Multimetallic complexes based on a diphosphine-dithiocarbamate "janus" ligand

Article abstract of DOI:10.1021/ic5028527

The HCl salt of the aminodiphosphine ligand HN(CH₂CH₂PPh₂)₂ reacts with [M(CO)₄(pip)₂] (M = Mo, W; pip = piperidine) to yield [M{κ²-HN(CH₂CH₂PPh₂)₂}(CO)₄]. The molybdenum analogue readily loses a carbonyl ligand to form [Mo{κ³-HN(CH₂CH₂PPh₂)₂}(CO)₃], which was structurally characterized. The same ligand backbone is used to form the new bifunctional ligand, KS₂CN(CH₂CH₂PPh₂)₂, which reacts with nickel and cobalt precursors to yield [Ni{S₂CN(CH₂CH₂PPh₂)₂}₂] and [Co{S₂CN(CH₂CH₂PPh₂)₂}₃]. Addition of [AuCl(tht)] (tht = tetrahydrothiophene) to [Ni{S₂CN(CH₂CH₂PPh₂)₂}₂] leads to formation of the pentametallic complex, [Ni{S₂CN(CH₂CH₂PPh₂AuCl)₂}₂]. In contrast, addition of [PdCl₂(py)₂] (py = pyridine) to [Ni{S₂CN(CH₂CH₂PPh₂)₂}₂] does not lead to a trimetallic complex but instead yields the transmetalated cyclic compound [Pd{S₂CN(CH₂CH₂PPh₂)₂}]₂, which was structurally characterized. The same product is obtained directly from [PdCl₂(py)₂] and KS₂CN(CH₂CH₂PPh₂)₂. In contrast, the same reaction with [PtCl₂(NCPh)₂] yields the oligomer, [Pt{S₂CN(CH₂CH₂PPh₂)₂}]_n. Reaction of KS₂CN(CH₂CH₂PPh₂)₂ with cis-[RuCl₂(dppm)₂] provides [Ru{S₂CN(CH₂CH₂PPh₂)₂}(dppm)₂]⁺, which reacts with [AuCl(tht)] to yield [Ru{S₂CN(CH₂CH₂PPh₂AuCl)₂}(dppm)₂]⁺. Addition of [M(CO)₄(pip)₂] (M = Mo, W) to the same precursor leads to formation of the bimetallic compounds [(dppm)₂Ru{S₂CN(CH₂CH₂PPh₂)₂}M(CO)₄]⁺, while treatment with [ReCl(CO)₅] yields [(dppm)₂Ru{S₂CN(CH₂CH₂PPh₂)₂}ReCl(CO)₃]⁺. Reaction of KS₂CN(CH₂CH₂PPh₂)₂ with [Os(CH=CHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃)₂] (BTD = 2,1,3-benzothiadiazole) provides [Os(CH=CHC₆H₄Me-4){S₂CN(CH₂CH₂PPh₂)₂}(CO)(PPh₃)₂], but reaction with the analogous ruthenium precursor fails to yield a clean product.

Full text of DOI:10.1021/ic5028527

Article
pubs.acs.org/IC
Multimetallic Complexes Based on a Diphosphine-Dithiocarbamate
“Janus” Ligand
Rebecca Sherwood,† Ferran Gonzalez de Rivera,†,‡ Jane Hui Wan,† Qi Zhang,§ Andrew J. P. White,†
̀
Oriol Rossell,‡ Graeme Hogarth,∥ and James D. E. T. Wilton-Ely*,†
†Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, U.K.
‡Departament de Química Inorgan
̀ ̀
ica, Universitat de Barcelona, Martí Franques 1-11, 08028, Barcelona, Spain
§Hainan Provincial Key Laboratory of Fine Chemicals, Hainan University, Haikou, Hainan 570228, China
∥Department of Chemistry, King’s College London, Britannia House, 7 Trinity Street, London SE1 1DB, U.K.
S
* Supporting Information
ABSTRACT: The HCl salt of the aminodiphosphine ligand
HN(CH2CH2PPh2)2 reacts with [M(CO)4(pip)2] (M = Mo, W;
pip = piperidine) to yield [M{κ2-HN(CH2CH2PPh2)2}(CO)4]. The
molybdenum analogue readily loses a carbonyl ligand to form
[Mo{κ3-HN(CH2CH2PPh2)2}(CO)3], which was structurally charac-
terized. The same ligand backbone is used to form the new
bifunctional ligand, KS2CN(CH2CH2PPh2)2, which reacts with nickel
and cobalt precursors to yield [Ni{S2CN(CH2CH2PPh2)2}2] and
[Co{S2CN(CH2CH2PPh2)2}3]. Addition of [AuCl(tht)] (tht =
tetrahydrothiophene) to [Ni{S2CN(CH2CH2PPh2)2}2] leads to
formation of the pentametallic complex, [Ni{S2CN(CH2CH2PPh2-
AuCl)2}2]. In contrast, addition of [PdCl2(py)2] (py = pyridine) to
[Ni{S2CN(CH2CH2PPh2)2}2] does not lead to a trimetallic complex but instead yields the transmetalated cyclic compound
[Pd{S2CN(CH2CH2PPh2)2}]2, which was structurally characterized. The same product is obtained directly from [PdCl2(py)2]
and KS2CN(CH2CH2PPh2)2. In contrast, the same reaction with [PtCl2(NCPh)2] yields the oligomer, [Pt{S2CN(CH2CH2-
PPh2)2}]n. Reaction of KS2CN(CH2CH2PPh2)2 with cis-[RuCl2(dppm)2] provides [Ru{S2CN(CH2CH2PPh2)2}(dppm)2]+,
which reacts with [AuCl(tht)] to yield [Ru{S2CN(CH2CH2PPh2AuCl)2}(dppm)2]+. Addition of [M(CO)4(pip)2] (M = Mo, W)
to the same precursor leads to formation of the bimetallic compounds [(dppm)2Ru{S2CN(CH2CH2PPh2)2}M(CO)4]+, while
treatment with [ReCl(CO)5] yields [(dppm)2Ru{S2CN(CH2CH2PPh2)2}ReCl(CO)3]+. Reaction of KS2CN(CH2CH2PPh2)2
with [Os(CHCHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) provides [Os(CHCHC6H4Me-
4){S2CN(CH2CH2PPh2)2}(CO)(PPh3)2], but reaction with the analogous ruthenium precursor fails to yield a clean product.
dithiocarbamate ligands (e.g., coordination to other metals,5−7
INTRODUCTION
■
alkene metathesis8) in order to address applications such as d-f
Alongside thiolate compounds, dithiocarbamate complexes
hybrids with the potential for medical imaging.9 For over a
MS2CNR2 feature at the forefront of S-ligand transition metal
coordination chemistry. In the hundred years since the first
decade, renewed interest in dithiocarbamates has also focused
on their use as surface units for gold nanoparticles.10 Linked to
report of a transition metal bearing the dithiocarbamate ligand,1
a vast array of examples have been reported.2 Although
this development, a number of reports have probed the
significant advances have been achieved in recent years,2e,3 this
versatility has often remained unexploited in terms of extending
the ligand architecture beyond simple nitrogen substituents
potential of this method for placing metal units on the surface
of gold nanoparticles.6,8c,9,11
Bifunctional linkers bearing dithiocarbamates have been
employed in both multimetallic assemblies and metal-function-
(ligands with R = Me, Et are commercially available).
