879, 835 (nPF) cm-1. 31P NMR (CDCl3): -18.5, -6.0
16.8 Hz, JHP = 3.3 Hz) ppm. MS (ES +ve) m/z (abundance) =
1034 (68) [M]+; 772 (69) [M - PPh3]+. Analysis: Calculated for
C57H63N3OP2RuS2 (Mw = 1033.28): C 66.3%, H 6.2%, N 4.1%;
Found: C 66.2%, H 6.1%, N 3.9%.
1
(tv ¥ 2, dppm, JPP = 34.1 Hz) ppm. H NMR (CDCl3): 1.05 (t,
12H, NCH2CH3, JHH = 7.1 Hz); 2.40 (m, 4H, CH2NEt2); 2.57
(q, 8H, NCH2CH3, JHH = 7.1 Hz); 3.28, 3.81 (m ¥ 2, 2 ¥ 2H,
CH2NCS2); 4.63, 4.99 (m ¥ 2, 2 ¥ 2H, PCH2P); 6.54, 6.96, 7.04,
7.19, 7.26, 7.36, 7.61 (m ¥ 7, 40H, C6H5) ppm. MS (ES +ve)
m/z (abundance) = 1160 (100) [M]+. Analysis: Calculated for
C63H72F6N3P5RuS2 (Mw = 1305.33): C 58.0%, H 5.6%, N 3.2%;
Found: C 57.8%, H 5.5%, N 3.1%.
=
[Ru(CH CHCPh2OH){S2CN(CH2CH2CH2NMe2)2}(CO)-
(PPh3)2] (6)
=
[Ru(CH CHCPh2OH)Cl(CO)(BTD)(PPh3)2]
(300
mg,
0.290 mmol) gave 215 mg of pale yellow product (66%). IR
(solid state): 1913 (nCO), 1552, 1447(nCN), 1374, 1313, 1257(nSCS),
1236, 990, 892, 837 cm-1. 31P NMR (CDCl3): 39.9 (s, PPh3) ppm.
1H NMR (CDCl3): 1.09, 1.29 (m ¥ 2, 2 ¥ 2H, NCH2CH2CH2N);
1.99 (t, 2H, CH2NMe2; JHH = 6.9 Hz); 2.04 (t, 2H, CH2NMe2;
JHH = 7.0 Hz); 2.11, 2.15 (s ¥ 2, 2 ¥ 6H, NMe2); 2.60 (s(br), 1H,
OH); 2.77, 3.09 (m ¥ 2, 2 ¥ 2H, CH2NCS2); 5.51 (d, 1H, Hb,
[Ru{S2CN(CH2CH2OMe)2}(dppm)2]PF6 (3)
Reaction of two equivalents of KS2CN(CH2CH2OMe)2 with cis-
[RuCl2(dppm)2] (80 mg, 0.085 mmol) gave 90.7 mg of colourless
product (87%). IR (solid state): 1424, 1359, 1310, 1284, 1243, 1194,
1116, 975, 920, 831 (nPF) cm-1. 31P NMR (CD2Cl2): -18.6, -5.2 (tv ¥
JHH = 16.6 Hz); 6.83 (m, 4H, CC6H5); 6.96 (dt, 1H, Ha, JHH
=
16.6 Hz, JHP unresolved); 7.13 (m, 6H, CC6H5); 7.27–7.52 (m,
30H, PC6H5) ppm. MS (ES +ve) m/z (abundance) = 1126 (3)
[M]+; 1108 (68) [M–OH2]+; 846 (40) [M–OH2–PPh3]+. Analysis:
Calculated for C63H67N3O2P2RuS2 (Mw = 1125.38): C 67.2%, H
6.0%, N 3.7%; Found: C 67.3%, H 6.1%, N 3.8%.
1
2, dppm, JPP = 34.3 Hz) ppm. H NMR (CD2Cl2): 3.38 (s, 6H,
OCH3); 3.51 (m, 4H, CH2OMe); 3.79 (m, 4H, CH2NCS2); 4.48,
4.95 (m ¥ 2, 2 ¥ 2H, PCH2P); 6.48, 6.99, 7.10, 7.32, 7.41, 7.49, 7.69
(m ¥ 7, 40H, C6H5) ppm. MS (ES +ve) m/z (abundance) = 1078
(100) [M]+. Analysis: Calculated for C57H58F6NO2P5RuS2 (Mw
1223.14): C 56.0%, H 4.8%, N 1.2%; Found: C 55.9%, H 4.7%, N
1.1%.
