Bifunctional Chalcogen Linkers for the Stepwise Generation of Multimetallic Assemblies and Functionalized Nanoparticles

Article abstract of DOI:10.1021/acs.inorgchem.6b02409

The disulfide ligand (SC₆H₄CO₂H-4)₂ acts as a simple but versatile linker for a range of group 8 transition metals through reaction of the oxygen donors. This leads to a range of homobimetallic ruthenium and osm

Full text of DOI:10.1021/acs.inorgchem.6b02409

Article
pubs.acs.org/IC
Bifunctional Chalcogen Linkers for the Stepwise Generation of
Multimetallic Assemblies and Functionalized Nanoparticles
†
,§
†,‡,§
†
†
Jonathan A. Robson †, Ferran Gonzal
̀
ez de Rivera,
Khairil A. Jantan, Margot N. Wenzel,
‡
,†
Andrew J. P. White, Oriol Rossell, 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
*
S Supporting Information
ABSTRACT: The disulfide ligand (SC H CO H-4) acts as a
6
4
2
2
simple but versatile linker for a range of group 8 transition
metals through reaction of the oxygen donors. This leads to a
range of homobimetallic ruthenium and osmium alkenyl
compounds, [{M(CHCHR)(CO)(PPh ) (O CC H S-
3
2
2
6
4
4
)} ] (M = Ru, Os; R = C H Me-4). Additional metal-based
2 6 4
functionality can be added through the use of precursors
incorporating rhenium bipyridine units (R = (bpy)ReCl-
(
(
CO) ). The more robust diphosphine ligands in [{Ru-
3
2
+
dppm) (O CC H S-4)} ] (dppm = diphenylphosphino-
2
2
6
4
2
methane) allow reduction of the disulfide bond with sodium
borohydride to yield the thiol complex [Ru(O CC H SH-
2
6
4
+
4
4
)(dppm) ] . This complex reacts with [AuCl(PPh )] to afford the bimetallic compound [Ru(dppm) (O CC H S-
2 3 2 2 6 4
+
)Au(PPh )] . However, an improved route to the same and related heterobimetallic compounds is provided by the reaction
3
of cis-[RuCl (dppm) ] with [Au(SC H CO H-4)(L)] (L = PPh , PCy , PMe , IDip) in the presence of base and NH PF (IDip
=
2
2
6
4
2
3
3
3
4
6
+
1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). The heterotrimetallic compound [Au(SC H CO Ru(dppm) ) ] is
6 4 2 2 2
accessible through the reaction of the homoleptic gold(I) dithiolate [Au(SC H CO H-4) ]PPN (PPN = bis-
6
4
2
2
(
triphenylphosphine)iminium) with cis-[RuCl (dppm) ]. Without departure from the same methodology, greater complexity
2 2
2
+
can be incorporated into the system to provide the penta- and heptametallic assemblies [(dppf){AuSC H CO Ru(dppm) } ]
6
4
2
2 2
and [(dppf){AuSC H CO Os(CHCH-bpyReCl(CO) )(CO)(PPh ) } ]. The same stepwise approach provides the dinuclear
6
4
2
3
3 2 2
organometallic complexes [(L)Au(SC H CO -4)M(CHCHC H Me-4)(CO)(PPh ) ] (M = Ru, Os; L = PPh , IDip).
6
4
2
6
4
3 2
3
Complexes containing three metals from different groups of the periodic table [(L)Au(SC H CO -4)M{CHCH-
6
4
2
bpyReCl(CO) }(CO)(PPh ) ] (M = Ru, Os) can also be prepared, with one ruthenium example (L = PPh ) being structurally
3
3 2
3
characterized. In order to illustrate the versatility of this approach, the synthesis and characterization (IR and NMR spectroscopy,
+
TEM, EDS, and TGA) of the functionalized gold and palladium nanoparticles Au@[SC H CO Ru(dppm) ] and
6
4
2
2
+
Pd@[SC H CO Ru(dppm) ] is reported.
6
4
2
2
INTRODUCTION
to the need for strategies suited to linking different metals
together in a consistent and controllable manner. While
protection/deprotection approaches offer a solution to this
problem, an alternative, more synthetically straightforward
option is to tailor bifunctional linkers to the metals involved
■
The incorporation of multiple metal centers within the same
assembly, whether molecular or nanoscale in nature, opens up
new possibilities in a variety of applications. The potential for