alized nanoparticles. Examples with additional dithiocarbama-
The rationale for the construction of multimetallic assemblies
te,5a−d,6,12 bipyridine,11a terpyridine,11b and porphyrin11c units
through careful choice of bifunctional linkers was proposed
over a decade ago.4a The pioneering work of Lang and co-
have been demonstrated to allow incorporation of additional
workers,4b−k in particular, has demonstrated how bifunctional
metal units beyond the dithiocarbamate unit itself. This can be
achieved through generation of the second donor site after
linkers such as bpyCCH and HCCC6H4PPh2-4 allow the
attachment of the first metal, as demonstrated by the treatment
stepwise construction of compounds such as [(dppf)CpRu-
(CCC6H4PPh2-4)Au{CC-bpyReCl(CO)3}].4c Our recent
contributions in the this area have attempted to tap into this
potential through manipulation of the NR2 substituents of
Received: November 28, 2014
Published: April 16, 2015
© 2015 American Chemical Society
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Figure 1. Examples of amine-terminated dithiocarbamate complexes.
of [Ru(S2CNC4H8NH2)(dppm)2]2+ with base, carbon disulfide,
and a metal to provide [Ru(S2CNC4H8NCS2MLn)-
(dppm)2]m+.5a,b,6a Alternatively, addition of further metals to
the system can be achieved through the preference of the new
metal (e.g., lanthanide ions) for the harder oxygen and nitrogen
donors of a macrocycle.9
Scheme 1. Reactivity of the Aminophosphine Backbone
a
Used in This Work
While bifunctional phosphine-thiol linkers have been used
successfully to modify the surface of nanoparticles,13 to our
knowledge, no linker has been reported that bears both
dithiocarbamate and diphosphine functionalities. Given the
ubiquity of phosphine ligands in applications of transition
metals, this linker was considered a promising route to
multimetallic complexes with potential for roles in catalysis.
Previous work by some of us has exploited bifunctional
phosphine units for the preparation of large dendrimer14a and
nanoparticle14b assemblies for application in this area. As
described below, while the novel dithiocarbamate-diphosphine
ligand described here proved to be a successful linker in a
number of cases, unexpected coordination chemistry was also
encountered. In discussing this reactivity, it is useful to draw
upon the analogous amino-functionalized complexes reported
in 2009 (Figure 1)5f and amine-phosphine complexes based on
the same RN(CH2CH2PPh2)2 backbone (vide infra).
a
dba = dibenzylideneacetone; pip = piperidine; DCC = dicyclohex-
ylcarbodiimide; DMAP = N,N-(dimethylamino)pyridine; R = C(O)-
C6H4OMe-4.
nitrogen unit for further functionalization, molybdenum and
tungsten complexes were investigated (Scheme 1).
RESULTS AND DISCUSSION
■
Treatment of the versatile zerovalent molybdenum precursor
[Mo(CO)4(pip)2] (pip = piperidine) with 1 equiv of
[H2N(CH2CH2PPh2)2]Cl (prepared using the literature
method16) led initially to bidentate coordination through the
phosphines. The product was formulated as the tetracarbonyl
species [Mo{κ2-HN(CH2CH2PPh2)2}(CO)4] (4) on the basis
of the solid state infrared spectrum (absorptions between 1862
and 2013 cm−1) and a molecular ion in the mass spectrum at
m/z 650. In addition to a singlet in the 31P{1H} NMR spectrum
Preparation of Amino-Diphosphine Compounds.
Chelates combining phosphine and amine (or amide) donors
have been used widely in transition metal chemistry and have
found particularly frequent application in catalysis.15 Ligands of
the type RN(CH2CH2PPh2)2 show a range of coordination
modes, which illustrate the flexibility of the ethylene bridges
(Scheme 1). Bis[2-(diphenylphosphino)ethyl]amine is readily
accessible from commercially available bis(2-chloroethyl)amine
and diphenylphosphine in the presence of KOtBu. Acid workup
is also often employed to furnish the hydrochloride salt,16
which is a convenient starting point for further functionaliza-
tion.17
With zerovalent palladium precursors such as [Pd2(dba)3]
(dba = dibenzylideneacetone), bidentate diphosphine chelates
are observed (1), which are in equilibrium with the tridentate
PNP donor combination in coordinating solvents.17 With
Pd(II) precursors, cationic complexes are isolated (2)18 in
which the phosphine ligands have been crystallographically
determined to adopt a trans arrangement. A different, cyclic
coordination mode (3) is observed on reaction of equimolar
amounts of the diphosphine ligand and [PdCl2(NCMe)2].17
In order to explore the coordination possibilities of this
framework further and to establish the availability of the
1
at 19.8 ppm, H NMR analysis revealed resonances for the
ethylene bridges at 1.66 and 2.71 ppm. The resonance at 4.25
ppm (integrating to single proton) was assigned as the amine
proton, indicating that the piperidine ligands lost from the
starting material had deprotonated the ammonium moiety.
Although some spectroscopic data could be obtained,
isolating 4 proved to be challenging as spontaneous loss of a
carbonyl ligand was found to occur even under mild conditions,
leading to coordination of the nitrogen donor to give the
tricarbonyl product [Mo{κ3-HN(CH2CH2PPh2)2}(CO)3] (5).
1
The features displayed in the H NMR spectrum did not
change substantially; however, a simplification of the
absorptions in the infrared spectrum was observed and a new
resonance was noted in the 31P{1H} NMR spectrum at 39.2
ppm. This complex has been reported previously by Ellermann
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and co-workers, whose data are in good agreement with those
obtained in this work.19 In order to provide structural data and
to investigate the flexibility of the phosphine arms of the
chelate, single crystals of 5 were successfully grown and a
structural study was undertaken (Figure 2).
123° and 106° for the interactions involving the substituents on
the P2 and P1 atoms, respectively. More substantial interactions
are observed between the N−H hydrogen and oxygen atoms in
neighboring molecules. These are linked through the N−H
hydrogen and the O3 carbonyl oxygen atom in a Ci related
molecule (and vice versa) forming a dimer pair [the N···O
distance is 3.085 Å and the H···O distance is 2.29 Å with the
N−H angle of 148° and the bond distance set at 0.9 Å]. These
interactions are illustrated in Figure S2 in the Supporting
Information.
The tungsten analogue [W{κ2-HN(CH2CH2PPh2)2}(CO)4]
(6) was also prepared by the same route from [W-
(CO)4(pip)2]. Similar spectroscopic data were observed for
this compound as for 4, apart from the presence of tungsten
satellites (JPW = 234.0 Hz) in the 31P{1H} NMR spectrum for
the resonance at 2.9 ppm. The formulation was further
supported by good agreement of elemental analysis with
calculated values and a molecular ion in the mass spectrum at
m/z 738. The tungsten analogue of 5, [W{κ3-HN-
(CH2CH2PPh2)2}(CO)3], is known, although is prepared by
a different route.19 However, in contrast to the reaction shown
by 4, compound 6 showed no tendency to form this tricarbonyl
product, allowing the reactivity of the pendant amine to be
explored as an alternative route to multimetallic complexes.
Taken together, the structural diversity of these compounds
established the reactivity of the phosphine donors and that of
the bridgehead nitrogen in the HN(CH2CH2PPh2)2 ligand.
The effect of transforming the nitrogen into a dithiocarbamate
to provide a sulfur-phosphine donor combination in place of
the PNP arrangement was then investigated.