=
t
t
≡
=
[Ru{C(C C Bu) CH Bu}{S2CN(CH2CH2CH2NMe2)2}(CO)-
(PPh3)2] (7)
t
t
≡
=
[Ru{C(C C Bu) CH Bu}Cl(CO)(PPh3)2] (100 mg, 0117 mmol)
gave 17 mg of pale yellow product (13%). Product was soluble
in methanol resulting in low yield. A further crop was obtained
by ultrasonic trituration in diethylether. IR (solid state): 2221
t
=
[Ru(CH CH Bu){S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2] (4)
t
=
[Ru(CH CH Bu)Cl(CO)(BTD)(PPh3)2] (100 mg, 0.110 mmol)
gave 66 mg of pale yellow product (60%). IR (solid state):
4086 | Dalton Trans., 2010, 39, 4080–4089
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=
(nC≡C), 1911 (nCO), 1574, 1785, 1459 (nCN), 1387, 1356, 1259, 915,
[Ru(CH CHCPh2OH){S2CN(CH2CH2NEt2)2}(CO)(PPh3)2]
1
843, 825 cm-1. 31P NMR (CDCl3): 38.2 (s, PPh3) ppm. H NMR
(11)
(CDCl3): 0.60 (s, 9H, tBu); 1.22 (m, 4H, NCH2CH2CH2N); 1.33 (s,
9H, tBu); 2.02 (m, 4H, CH2NMe2); 2.10, 2.14 (s ¥ 2, 2 ¥ 6H, NMe2);
2.87, 2.98 (m ¥ 2, 2 ¥ 2H, CH2NCS2); 5.19 (s, 1H, Hb); 7.24–7.36,
7.59 (m ¥ 2, 30H, C6H5) ppm. MS (ES +ve) m/z (abundance) =
1080 (42) [M]+; 818 (95) [M - PPh3]+. Analysis: Calculated for
C60H73N3OP2RuS2 (Mw = 1079.39): C 66.8%, H 6.8%, N 3.9%;
Found: C 66.7%, H 6.7%, N 4.0%.
=
[Ru(CH CHCPh2OH)Cl(CO)(BTD)(PPh3)2]
(100
mg,
0.097 mmol) gave 34 mg of pale yellow product (30%). The
product was found to be partially soluble in ethanol and a further
crop was obtained by ultrasonic trituration in diethylether. IR
(solid state): 1914 (nCO), 1550, 1446 (nCN), 1387, 1235, 1174,
988, 850 cm-1. 31P NMR (CDCl3): 40.2 (s, PPh3) ppm. H NMR
1
(CDCl3): 0.94, 0.98 (t ¥ 2, 2 ¥ 6H, NCH2CH3, JHH = 7.1 Hz); 1.93,
2.16 (m ¥ 2, 2 ¥ 2H, CH2NEt2); 2.44 (m, 8H, NCH2CH3); 2.81,
3.18 (m ¥ 2, 2 ¥ 2H, CH2NCS2); 5.51 (d, 1H, Hb, JHH = 16.6 Hz);
6.82–6.86 (m, 4H, CC6H5); 6.97 (dt, 1H, Ha, JHH = 16.6 Hz,
JHP = 2.5 Hz); 7.08–7.15 (m, 6H, CC6H5); 7.28–7.38, 7.47–7.52
(m ¥ 2, 30H, PC6H5) ppm. MS (ES +ve) m/z (abundance) =
1154 (12) [M]+; 1136 (46) [M - OH2]+; 874 (47) [M–OH2–PPh3]+.
Analysis: Calculated for C65H71N3O2P2RuS2 (Mw = 1153.43): C
67.7%, H 6.2%, N 3.6%; Found: C 67.8%, H 6.1%, N 3.5%.