Synthesis of Homonuclear Dithiocarbamate Com-
plexes. Various bases (KOH, NEt3, DBU) were explored for
the deprotonation of the hydrochloride salt, [H2N(CH2-
CH2PPh2)2]Cl in the presence of carbon disulfide; however,
potassium carbonate in dry acetonitrile was found to be most
effective. Using this approach, KS2CN(CH2CH2PPh2)2 (7) was
isolated in 91% yield. A new singlet was observed in the
31P{1H} NMR spectrum at −20.1 ppm, while the ethylene
protons appeared as multiplets at 2.48 and 4.11 ppm in the 1H
NMR spectrum. The presence of the CS2 unit was confirmed
by a resonance at a typically downfield chemical shift2d of 211.5
ppm in the 13C{1H} NMR spectrum. In the electrospray mass
spectrum, a [M + H2O]− ion was observed at m/z 532. Good
agreement of determined elemental analysis values with
calculated values further supported the formulation of 7
shown in Scheme 2.
Figure 2. Molecular structure of [Mo{κ3-HN(CH2CH2PPh2)2}-
(CO)3] (5). Selected bond lengths (Å) and angles (deg): Mo(1)−
C(1) = 1.9491(15), Mo(1)−C(3) = 1.9497(15), Mo(1)−C(2) =
1.9772(15), Mo(1)−N(1) = 2.3340(12), Mo(1)−P(2) = 2.5292(4),
Mo(1)−P(1) = 2.5400(4), O(1)−C(1) = 1.1635(19), O(2)−C(2) =
1.1580(19), O(3)−C(3) = 1.1680(18), C(1)−Mo(1)−N(1) =
174.97(5), N(1)−Mo(1)−P(1) = 77.22(3), N(1)−Mo(1)−P(2) =
78.31(3), C(1)−Mo(1)−P(2) = 100.19(5).
The complex adopts a distorted octahedral structure with cis-
interligand angles in the range 77.22(3)−100.19(5)°. The P−
N−P ligand is chelated in a facial manner through five-
membered metallacycles, in which some degree of strain is
evident, with the smallest angles between cis donors being the
N−Mo−P angles. The facial coordination in this complex was
inferred previously from spectroscopic data, in contrast to the
chromium analogue which is thought to adopt a mer-
arrangement.19 Ellermann and co-workers also proposed
interactions between the carbonyl ligands and the ortho-
protons of the phenyl rings (in line with their previous work20).
In the structure of 5, the PNP ligand adopts a low symmetry
arrangement such that the closest C−O approach to an ortho-
phenyl proton attached to the P2 phosphorus is around 2.80 Å,
whereas the closest interaction involving the protons of the aryl
substituents attached to P1 is approximately 3.00 Å. In both
cases the C−H···O hydrogen bonding interactions deviate
substantially from the usual 180° angle, displaying angles of
Nickel bis(dithiocarbamate) complexes occupy a reliable and
well-established chapter in the library of dithiocarbamate
complexes.2 However, most known [Ni(S2CNR2)2] com-
pounds possess NR2 units with unreactive substituents. In the
project described here, it was not immediately obvious whether
the reaction would be limited to the sulfur donors of 7.
Treatment of NiCl2·6H2O with 2 equiv of 7 in methanol led to
formation of a green product in good yield. 31P{1H} NMR
analysis revealed a resonance at −20.4 ppm (cf., −20.1 ppm for
Scheme 2. Preparation of the Diphosphine Bis(dithiocarbamate) Ligand 7
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Scheme 3. Reaction of Bifunctional 7 with Chloride Compounds of Group 10
7), indicating that no reaction had taken place at the
phosphines. A shift was observed in the ethylene resonances
1
of 2.34 and 3.56 ppm in the H NMR spectrum relative to the
precursor. A displacement of the chemical shift of the CS2
resonance to 206.9 ppm was noted in the 13C{1H} NMR
spectrum. On the basis of these data as well as mass
spectrometry and elemental analysis results, the product was
formulated as [Ni{S2CN(CH2CH2PPh2)2}2] (8), as shown in
Scheme 3. These data agree well with the values recorded for
the corresponding amine-terminated literature complex [Ni-
{S2CN(CH2CH2NEt2)2}2].5f
After the successful reaction of 7 with nickel(II) chloride, it
was expected that the same reaction pathway would be followed
on treatment of 7 with [PdCl2(py)2], as has been observed in
the formation of the amino-derivative [Pd{S2CN-
(CH2CH2NEt2)2}2].5f The reaction of 7 and [PdCl2(py)2] in
a 2:1 ratio yielded a yellow product in modest yield. The most
informative technique was again 31P{1H} NMR spectroscopy,
which revealed a change of more than 28 ppm in the chemical
shift values of the phosphorus nuclei to 8.2 ppm. The
resonances for the CH2 bridges were found to be split into
four separate resonances of equal intensity in the H NMR
spectrum between 3.13 and 4.93 ppm. Mass spectrometry and
elemental analysis data were found to be consistent for a 1:1
metal/ligand complex rather than a ratio of 1:2. Slow
evaporation of a solution of the complex in methanol yielded
single crystals suitable for X-ray diffraction. The structure was
determined to reveal a cyclic formulation, [Pd{S2CN(CH2CH2-
PPh2)2}]2(Cl)2 (9), as shown in Figure 3.
Figure 3. Molecular structure of the dication in [Pd{S2CN(CH2CH2-
PPh2)2}]2(Cl)2 (9) with the counteranions omitted for clarity.
Selected bond lengths (Å) and angles (deg): Pd(1)−P(10) =
2.2702(10), Pd(1)−P(7) = 2.2978(11), Pd(1)−S(1A) = 2.3371(10),
Pd(1)−S(3A) = 2.3438(10), S(1)−C(2) = 1.714(4), S(1)−Pd(1A) =
2.3372(10), C(2)−N(4) = 1.327(5), C(2)−S(3) = 1.725(4), S(3)−
Pd(1A) = 2.3438(10), P(10)−Pd(1)−P(7) = 97.21(4), P(10)−
Pd(1)−S(1A) = 95.97(4), P(7)−Pd(1)−S(3A) = 91.02(4), S(1A)−
Pd(1)−S(3A) = 74.99(3), S(1)−C(2)−S(3) = 111.9(2).
1
The structural study revealed a square planar arrangement for
this bimetallic dication (9) in which the two palladium centers
are incorporated in a 14-membered ring. The sum of the bond
angles around the palladium centers is 359.2°, indicating a
relatively low level of distortion from an ideal square planar
geometry. The cis-interligand angles are 74.99(3)−97.21(4)°
with the smallest angle being the S(1A)−Pd(1)−S(3A) angle
and the largest that between the two phosphines. This angle
and the bond lengths Pd(1)−S(1A) [2.3371(10) Å] and
Pd(1)−S(3A) [2.3438(10) Å] are similar to comparable
palladium dithiocarbamate compounds, such as [(dppm)2Ru-
(S2CNC4H8NCS2)Pd(PPh3)2](BF4)2.6a The C(2)−N(4) bond
distance of 1.327(5) Å is clearly multiple in nature, falling
between typical distances for C−N and CN lengths of 1.47
and 1.29 Å, respectively.21 The synthesis of 9 was optimized
from [PdCl2(py)2] using only 1 equiv of ligand 7. The same
product was also obtained in attempts to add “PdCl2” units to 8
through reaction with [PdCl2(py)2].
This fascinating departure from the reactivity shown with
nickel(II) chloride led to the same reaction being investigated
with the platinum(II) chloride precursor [PtCl2(NCPh)2]. This
reaction resulted in the formation of a yellow precipitate, which
proved insoluble in all common laboratory solvents at room
temperature. However, after many attempts, NMR analysis did
finally prove possible in deuterated dimethyl sulfoxide at 80 °C.
1
This revealed broad resonances in the H NMR spectrum at
3.42 and 4.52 ppm for the ethylene units and a multiplet at 7.70
ppm for the aromatic protons. This was supported by infrared
spectroscopy, which confirmed the presence of the [S2CN-
(CH2CH2PPh2)2]− ligand, while elemental analysis suggested
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a
Scheme 4. Reaction To Form Mono-, Di-, Tri-, and Pentametallic Compounds
a
tht = tetrahydrothiophene, pip = piperidine, nbd = norbornadiene.
the ratio of 1:1 for the metal/ligand relationship. On the basis
of these data and its insoluble nature, the product was
resonances in the 31P{1H} NMR spectrum at −18.6 and −5.7
ppm showing mutual coupling of 34.4 Hz, while the presence of
the pendant phosphines was indicated by a singlet at −21.3
ppm.
formulated as
a cationic oligomer [Pt{S2 CN-
+
(CH2CH2PPh2)2]n (10). Repeated attempts to grow crystals
suitable for a structural determination through layering separate
solvents with the metal precursor and the ligand proved
unsuccessful and only provided a fine powder.
The chelation of the dppm ligands in 12 afforded protection
against further reaction of the pendant phosphine units with the
metal center. However, the need for this precaution was probed
using the triphenylphosphine vinyl complex [Ru(CH
CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzo-
thiadiazole), which has been shown to readily react with
dithiocarbamates5c,6a,8a,b and be susceptible to the loss of
phosphines.22 Reaction of 7 with the ruthenium vinyl precursor,
when followed by NMR spectroscopy, led to relatively rapid
substitution (within an hour in solution) of a PPh3 ligand and a
mixture of products, possibly oligomeric in nature. However,
the osmium analogue [Os(CHCHC6H4Me-4)Cl(CO)-
(BTD)(PPh3)2]23 possesses stronger M−P bonds and was
considered likely to be more resistant to phosphine loss. The
reaction between this compound and 7 led to the formation of
[Os(CHCHC6H4Me-4){S2CN(CH2CH2PPh2)2}(CO)-
(PPh3)2] (13), which was isolated rapidly before further
reaction could occur (Scheme 4). A new singlet resonance was
observed in the 31P{1H} NMR spectrum at 7.8 ppm alongside
the resonances of the pendant phosphine units at −20.4 and
−21.3 ppm. These environments were rendered inequivalent by
the lower symmetry of the complex compared to 12. Retention
of the vinyl ligand was indicated by typical features, such as
multiplets for the Hα (dt) and Hβ (d) protons at 8.37 and 5.51
ppm, respectively. Mass spectrometry and elemental analysis
data confirmed the overall composition of the compound.
In order to explore further geometries beyond 4-coordinate
square planar arrangements, the reaction between cobalt(II)
acetate and 3 equiv of 7 was investigated. Despite the use of a
cobalt(II) precursor, oxidation to the trivalent product is
universally observed in dithiocarbamate complexes of the type
[Co(S2CNR2)3].2d Coordination solely through the sulfur
donors of the ligand was confirmed by 31P{1H} NMR
spectroscopy, while the ethylene bridges appeared as broad
multiplets in the 1H NMR spectrum between 1.9 and 4.1 ppm.
The formulation of the product was confirmed as [Co{S2CN-
(CH2CH2PPh2)2}3] (11) on the basis of an [M + Na]+ ion at
m/z 1630 in the mass spectrum (ES, positive mode) and good
agreement of elemental analysis between determined and
calculated values (Scheme 4).
Once the reactivity of the bifunctional linker 7 had been
investigated in the preparation of homoleptic examples, the
pendant phosphine groups were explored as a starting point for
the generation of multimetallic compounds. Of the group 10
homoleptic compounds reported here, only 8 was found to
exhibit pendant phosphines.
In order to expand precursor options, the complex
[Ru{S2CN(CH2CH2PPh2)2}(dppm)2]PF6 (12) was prepared
from the versatile starting material cis-[RuCl2(dppm)2]. The
retention of the coordinated dppm ligands was confirmed by
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Synthesis of Heteronuclear Complexes. Treatment of 8
with 4 equiv of [AuCl(tht)] (tht = tetrahydrothiophene) led to
displacement of the thiacycle to form the yellow-green
pentametallic compound, [Ni{S2CN(CH2CH2PPh2AuCl)2}2]
(14) in good yield (Scheme 4). A dramatic shift of the singlet
resonance in the 31P{1H} NMR spectrum by over 40 ppm from
the precursor value to 23.9 ppm indicated that metalation of
the phosphorus donors had been achieved. Relatively little
change was observed in the 1H nuclear magnetic resonances of
the ethylene bridges. A reasonably abundant ion corresponding
to loss of one chloride ([M-Cl]+) was found at m/z 1983 in the
electrospray mass spectrum (positive mode).
complexes with pendant phosphines, which were then used to
synthesize bi-, tri-, and pentametallic complexes incorporating
the metals Mo, W, Re, Ru, Ni, Pd, Pt and Au. This reactivity
was well controlled in heteroleptic assemblies, allowing
multimetallic complexes to be constructed in a stepwise
manner. However, for homoleptic arrangements, monomeric
(8), cyclic (9), or oligomeric (10) examples were observed.
This reactivity shows the potential for 7 in the stepwise
construction of multimetallic assemblies but also illustrates the
pitfalls that exist when using such bifunctional linkers.
EXPERIMENTAL SECTION
■
Addition of [AuCl(tht)] to 12 also yielded the aurated
product [Ru{S2CN(CH2CH2PPh2AuCl)2}(dppm)2]PF6 (15),
which was characterized on the basis of multinuclear NMR and
infrared spectroscopy as well as analytical data. Compound 12
was used as a starting point for the addition of metals from
groups 6 and 7 of the Periodic Table. Treatment of 12 with
[Mo(CO)4(pip)2] or [Mo(CO)4(nbd)] (nbd = norborna-
diene) under nitrogen provided [(dppm)2Ru{S2CN-
(CH2CH2PPh2)2}Mo(CO)4]PF6 (16) in good yield. A
significant shift in the resonance for the pendant phosphines
in the 31P{1H} NMR to 31.2 ppm was observed, and new
activity was observed in the solid state infrared spectrum in the
typical region for terminal carbonyl absorptions (1874−2018
cm−1). In the electrospray mass spectrum (positive mode), a
molecular ion was seen at m/z 1594 confirming the overall
composition of the compound. The tungsten analogue
[(dppm)2Ru{S2CN(CH2CH2PPh2)2}W(CO)4]PF6 (17) was
prepared in the same way, though requiring longer stirring
(17 h) to achieve full reaction (Scheme 4). This yellow
complex was found to show similar spectroscopic features to
the molybdenum compound apart from the presence of
tungsten satellites (JWP = 244.0 Hz) associated with the singlet
resonance at 17.5 ppm in the 31P{1H} NMR spectrum.