=
[Os(CH CHC6H4Me-4){S2CN(CH2CH2CH2NMe2)2}(CO)-
(PPh3)2] (8)
=
[Os(CH CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
(20
mg,
0.019 mmol) gave 7 mg of pale yellow product (33%). The
product was found to be partially soluble in ethanol and a further
crop was obtained by ultrasonic trituration in diethylether. IR
(solid state): 1894 (nCO), 1638, 1364, 1228, 1118 cm-1. 31P NMR
1
(CDCl3): 7.4 (s, PPh3) ppm. H NMR (CDCl3): 1.21, 1.35 (m ¥
t
t
2, 2 ¥ 2H, NCH2CH2CH2N); 2.02 (t, 2H, CH2NMe2; JHH
=
≡
=
[Ru{C(C C Bu) CH Bu}{S2CN(CH2CH2NEt2)2}(CO)(PPh3)2]
7.5 Hz); 2.06 (t, 2H, CH2NMe2; JHH = 7.3 Hz); 2.09, 2.15 (s ¥ 2,
2 ¥ 6H, NMe2); 2.23 (s, 3H, CCH3); 2.82, 3.11 (m ¥ 2, 2 ¥ 2H,
CH2NCS2); 5.49 (d, 1H, Hb, JHH = 17.1 Hz); 6.38, 6.83 (AB, 4H,
C6H4, JAB = 8.0 Hz); 7.27–7.33, 7.53–7.59 (m ¥ 2, 30H, C6H5);
8.34 (dt, 1H, Ha, JHH = 17.1 Hz, JHP = 2.5 Hz) ppm. MS (ES
+ve) m/z (abundance) = 1124 (98) [M]+; 862 (39) [M - PPh3]+.
Analysis: Calculated for C57H63N3OOsP2S2 (Mw = 1122.44): C
61.0%, H 5.7%, N 3.7%; Found: C 59.0%, H 5.6%, N 3.7%.
(12)
t
t
≡
=
[Ru{C(C C Bu) CH Bu}Cl(CO)(PPh3)2] (100 mg, 0.117 mmol)
gave 60.3 mg of pale yellow product (47%). IR (solid state): 2164
(nC≡C), 1912 (nCO), 1547, 1420, 1384, 1354, 1257, 1202, 1174, 916,
844, 826 cm-1. 31P NMR (CDCl3): 38.0 (s, PPh3) ppm. H NMR
1
t
(CDCl3): 0.60 (s, 9H, Bu); 0.92, 0.98 (t ¥ 2, 2 ¥ 6H, NCH2CH3,
JHH = 7.0 Hz); 1.32 (s, 9H, tBu); 2.04 (m, 4H, CH2NEt2); 2.44 (m,
8H, NCH2CH3); 2.97, 3.04 (m ¥ 2, 2 ¥ 2H, CH2NCS2); 5.22 (s, 1H,
Hb); 7.24–7.35, 7.58 (m ¥ 2, 30H, C6H5) ppm. MS (ES +ve) m/z
(abundance) = 1108 (100) [M]+; 846 (70) [M - PPh3]+; 817 (46)
[M - CO - PPh3]+. Analysis: Calculated for C62H77N3OP2RuS2
(Mw = 1107.44): C 67.2%, H 7.0%, N 3.8%; Found: C 67.4%, H
7.0%, N 3.7%.
t
=
[Ru(CH CH Bu){S2CN(CH2CH2NEt2)2}(CO)(PPh3)2] (9)
t
=
[Ru(CH CH Bu)Cl(CO)(BTD)(PPh3)2] (100 mg, 0.110 mmol)
gave 59.8 mg of pale yellow product (53%). IR (solid state): 1898
(nCO), 1573, 1384, 1372, 1285, 1228, 1176, 984, 914 cm-1. 31P NMR
(CDCl3): 39.5 (s, PPh3) ppm. 1H NMR (CDCl3): 0.38 (s, 9H, tBu);
0.95 (m, 12H, NCH2CH3); 1.93, 2.21 (m ¥ 2, 2 ¥ 2H, CH2NEt2);
2.43 (m, 8H, NCH2CH3); 2.83, 3.28 (m ¥ 2, 2 ¥ 2H, CH2NCS2);
4.59 (d, 1H, Hb, JHH = 16.4 Hz); 6.28 (dt, 1H, Ha, JHH = 16.4 Hz,
JHP = 2.7 Hz); 7.29–7.34, 7.55–7.59 (m ¥ 2, 30H, C6H5) ppm. MS
(ES +ve) m/z (abundance) = 1028 (100) [M]+; 766 (60) [M - PPh3]+.
Analysis: Calculated for C56H69N3OP2RuS2 (Mw = 1027.32): C
65.5%, H 6.8%, N 4.1%; Found: C 65.3%, H 6.8%, N 4.0%.
=
[Os(CH CHC6H4Me-4){S2CN(CH2CH2NEt2)2}(CO)(PPh3)2]
(13)
=
[Os(CH CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
(20
mg,
0.019 mmol) gave 14 mg of pale yellow product (64%). IR
(solid state): 1893 (nCO), 1495, 1453 (nCN), 1384, 1350, 1282, 1242,
974, 831 cm-1. 31P NMR (CDCl3): 7.4 (s, PPh3) ppm. H NMR
1
(CDCl3): 0.93, 0.97 (t ¥ 2, 2 ¥ 6H, NCH2CH3, JHH = 7.1 Hz);
2.08, 2.21 (m ¥ 2, 2 ¥ 2H, CH2NEt2); 2.23 (s, 3H, CCH3); 2.43 (m,
8H, NCH2CH3); 2.86, 3.19 (m ¥ 2, 2 ¥ 2H, CH2NCS2); 5.50 (d,
1H, Hb, JHH = 17.1 Hz); 6.38, 6.83 (AB, 4H, C6H4, JAB = 7.9 Hz);
=
[Ru(CH CHC6H4Me-4){S2CN(CH2CH2NEt2)2}(CO)(PPh3)2]
(10)
=
[Ru(CH CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
(100
mg,
7.29–7.31, 7.55–7.57 (m ¥ 2, 30H, C6H5); 8.33 (dt, 1H, Ha, JHH
=
0.106 mmol) gave 73 mg of pale yellow product (65%). IR
(solid state): 1906(nCO), 1543, 1455(nCN), 1384, 1282, 1230, 1204,
1177, 969.6, 832.1 cm-1. 31P NMR (CDCl3): 39.3 (s, PPh3) ppm.
17.1 Hz, JHP = 2.4 Hz) ppm. MS (ES +ve) m/z (abundance) =
1152 (100) [M]+; 1007 (4) [M–CO–alkenyl]+; 890 (8) [M - PPh3]+.
Analysis: Calculated for C59H67N3OOsP2S2 (Mw = 1150.49): C
61.6%, H 5.9%, N 3.7%; Found: C 61.7%, H 5.8%, N 3.6%.
1H NMR (CDCl3): 0.94, 0.98 (t ¥ 2, 2 ¥ 6H, NCH2CH3, JHH
=
7.1 Hz); 2.07, 2.17 (m ¥ 2, 2 ¥ 2H, CH2NEt2); 2.24 (s, 3H, CCH3);
2.43 (m, 8H, NCH2CH3); 2.98, 3.27 (m ¥ 2, 2 ¥ 2H, CH2NCS2);
5.53 (d, 1H, Hb, JHH = 16.6 Hz); 6.37, 6.83 (AB, 4H, C6H4,
JAB = 8.0 Hz); 7.27–7.34, 7.53–7.57 (m ¥ 2, 30H, C6H5); 7.70
(dt, 1H, Ha, JHH = 16.7 Hz, JHP = 3.3 Hz) ppm. MS (ES +ve)
m/z (abundance) = 1062 (100) [M]+; 917 (6) [M–CO–alkenyl]+;
800 (55) [M - PPh3]+. Analysis: Calculated for C59H67N3OP2RuS2
(Mw = 1061.33): C 66.8%, H 6.4%, N 4.0%; Found: C 66.7%, H
6.2%, N 4.0%.