Due to the difficulty in isolating [Mo{κ2-HN(CH2-
CH2PPh2)2}(CO)4] (4) before spontaneous coordination of
the nitrogen donor to the metal, the reactivity of the nitrogen
donor toward carbon disulfide could not be investigated.
However, the tungsten analogue (6) does not undergo the
bidentate to tridentate transformation, even after many hours in
solution. Accordingly, an alternative route to 17 was attempted
through sequential treatment of 6 with K2CO3, CS2, and cis-
[RuCl2(dppm)2]. Although this did yield 17 in modest yield,
additional products were also obtained. This is possibly due to
the dithiocarbamate generated then coordinating to unreacted
6. Zerovalent dithiocarbamate examples [W(S2CNR2)(CO)4]−
are known.24
General Comments. Unless otherwise stated, all experiments
were carried out in air. The complexes obtained appear stable toward
the atmosphere, whether in solution or in the solid state. Reagents and
solvents were used as received from commercial sources. Petroleum
ether is the fraction boiling in the 40−60 °C range. The following
compounds were prepared as described elsewhere: [H2N(CH2CH2-
PPh2 )2 ]Cl,16 [PdCl2 (py)2 ],2 5 [PtCl2 (NCPh)2 ],2 6 cis-
[RuCl2(dppm)2],27 [AuCl(tht)],28 [M(CO)4(pip)2] (M = Mo,
W),29 and [Mo(CO)4(nbd)].30 Electrospray (ES) and Fast Atom
Bombardment (FAB) mass data were obtained using Micromass LCT
Premier and Autospec Q instruments, respectively. 3-Nitrobenzylalco-
hol (nba) was used as a matrix in some measurements. Infrared data
were obtained using a PerkinElmer Spectrum 100 FT-IR spectrometer.
Selected data are included and characteristic triphenylphosphine-
associated infrared features are not reported. NMR spectroscopy was
performed at 25 °C using Varian Mercury 300 and Bruker AV400
spectrometers in CDCl3 unless stated otherwise. All coupling
constants are in Hertz. Resonances in the 31P{1H} NMR spectra
due to the hexafluorophosphate counteranion were observed where
the formulation indicates but are not included below. Elemental
analysis data were obtained from London Metropolitan University.
1
Solvates were determined by integration of the H NMR spectrum in
each case. The procedures given provide materials of sufficient purity
for synthetic and spectroscopic purposes.
[Mo{κ2-HN(CH2CH2PPh2)2}(CO)4] (4). [Mo(CO)4(pip)2] (15 mg,
0.040 mmol) and bis[2-(diphenylphosphino)ethyl]amine hydro-
chloride (19 mg, 0.040 mmol) were dissolved in dichloromethane
(10 mL) and methanol (5 mL) and stirred for 10 min. The solvent was
removed and diethyl ether (10 mL) was added. Ultrasonic trituration
yielded a yellow-brown product, which was washed with cold
methanol (2 mL) and diethyl ether (10 mL) before being dried.
Yield: 16 mg (62%). IR (solid state): 2950, 2803, 2734, 2013 ν(CO),
1906 ν(CO), 1887 ν(CO), 1862 ν(CO), 1821, 1790, 1592, 1459,
1
1433, 1307, 1028, 827, 739, 692 cm−1. NMR H: δ 1.66 (m, 4H,
PCH2), 2.71 (m, 4H, NCH2), 4.25 (s(br), 1H, NH), 7.19−7.58 (m,
20H, C6H5). 31P{1H}: δ 19.8 (s, PPh2) ppm. MS (ES negative) m/z
(abundance %): 650 (11) [M]+. Analysis: Could not be obtained due
to the spontaneous loss of carbon monoxide from the complex.
[Mo{κ3-HN(CH2CH2PPh2)2}(CO)3] (5). [Mo(CO)4(pip)2] (25 mg,
0.066 mmol) and [H2N(CH2CH2PPh2)2]Cl (32 mg, 0.067 mmol)
were dissolved in degassed dichloromethane (10 mL) and stirred at
reflux under nitrogen for 3 h. Methanol (10 mL) was added and the
solvent volume was reduced until precipitation of a yellow solid was
complete. This was washed with methanol (10 mL) and diethyl ether
(10 mL) and dried. Yield: 33 mg (81%). IR (solid state): 3290, 3240,
1911 ν(CO), 1816 ν(CO), 1793 ν(CO), 638 cm−1. NMR 1H: δ 2.32,
2.44 (m × 2, 4H, PCH2), 2.91, 3.12 (m × 2, 4H, NCH2), 4.15 (s(br),
1H, NH), 6.91, 7.13, 7.39, 7.77 (m × 4, 20H, C6H5). 31P{1H}: δ 39.2
(s, PPh2) ppm. MS (ES positive) m/z (abundance %): 622 (20) [M]+.
Analysis: Calculated for C31H29MoNO3P2: C, 59.9; H, 4.7; N, 2.3%.
Found: C, 60.2; H, 4.8; N, 2.1%.
Stirring 12 with [ReCl(CO)5] under nitrogen led to the
formation of [(dppm)2Ru{S2CN(CH2CH2PPh2)2}ReCl-
(CO)3]PF6 (18) in 84% yield to provide a heterobimetallic
example combining metals from groups 7 and 8 of the
transition series. The presence of the rhenium unit was
indicated by the presence of new absorptions in the solid state
infrared spectrum between 2036 and 1960 cm−1, while a new
singlet was observed at 31.7 ppm in the 31P NMR spectrum.
CONCLUSIONS
■
The new bifunctional diphosphine-dithiocarbamate “Janus”
ligand, KS2CN(CH2CH2PPh2)2 (7), has been prepared in
good yield in only two steps from commercially available bis(2-
chloroethyl)amine. Ligand 7 reacts preferentially through the
sulfur donors to yield nickel, ruthenium, cobalt, and osmium
[W{κ2-HN(CH2CH2PPh2)2}(CO)4] (6). [W(CO)4(pip)2] (60.0 mg,
0.129 mmol) and [H2N(CH2CH2PPh2)2]Cl (62.0 mg, 0.130) were
dissolved in degassed dichloromethane (20 mL) and stirred at reflux
under nitrogen for 21 h. The resulting solution was filtered through
Celite and then methanol (20 mL) was added. The solvent volume
4227
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Inorg. Chem. 2015, 54, 4222−4230

Inorganic Chemistry
Article
was reduced to approximately 5 mL, and the solution was stored at
−20 C until precipitation of a pale yellow solid was complete. This was
washed with cold methanol (5 mL) and diethyl ether (10 mL) and
dried. Yield: 70 mg (74%). IR (solid state): 3059, 2959, 2817, 2008
ν(CO), 1899 ν(CO), 1874 ν(CO), 1850 ν(CO), 1433, 1280, 1090,
(solid state): 1506, 1498, 1434, 1390, 1323, 1187, 1098, 1028, 998,
1
930, 810, 740, 690 cm−1. NMR H (DMSO-d6, 353 K): δ 3.42, 4.52
(m(br) × 2, 8H, CH2), 7.70 (m, 20H, C6H5) ppm. 31P{1H} (DMSO-
d6, 353 K): δ 15.1 (s(br), PPh2) ppm. MS (ES positive) m/z
(abundance %): 1541 (6) [2M + 3K]+. Analysis: Calculated for
C29H28ClNP2PtS2: C, 46.6; H, 3.8; N, 1.9%. Found: C, 46.3; H, 3.5; N,
2.0%.