t
=
[Ru(CH CHBu ){S2CN(CH2CH2OMe)2}(CO)(PPh3)2] (14)
Reaction of 1.2 equivalents of KS2CN(CH2CH2OMe)2 with
[Ru(CH CH Bu)Cl(CO)(BTD)(PPh3)2] (100 mg, 0.110 mmol)
gave 99 mg of pale yellow product (95%). IR (solid state): 1896
(nCO), 1711, 1414, 1359, 1273, 1222, 1194, 1109, 913 cm-1. 31P
NMR (CDCl3): 39.7 (s, PPh3) ppm. H NMR (CDCl3): 0.41 (s,
9H, But); 2.85 (t, 2H, CH2, JHH = 5.9 Hz); 3.07 (t, 2H, CH2,
t
=
1
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Dalton Trans., 2010, 39, 4080–4089 | 4087
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JHH = 5.9 Hz); 3.18 (t, 2H, CH2, JHH = 6.0 Hz); 3.19, 3.20 (s ¥
2, 2 ¥ 3H, OCH3); 3.48 (t, 2H, CH2, JHH = 5.9 Hz); 4.56 (dt,
for C67H74F12N3O4P5RuS2 (Mw = 1533.37): C 52.5%, H 4.9%, N
2.7%; Found: C 52.4%, H 4.9%, N 2.7%.
1H, Hb, JHH = 16.4 Hz, JHP = 1.6 Hz); 6.31 (dt, 1H, Ha, JHH
=
16.4 Hz, JHP = 2.6 Hz); 7.29–7.33, 7.56–7.61 (m ¥ 2, 30H, C6H5)
ppm. MS (ES +ve) m/z (abundance) = 968 (61) [M + Na]+; 945 (3)
[M]+. Analysis: Calculated for C50H55NO3P2RuS2 (Mw = 945.13):
C 63.5%, H 5.9%, N 1.5%; Found: C 63.5%, H 5.8%, N 1.6%.
t
=
[Ru(CH CH Bu){S2CN(CH2CH2CH2NHMe2)2}(CO)(PPh3)2]-
(O2CCF3)2 (18)
t
=
A solution of [Ru(CH CH Bu){S2CN(CH2CH2CH2NMe2)2}-
(CO)(PPh3)2] (40 mg, 0.040 mmol) in dichloromethane (10 mL)
=
[Ru(CH CHC6H4Me-4){S2CN(CH2CH2OMe)2}(CO)(PPh3)2]
was treated with
2 equivalents of trifluoroacetic acid in
(15)
dichloromethane (1 mL) and stirred for 5 min. All solvent was
removed (rotary evaporator) and the crude product triturated
ultrasonically in diethyl ether (20 mL) to give a pale yellow
product. This was washed with diethyl ether (10 mL) and dried
to yield 37.3 mg of product (76%). IR (solid state): 2776 (nNH),
1915 (nCO), 1674 (nC=O), 1412, 1385, 1366, 1307, 1286, 1256, 1236,
1197, 1170, 1125, 1091, 1029, 999, 969, 951, 829 cm-1. 31P NMR
(CDCl3): 39.2 (s, PPh3) ppm. 1H NMR (CDCl3): 0.41 (s, 9H, tBu);
1.42, 1.73 (m ¥ 2, 2 ¥ 2H, NCH2CH2CH2N); 2.66, 2.72 (s ¥ 2, 2 ¥
6H, NMe2); 2.80, 2.88 (m ¥ 2, 2 ¥ 2H, CH2NMe2); 3.28, 3.51 (m ¥
Reaction of 1.2 equivalents of KS2CN(CH2CH2OMe)2 with
=
[Ru(CH CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2]
0.106 mmol) gave 83 mg of pale yellow product (80%). IR
(100
mg,
(solid state): 1907 (nCO), 1712, 1541, 1506, 1413, 1361, 1274, 1179,
1
1110, 969, 829 cm-1. 31P NMR (CDCl3): 39.3 (s, PPh3) ppm. H
NMR (CDCl3): 2.25 (s, 3H, CCH3); 3.00 (t, 2H, CH2, JHH
=
5.8 Hz); 3.14 (t, 2H, CH2, JHH = 5.7 Hz); 3.19, 3.24 (s ¥ 2, 2 ¥ 3H,
OCH3); 3.24 (t, 2H, CH2, JHH = 5.9 Hz); 3.50 (t, 2H, CH2, JHH
=
5.7 Hz); 5.53 (d, 1H, Hb, JHH = 16.8 Hz); 6.43, 6.85 (AB, 4H,
C6H4, JAB = 7.9 Hz); 7.29–7.36, 7.55–7.59 (m ¥ 2, 30H, C6H5);
7.72 (dt, 1H, Ha, JHH = 16.8 Hz, JHP = 3.2 Hz) ppm. MS (ES
+ve) m/z (abundance) = 1002 (20) [M + Na]+, 1002 (9) [M]+, 862
(39) [M - alkenyl]+. Analysis: Calculated for C53H53NO3P2RuS2
(Mw = 979.14): C 65.0%, H 5.5%, N 1.4%; Found: C 65.1%, H
6.1%, N 1.7%.
2, 2 ¥ 2H, CH2NCS2); 4.60 (dt, 1H, Hb, JHH = 16.4 Hz; JHP
=
1.6 Hz); 6.31 (dt, 1H, Ha, JHH = 16.4 Hz, JHP = 2.7 Hz); 7.32–
7.36, 7.52–7.57 (m ¥ 2, 30H, C6H5), 12.80 (s(br), 2H, NHMe2)
ppm. MS (ES +ve) m/z (abundance) = 1000 (95) [M]+; 738 (75)
[M - PPh3]+. Analysis: Calculated for C58H67F6N3O5P2RuS2 (Mw =
1227.31): C 56.8%, H 5.5%, N 3.4%; Found: C 56.8%, H 5.7%,
N 3.3%.
t
t
≡
=
[Ru{C(C C Bu) CH Bu}{S2CN(CH2CH2OMe)2}(CO)(PPh3)2]
=
=
(16)
[Ru( CHCH CPh2){S2CN(CH2CH2CH2NHMe2)2}(CO)-
(PPh3)2](O2CCF3)3 (19)
Reaction of 1.2 equivalents of KS2CN(CH2CH2OMe)2 with
t
t
≡
=
=
solution of [Ru(CH CHCPh2OH){S2CN(CH2CH2CH2-
[Ru{C(C C Bu) CH Bu}Cl(CO)(PPh3)2] (100 mg, 0.117 mmol)
gave 83 mg of pale yellow product (69%). IR (solid state): 2166
(nC≡C), 1911 (nCO), 1413, 1387, 1356, 1305, 1275, 1260, 1232, 1195,
1111, 964 cm-1. 31P NMR (CDCl3): 38.3 (s, PPh3) ppm. 1H NMR
(CDCl3): 0.61 (s, 9H, But); 3.01, 3.13 (m ¥ 2, 2 ¥ 4H, CH2);
1.31 (s, 9H, But); 3.19, 3.22 (s ¥ 2, 2 ¥ 3H, OCH3); 5.19 (s, 1H,
Hb); 7.26–7.36, 7.59 (m ¥ 2, 30H, C6H5) ppm. MS (ES +ve) m/z
(abundance) = 1048 (19) [M + Na]+; 1026 (22) [M]+. Analysis:
Calculated for C56H63NO3P2RuS2 (Mw = 1025.25): C 65.6%, H
6.2%, N 1.4%; Found: C 65.7%, H 6.3%, N 1.5%.
A
NMe2)2}(CO)(PPh3)2] (100 mg, 0.089 mmol) in dichloromethane
(30 mL) was treated with excess trifluoroacetic acid (15 drops) in
dichloromethane (1 mL) and stirred for 5 min leading to a deep red
colour. All solvent was removed (rotary evaporator) and the crude
product triturated ultrasonically in petroleum ether (20 mL) to give
a dark red product. This was washed with petroleum ether (10 mL)
and dried to yield 110 mg of product (85%). IR (solid state): 2721
(nNH), 1952 (nCO), 1782, 1739, 1673 (nC=O), 1600, 1575, 1384, 1309,
1174, 1127, 938, 830, 798 cm-1. 31P NMR (CDCl3): 32.0 (s, PPh3)
1
ppm. 13C{ H} NMR (CD2Cl2): 310.5 (t, RuC, JCP = 8.6 Hz); 204.8
(s, CS2); 201.4 (t, CO, JCP = 12.8 Hz); 161.3 (s, CPh2); 160.9 (q,
O2C, JCF = 37.8 Hz); 147.1 (t, Cb, JCP = unresolved); 140.0, 138.1
(s ¥ 2, 2 ¥ CC6H5); 134.6 (tv, o/m-PC6H5, JCP = 4.7 Hz); 133.5,
131.9 (s ¥ 2, 2 ¥ CC6H5); 131.4 (s, p-PC6H5); 131.1 (s, CC6H5);
130.3 (tv, ipso-PC6H5, JCP = 24.1 Hz); 129.5 (s, CC6H5); 128.7
(tv, o/m-PC6H5, JCP = 4.5 Hz); 128.6 (s, CC6H5); 116.3 (q, CF3,