1
913, 799, 740, 690 cm−1. NMR H: δ 2.48 (m, 4H, PCH2), 2.72 (m,
4H, NCH2), 3.77 (s(br), 1H, NH), 7.36−7.54 (m, 20H, C6H5).
31P{1H}: δ 2.9 (s, PPh2, JPW = 234.0 Hz) ppm. MS (ES positive) m/z
(abundance %): 738 (100) [M]+. Analysis: Calculated for
C32H29NO4P2W·CH2Cl2: C, 48.2; H, 3.8; N, 1.7%. Found: C, 48.3;
H, 4.1; N, 1.9%.
[Co{S2CN(CH2CH2PPh2)2}3] (11). A solution of ligand 7 (100 mg,
0.180 mmol) and [Co(OAc)2]·4H2O (15 mg, 0.060 mmol) in
degassed methanol (3 mL) was stirred at room temperature for 2 h. All
solvent was removed under reduced pressure, and the resulting residue
was dissolved in a minimum volume of dichloromethane and filtered
through Celite. The solution was concentrated to approximately 2 mL
and pentane (10 mL) added to precipitate the dark brown product,
which was dried under a vacuum. Yield: 66 mg (68%). IR (solid state):
KS2CN(CH2CH2PPh2)2 (7). A mixture of [H2N(CH2CH2PPh2)2]Cl
(1.00 g, 2.10 mmol) and potassium carbonate (2.31 g, 16.72 mmol) in
dry, degassed acetonitrile (25 mL) was treated with carbon disulfide
(0.127 mL, 2.11 mmol). The resultant mixture was stirred at room
temperature for 1 h. The pale yellow solution was filtered, and all
solvent was removed under reduced pressure. The crude solid was
dissolved in the minimum amount of dichloromethane and filtered
through Celite. All solvent was removed under reduced pressure to
yield the product as a yellow foamy solid which was dried under a
vacuum overnight. Yield: 1.06 g (91%). IR (solid state): 1478, 1432,
1
1478, 1431, 999, 735, 692 cm−1. NMR H: δ 1.9−4.1 (m(br), 24H,
CH2), 7.06−7.84 (m, 60 H, PPh2) ppm. 31P{1H}: δ −20.4 (s, PPh2)
ppm. MS (ES positive) m/z (abundance %): 1630 (20) [M + Na]+.
Analysis: Calculated for C87H84CoN3P6S6: C, 65.0; H, 5.3; N, 2.6%.
Found: C, 65.3; H, 5,2; N, 2.7%.
[Ru{S2CN(CH2CH2PPh2)2}(dppm)2]PF6 (12). A yellow solution of
ligand 7 (50 mg, 0.090 mmol) and cis-[RuCl2(dppm)2] (83.4 mg,
0.089 mmol) in degassed dichloromethane (20 mL) was treated with a
solution of ammonium hexafluorophosphate (29.0 mg, 0.178 mmol)
in degassed methanol (10 mL). The solution was heated at reflux for
10 min followed by stirring at room temperature for 4 h. All solvent
was removed under reduced pressure to yield the yellow crude
product, which was dissolved in a minimum volume of dichloro-
methane and filtered through Celite to remove KCl. All solvent was
again removed before ultrasonic trituration in diethyl ether (25 mL).
The yellow product was washed with diethyl ether (10 mL), then
filtered, and dried under a vacuum. Yield: 85 mg (62%). IR (solid
state): 1748, 1484, 1435, 1370, 1292, 1188, 1098, 1000, 836 (νPF), 695
1
997, 731, 692 cm−1. NMR H: δ 2.48 (m, 4H, PCH2), 4.11 (m, 4H,
NCH2), 7.27, 7.43 (m × 2, 20H, C6H5) ppm. 13C{1H}: δ 211.5 (CS2),
138.1 (d, ipso-C6H5, JCP = 12.0 Hz), 132.8 (d, o-C6H5, JCP = 18.6 Hz),
128.6 (s, p-C6H5), 128.5 (d, m-C6H5, JCP = 6.7 Hz), 51.0 (d, PCH2, JCP
= 25.4 Hz), 25.7 (d, NCH2, JCP = 14.0 Hz) ppm. 31P{1H}: δ −20.1 (s,
PPh2) ppm. MS (ES positive) m/z (abundance %): 532 (100) [M +
H2O]−. Analysis: Calculated for C29H28KNP2S2: C, 62.7; H, 5.1; N,
2.5%. Found: C, 63.0; H, 5.2; N, 2.4%.
[Ni{S2CN(CH2CH2PPh2)2}2] (8). A solution of NiCl2·6H2O (21.2 mg,
0.089 mmol) in degassed methanol (2 mL) was added to a solution of
7 (100 mg, 0.180 mmol) in degassed methanol (4 mL), and the was
reaction stirred at room temperature for 2 h leading to the formation
of a green precipitate. All solvent was removed under reduced
pressure, and the solid was dissolved in the minimum amount of
dichloromethane and filtered through Celite. The solution was
concentrated to approximately 2 mL and methanol (10 mL) was
added. The flask was kept at −20 °C overnight, and the resulting green
product was filtered, washed with methanol (10 mL) and hexane (2 ×
5 mL) and dried under a vacuum. Yield: 70 mg (72%). IR (solid
1
cm−1. NMR H (CD2Cl2): δ 1.97, 2.16 (m × 2, 4H, PCH2CH2N),
3.31, 3.78 (m × 2, 4H, PCH2CH2N), 4.58, 4.90 (m × 2, 4H, PCH2P),
6.47 (m, 4H, C6H5-dppm), 6.93−7.08, 7.18−7.65, (m × 2, 56H,
C6H5) ppm. 31P{1H} (CD2Cl2): δ −21.3 (s, PPh2), −18.6, −5.7
(pseudotriplet × 2, dppm, JPP = 34.4 Hz) ppm. MS (MALDI positive)
m/z (abundance %) 1422 (100) [M + 2H2O]+. Analysis: Calculated
for C79H72F6NP7RuS2: C, 62.0; H, 4.7; N, 0.9%. Found: C, 61.8; H,
4.6; N, 1.0%.
1
state): 3048, 2913, 1480, 1432, 998, 737, 694 cm−1. NMR H: δ 2.34
(m, 8H, PCH2), 3.56 (m, 8H, NCH2), 7.24−7.50 (m, 40H, C6H5).
13C{1H}: δ 206.9 (CS2), 136.8 (d, ipso-C6H5, JCP = 10.6 Hz), 132.6 (d,
o-C6H5, JCP = 17.5 Hz), 129.4 (s, p-C6H5), 128.7 (s(br), m-C6H5), 47.0
(d, PCH2, JCP = 20.4 Hz), 25.9 (d, NCH2, JCP = 14.8 Hz) ppm.
31P{1H}: δ −20.4 (s, PPh2) ppm. MS (ES positive) m/z (abundance
%): 1321 (21) [M + 2K + nba]+. Analysis: Calculated for
C58H56N2NiP4S4: C, 63.8; H, 5.2; N, 2.6%. Found: C, 63.6; H, 5.3;
N, 2.5%.
[Pd{S2CN(CH2CH2PPh2)2}]2(Cl)2 (9). [PdCl2(py)2] (70.0 mg, 0.209
mmol) was added to a solution of 7 (116 mg, 0.209 mmol) in dry,
degassed dichloromethane (15 mL). The yellow mixture was stirred at
reflux under N2 for 2 h. The resulting yellow precipitate was filtered,
dissolved in methanol, and filtered through Celite. All solvent was then
removed under reduced pressure, and the resulting yellow solid was
washed with dichloromethane (10 mL), water (10 mL), and acetone
(10 mL) before drying under a vacuum. Yield: 195 mg (71%). IR
(solid state): 1496, 1483, 1432, 1132, 1125, 890 cm−1. NMR 1H
(methanol-d4): δ 3.13, 3.53 (m × 2, 8H, PCH2CH2N), 4.27, 4.93 (m ×
2, 8H, PCH2CH2N), 7.57−7.16 (m, 40H, C6H5) ppm. 31P{1H}
(methanol-d4): δ 8.2 (s, PPh2) ppm. MS (ES positive) m/z
(abundance %): 1245 (5) [M]+. Analysis: Calculated for
C58H56Cl2N2P4Pd2S4: C, 52.9; H, 4.3; N, 2.1%. Found: C, 52.8; H,
4.0; N, 2.2%.
[Os(CHCHC6H4Me-4){S2CN(CH2CH2PPh2)2}(CO)(PPh3)2] (13). Li-
gand 7 (25 mg, 0.045 mmol) and [Os(CHCHC6H4Me-4)Cl(CO)-
(BTD)(PPh3)2] (45 mg, 0.044 mmol) were dissolved in dichloro-
methane (5 mL) and stirred at room temperature for 1 min. The
solution was filtered through Celite, and then all solvent was removed.
Petroleum ether (10 mL) was added, and a cream solid was obtained
by trituration in an ultrasound bath. The product was filtered and
washed with petroleum ether (10 mL) and dried under a vacuum.
Yield: 28 mg (46%). IR (solid state): 1901 (νCO), 1573, 1547, 1507,
1481, 1433, 1348, 1278, 1186, 1158, 1116, 1091, 999, 848, 740 cm−1.
1
NMR H (CD2Cl2): δ 1.70, 1.91 (m x 2, 4H, PCH2CH2N), 2.21 (s,
3H, Me), 2.71, 3.12 (m × 2, 4H, PCH2CH2N), 5.51 (d, 1H, Hβ, JHH
=
17.1 Hz), 6.47, 6.83 (AB, 4H, C6H4, JAB = 8.0 Hz), 6.92−7.53 (m,
50H, C6H5), 8.37 (dt, 1H, Hα, JHH = 17.1 Hz, JHP = 2.2 Hz) ppm.
31P{1H} (CD2Cl2): δ −21.3, −20.4 (s × 2, PPh2), 7.8 (s, OsPPh3)
ppm. MS (ES positive) m/z (abundance %) 1412 (3) [M + 2H2O]+.
Analysis: Calculated for C75H67NOOsP4S2: C, 65.4; H, 4.9; N, 1.0%.
Found: C, 65.6; H, 5.0; N, 1.0%.
[Ni{S2CN(CH2CH2PPh2AuCl)2}2] (14). A solution of [AuCl(tht)]
(200 mg, 0.624 mmol) in degassed dichloromethane (5 mL) was
added dropwise to a solution of 8 (150 mg, 0.137 mmol) in degassed
dichloromethane (5 mL), and the resulting solution was stirred at
room temperature for 1 h. Under reduced pressure, the solvent volume
was concentrated to approximately 2 mL and diethyl ether (10 mL)
added leading to the precipitation of a yellow solid. The solid was left
to settle at −20 °C overnight, then filtered, and dried under a vacuum.
Yield: 200 mg (72%). IR (solid state): 1751, 1482, 1436, 1410, 1353,
1285, 1177, 1104, 998, 742, 690 cm−1. NMR 1H (CD2Cl2): δ 3.03 (m,
8H, PCH2CH2N), 3.93 (m, 8H, PCH2CH2N), 7.50, 7.69 (m × 2, 40
{[Pt{S2CN(CH2CH2PPh2)2}]Cl}n (10). [PtCl2(NCPh)2] (25 mg, 0.053
mmol) in degassed dichloromethane (3 mL) was added to a solution
of 7 (29 mg, 0.052 mmol) in degassed dichloromethane (3 mL) and
stirred at room temperature for 1 h. The yellow precipitate formed was
filtered, washed with dichloromethane (10 mL), water (10 mL), and
acetone (10 mL), and dried under a vacuum. Yield: 32 mg (81%). IR
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H, PPh2) ppm. 31P{1H} (CD2Cl2): δ 23.9 (s, PPh2) ppm. MS (LSIMS
positive) m/z (abundance %) 1983 (30) [M − Cl]+. Analysis:
Calculated for C58H56Au4Cl4N2NiP4S4: C, 34.5; H, 2.8; N, 1.4%.
Found: C, 34.9; H, 3.0; N, 1.5%.
PCH2CH2N), 3.59, 4.09 (m × 2, 4H, PCH2CH2N), 4.64, 5.03 (m × 2,
4H, PCH2P), 6.53 (m, 4H, C6H5-dppm), 6.82−7.96 (m, 56H, C6H5)
ppm. 31P{1H}: δ −18.1, −5.5 (pseudotriplet × 2, dppm, JPP = 33.4
Hz), 31.7 (s, RePPh2) ppm. MS (ES positive) m/z (abundance %)
1692 (8) [M]+. Analysis: Calculated for C82H72ClF6NO3P7ReRuS2: C,
53.6; H, 4.0; N, 0.8%. Found: C, 53.4; H, 3.9; N, 0.8%.
Crystallography. Crystals of 5 were grown by slow diffusion of
hexane into a solution of the complex in dichloromethane. Data were
taken from this sample on a Bruker SMART APEX CCD
diffractometer using graphite-monochromated Mo−Kα radiation (λ
= 0.71073 Å) at 150 2 K. Data reduction and integration was carried
out with SAINT+ and absorption corrections applied using the
program SADABS. The structures were solved by direct methods and
developed using alternating cycles of least-squares refinement and
difference-Fourier synthesis. All non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were placed in calculated positions
and their thermal parameters linked to those of the atoms to which
they were attached (riding model). Structure solution and refinement
used the SHELXTL PLUS V6.10 program package.30
[Ru{S2CN(CH2CH2PPh2AuCl)2}(dppm)2]PF6 (15). A solution of
[AuCl(tht)] (42 mg, 0.131 mmol) in degassed dichloromethane (3
mL) was added dropwise to a solution of 12 (100.0 mg, 0.065 mmol)
in degassed dichloromethane (3 mL), and the resulting solution was
stirred at room temperature for 1 h. All solvent was removed under
reduced pressure, and the resulting precipitate dissolved in the
minimum amount of dichloromethane and filtered through Celite. The
solution was concentrated to approximately 2 mL, and diethyl ether (5
mL) was added causing a yellow solid to precipitate. The product was
filtered and dried under a vacuum. Yield: 100 mg (77%). The product
was recrystallized by layering a dichloromethane solution of the
complex with diethyl ether. IR (solid state): 1737, 1484, 1436, 1365,
1
1189, 1102, 999, 836 (νPF), 739, 691 cm−1. NMR H (CD2Cl2): δ
2.31, 2.49 (m × 2, 4H, PCH2CH2N), 3.33, 3.71 (m × 2, 4H,
PCH2CH2N), 4.42, 4.82 (m × 2, 4H, PCH2P), 6.38 (m, 4H, C6H5-
dppm), 6.82−7.71 (m, 56H, C6H5) ppm. 31P{1H} (CD2Cl2): δ −17.4,
−6.0 (pseudotriplet × 2, dppm, JPP = 34.4 Hz), 25.4 (s, AuPPh2) ppm.