JCF = 289.1 Hz); 55.2, 55.1 (s ¥ 2, NCH2); 47.4 (s, NCH2), 43.5
(s, NHMe2); 22.3, 21.9 (s ¥ 2, CCH2C) ppm. 1H NMR (CDCl3):
1.41 (m, 2 ¥ 2H, NCH2CH2CH2N); 2.80, 2.83 (s ¥ 2, 2 ¥ 6H,
NMe2); 2.98 (m, 4H + 4H, CH2NMe2 + CH2NCS2); 6.14 (d, 2H,
ortho-CC6H5, JHH = 7.0 Hz); 7.11 (m, 4H, CC6H5); 7.29–7.85 (m,
30H + 4H, PC6H5 + CC6H5); 8.10 (d, 1H, Hb, JHH = 14.0 Hz);
11.83 (s(br), 2H, NHMe2); 14.68 (d, 1H, Ha, JHH = 14.0 Hz) ppm.
MS (FAB +ve) m/z (abundance) = 1108 (16) [M]+, 916 (40) [M -
alkenylcarbene]+, 846 (100) [M - PPh3]+. Analysis: Calculated for
C69H68F9N3O7P2RuS2·3CH2Cl2 (Mw = 1449.43): C 50.7%, H 4.4%,
N 2.5%; Found: C 51.2%, H 4.1%, N 2.5%.
[Ru{S2CN(CH2CH2NHEt2)2}(dppm)2](PF6)(O2CCF3)2 (17)
A solution of [Ru{S2CN(CH2CH2NEt2)2}(dppm)2](PF6) (40 mg,
0.031 mmol) in dichloromethane (10 mL) was treated with 2
equivalents of trifluoroacetic acid in dichloromethane (0.8 mL)
and stirred for 5 min. All solvent was removed (rotary evaporator)
and the crude product triturated ultrasonically in diethyl ether
(20 mL) to give a yellow product. This was washed with diethyl
ether (10 mL) and dried to yield 37.8 mg of product (80%). IR
(solid state): 2811 (nNH), 1670 (nC=O), 1310, 1241, 1198, 1177,
1127, 1096, 833 (nPF) cm-1. 31P NMR (CDCl3): -5.7, -17.5 (tv ¥
1
2, dppm, JPP = 34.4 Hz) ppm. H NMR (CDCl3): 1.29 (s(br),
12H, NCH2CH3); 2.66, 3.00 (m ¥ 2, 2 ¥ 2H, CH2NEt2); 3.14
(s(br), 8H, NCH2CH3); 3.65, 4.40 (m ¥ 2, 2 ¥ 2H, CH2NCS2);
4.45, 4.93 (m ¥ 2, 2 ¥ 2H, PCH2P); 6.46, 6.95, 7.12, 7.22–7.42,
7.60 (m ¥ 5, 40H, C6H5), 12.08 (s(br), 2H, NHEt2) ppm. MS (ES
+ve) m/z (abundance) = 1160 (100) [M]+. Analysis: Calculated
4088 | Dalton Trans., 2010, 39, 4080–4089
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View Article Online
Crystallography
7 (a) Y. H. Lin, N. H. Leung, K. B. Holt, A. L. Thompson and J. D. E. T.
Wilton-Ely, Dalton Trans., 2009, 7891–7901.
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10 For an overview of alkenyl chemistry of ruthenium(II), see: (a) M. K.
Whittlesey in Comprehensive Organometallic Chemistry III, eds.
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Single crystals of complexes 3 and 15 were grown by slow diffusion
of ethanol into a dichloromethane solution of each complex.
Crystal data for 3: [C57H58NO2P4RuS2](PF6), M = 1223.08,
monoclinic, P21/c (no. 14), a = 17.3740(3), b = 12.01286(19), c =
◦
3
˚
˚
26.6409(4) A, b = 95.1247(14) , V = 5538.04(15) A , Z = 4, Dc =
1.467 g cm-3, m(Mo-Ka) = 0.566 mm-1, T = 173 K, pale yellow
needles, Oxford Diffraction Xcalibur 3 diffractometer; 12994
independent measured reflections (Rint = 0.0300), F2 refinement,
R1(obs) = 0.0316, wR2(all) = 0.0721, 9490 independent observed
absorption-corrected reflections [|Fo| > 4s(|Fo|, 2qmax = 58◦],
705 parameters. CCDC 750274.
11 H. Werner, M. A. Esteruelas and H. Otto, Organometallics, 1986, 5,
2295–2299.
Crystal data for 15: C53H53NO3P2RuS2·0.3CH2Cl2, M
=
12 M. R. Torres, A. Vegas, A. Santos and J. Ros, J. Organomet. Chem.,
1986, 309, 169–177.
13 S. Jung, K. Ilg, C. D. Brandt, J. Wolf and H. Werner, Eur. J. Inorg.
Chem., 2004, 469–480.
14 M. A. Esteruelas, A. M. Lo´pez and E. On˜ate, Organometallics, 2007,
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Chem., 2001, 2305–2310.
¯
1004.57, triclinic, P1 (no. 2), a = 11.9999(3), b = 15.2412(3), c =
◦
˚
15.3608(4) A, a = 111.203(2), b = 106.398(2), g = 95.0213(18) ,
3
-3
˚
V = 2455.53(12) A , Z = 2, Dc = 1.359 g cm , m(Cu-Ka) =
4.631 mm-1, T = 173 K, pale yellow platy needles, Oxford
Diffraction Xcalibur PX Ultra diffractometer; 9694 independent
measured reflections (Rint = 0.0248), F2 refinement, R1(obs) =
0.0278, wR2(all) = 0.0713, 8842 independent observed absorption-
corrected reflections [|Fo| > 4s(|Fo|, 2qmax = 145◦], 629 param-
eters. CCDC 750275.
16 D. J. Huang, K. B. Renkema and K. G. Caulton, Polyhedron, 2006, 25,
459–468.
17 (a) A. F. Hill and R. P. Melling, J. Organomet. Chem., 1990, 396, C22–
C24; (b) A. F. Hill, M. C. J. Harris and R. P. Melling, Polyhedron,
1992, 11, 781–787; (c) M. C. J. Harris and A. F. Hill, Organometallics,
1991, 10, 3903–3906; (d) R. B. Bedford, A. F. Hill, A. R. Thompsett,
A. J. P. White and D. J. Williams, Chem. Commun., 1996, 1059–1060;
(e) A. F. Hill, A. J. P. White, D. J. Williams and J. D. E. T. Wilton-Ely,
Organometallics, 1998, 17, 4249–4258; (f) J. C. Cannadine, A. F. Hill,
A. J. P. White, D. J. Williams and J. D. E. T. Wilton-Ely, Organometallics,
1996, 15, 5409–5415; (g) A. F. Hill, C. T. Ho and J. D. E. T. Wilton-
Ely, Chem. Commun., 1997, 2207–2208; (h) A. F. Hill and J. D. E. T.
Wilton-Ely, J. Chem. Soc., Dalton Trans., 1998, 3501–3510; (i) A. R.
Cowley, A. L. Hector, A. F. Hill, A. White, D. J. Williams and J. D. E. T.
Wilton-Ely, Organometallics, 2007, 26, 6114–6125; (j) R. B. Bedford,
A. F. Hill, C. Jones, A. J. P. White, D. J. Williams and J. D. E. T. Wilton-
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Dalton Trans., 1997, 139–140.
The structures were refined using the SHELXTL and SHELX-
97 program systems.23 Further details can be found in the
Supporting Information.†
Acknowledgements
We gratefully acknowledge Johnson Matthey Ltd for a generous
loan of ruthenium and osmium salts and the Nuffield Foundation
for a bursary (E.O.).
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t
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≡
=
[Ru{C(C CBu ) CHBu }Cl(CO)(PPh3)2] in reference 17c.
23 SHELXTL PC version 5.1, Bruker AXS, Madison, WI, 1997; SHELX-
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This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 4080–4089 | 4089
©