MS (MALDI positive) m/z (abundance %) 1853 (28) [M]+. Analysis:
Calculated for C79H72Au2Cl2F6NP7RuS2·4CH2Cl2 C, 42.7; H, 3.5; N,
0.6%. Found: C, 42.7; H, 3.4; N, 0.9%.
Crystals of compound 9 were grown by slow evaporation of a
solution of the complex in methanol. Data were collected using an
Oxford Diffraction Xcalibur 3 diffractometer, and the structures were
refined based on F2 using the SHELXTL and SHELX-97 program
systems.31
Crystal data for 5. C H MoNO P , M = 621.43, triclinic, P1 (No.
̅
[(dppm)2Ru{S2CN(CH2CH2PPh2)2}Mo(CO)4]PF6 (16). Compound 12
(80 mg, 0.052 mmol) and [Mo(CO)4(nbd)] (18 mg, 0.060 mmol)
were dissolved in degassed dichloromethane (15 mL) and stirred at
room temperature for 2 h under nitrogen. The solution was filtered
through Celite, and all solvent was then removed. Petroleum ether (20
mL) was added, and an orange solid was obtained by trituration in an
ultrasound bath. The product was filtered and washed with petroleum
ether (10 mL) and dried under a vacuum. Yield: 63 mg (70%). Similar
yields are obtained using [Mo(CO)4(pip)2] as the starting material in
the same procedure. IR (solid state): 2018 (νCO), 1918 (νCO), 1874
(νCO), 1605, 1483, 1434, 1317, 1293, 1259, 1243, 1189, 1174, 1163,
31 29
3 2
2), a = 9.1979(5), b = 9.4053(5), c = 16.4401(9) Å, α = 99.193(1), β =
91.308(1), γ = 100.745(1)°, V = 1377.3(1) Å3, Z = 2, Dc = 1.498 g
cm−3, μ(Mo-Kα) = 0.626 mm−1, T = 150 K, yellow blocks, Bruker
Smart Apex diffractometer; 6328 independent measured reflections
(Rint = 0.0124), F2 refinement, R1(obs) = 0.0212, wR2(all) = 0.0541,
6134 independent observed absorption-corrected reflections [|F0| >
4σ(|F0|), 2θmax = 57°], 347 parameters. CCDC 1017334.
Crystal data for 9. [C58H56N2P4Pd2S4](Cl)2·2H2O·1.5MeOH, M =
1400.96, monoclinic, P21/n (No. 14), a = 11.4321(3), b = 17.1025(5),
c = 15.3940(5) Å, β = 100.016(3)°, V = 2963.93(16) Å3, Z = 2 [Ci
symmetry], Dc = 1.570 g cm−3, μ(Mo-Kα) = 0.993 mm−1, T = 173 K,
yellow blocks, Agilent Xcalibur 3E diffractometer; 6482 independent
measured reflections (Rint = 0.0604), F2 refinement, R1(obs) = 0.0501,
wR2(all) = 0.1077, 4736 independent observed absorption-corrected
reflections [|F0| > 4σ(|F0|), 2θmax = 57°], 334 parameters. CCDC
1017335.
1
1098, 1085, 1063, 1029, 997, 911, 827 (νPF), 812 cm−1. NMR H
(CD2Cl2): δ 2.41 (m, 4H, PCH2CH2N), 3.51, 3.81 (m × 2, 2H,
PCH2CH2N), 4.46, 4.92 (m × 2, 4H, PCH2P), 4.94 (m, 2H,
PCH2CH2N), 6.49 (m, 4H, C6H5-dppm), 6.85−7.71 (m, 56H, C6H5)
ppm. 31P{1H} (CD2Cl2): δ −17.9, −5.4 (pseudotriplet × 2, dppm, JPP
= 34.3 Hz), 31.2 (s, MoPPh2) ppm. MS (ES positive) m/z (abundance
%) 1594 (62) [M]+. Analysis: Calculated for C83H72F6MoNO4P7RuS2:
C, 57.3; H, 4.2; N, 0.8%. Found: C, 57.1; H, 4.3; N, 0.8%.
ASSOCIATED CONTENT
* Supporting Information
■
[(dppm)2Ru{S2CN(CH2CH2PPh2)2}W(CO)4]PF6 (17). Compound 12
(35 mg, 0.023 mmol) and [W(CO)4(pip)2] (13.4 mg, 0.029 mmol)
were dissolved in degassed dichloromethane (8 mL) and stirred at
room temperature for 17 h under nitrogen. The solution was filtered
through Celite, and all solvent was then removed. Petroleum ether (20
mL) was added, and a yellow solid was obtained by trituration in an
ultrasound bath. The product was filtered and washed with petroleum
ether (10 mL) and dried under vacuum. Yield: 29 mg (69%). IR (solid
state): 2008 (νCO), 1867 (νCO), 1829 (νCO), 1358, 1309, 1289, 1261,
S
Crystallographic data and anisotropic displacement ellipsoid
plots for the structures of 5 and 9. This material is available free
of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: j.wilton-ely@imperial.ac.uk.
■
1
1186, 1094, 1026, 1000, 833 (νPF) cm−1. NMR H (CD2Cl2): δ 2.64,
Notes
2.53 (m × 2, 4H, PCH2CH2N), 3.51 (m, 4H, PCH2CH2N), 4.49, 4.87
(m × 2, 4H, PCH2P), 6.49 (m, 4H, C6H5-dppm), 6.89−7.74 (m, 56H,
C6H5) ppm. 31P{1H} (CD2Cl2): δ −18.2, −5.2 (pseudotriplet × 2,
dppm, JPP = 33.9 Hz), 17.5 (s, WPPh2, JPW = 244.0 Hz) ppm. MS (ES
positive) m/z (abundance %) 1682 (31) [M]+. Analysis: Calculated
for C83H72F6NO4P7RuS2W·CH2Cl2: C, 52.8; H, 3.9; N, 0.7%. Found:
C, 53.0; H, 3.5; N, 0.8%.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to Johnson Matthey Ltd for a generous loan of
ruthenium salts. Contributions from T. Fovanna and C.
Roseren are acknowledged. J.H.W. would like to thank the
Santander Undergraduate Research Exchange (SURE) Pro-
gramme.
[(dppm)2Ru{S2CN(CH2CH2PPh2)2}ReCl(CO)3]PF6 (18). Compound
12 (40 mg, 0.026 mmol) and [ReCl(CO)5] (9.5 mg, 0.026 mmol)
were dissolved in degassed dichloromethane (10 mL) and stirred at
room temperature for 15 h under nitrogen. The solution was filtered
through Celite, and all solvent was then removed. Petroleum ether (20
mL) was added, and a yellow solid was obtained by trituration in an
ultrasound bath. The product was filtered and washed with petroleum
ether (10 mL) and dried under a vacuum. Yield: 40 mg (84%). IR
(solid state): 2036 (νCO), 1990 (νCO), 1960 (νCO), 1719, 1483, 1434,
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