multisite interactions, cooperative effects, and higher localized
7
8
1
2
(Chart 1). This approach has been used by us and others to
access molecular assemblies consisting of between two and six
metals, encompassing compounds in which up to six different
density of metal sites has been exploited in sensing, imaging,
3
and catalysis. In the last field, additional motivation has come
4
from the presence of bimetallic systems in nature. The linking
8c
metals are combined.
of organometallic compounds with (often highly conjugated)
organic linkers, such as acetylides, has also led to the
exploration of novel spectroscopic and photophysical proper-
9
In our earlier studies, sulfur ligands have dominated due to
their utility in both molecular and nanoparticle systems. These
approaches have been based principally on the versatile
dithiocarbamate ligand class, which can be introduced at a
late stage in the assembly of the systems in order to avoid
5
ties.
While the preparation of multimetallic compounds and
materials consisting of the same metal has been exploited
extensively in areas such as metal−organic frameworks
6
a−c
6d,e
(
MOFs)
and coordination polymers,
access to hetero-
Received: October 9, 2016
multimetallic systems has always proved more challenging due
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Chart 1. Simple Bifunctional Ligands Used in the Construction of Multimetallic Assemblies
a
Scheme 1. Synthesis of Bi- and Trimetallic Complexes
a
All charged complexes are hexafluorophosphate salts.
undesired reactivity with the molecular metal unit (“back-
biting”). Due to this potential problem, the use of thiols as a
donor component of bifunctional linkers is usually avoided in
systems containing “soft” metal centers. However, in this
contribution, the reactivity of 4-mercaptobenzoic acid is
explored, in both thiolate and disulfide form. The differing
reactivities of sulfur and oxygen donors and the lower reactivity
of the disulfide linkage allow the preparation of hetero-
multimetallic compounds based on Re, Ru, Os, and Au as well
as the surface functionalization of gold and palladium
nanoparticles.
of sodium methoxide and NH PF resulted in formation of a
4 6
pale yellow solid in 86% yield (Scheme 1). Two new
pseudotriplet resonances in the 31P{ H} NMR spectrum at
1
−12.0 and 8.9 ppm (J = 39.0 Hz) indicated the formation of a
PP
1
new compound. H NMR analysis revealed features attributed
to the dppm ligands, such as multiplets due to the PCH2P
protons at 3.95 and 4.63 ppm, while the resonances for the
C H protons were obscured by the remaining aromatic
6
4
13
1
features of the spectrum. In the C{ H} NMR spectrum, a
triplet at 43.6 ppm (JPC = 11.5 Hz) was assigned to the
bridgehead carbon nuclei of the dppm ligands, while a singlet at
In order to illustrate the potential for wide-ranging
application of this approach, a series of different metal units
were employed. These included representatives of common
geometries and a range of metals from groups 7, 8, and 11 from
all three periods of the d-block. In addition, the metal units
chosen also possess properties which are widely employed in
many applications, such as reliable redox behavior (Fe(II/III),
Ru(II/III)), photophysical attributes (Re(I)-diimine moieties),
and a common motif used in gold-based drugs (e.g., auranofin).
181.7 ppm was attributed to the CO unit. The formulation of
2
[{Ru(dppm) (O CC H S-4)} ](PF ) (2) was further sup-
2
2
6
4
2
6 2
ported by a molecular ion at m/z 2044 in the mass spectrum
(FAB, positive mode) and good agreement between calculated
and experimentally determined values for elemental composi-
tion.
In order to add a second metal unit to 2, scission of the
disulfide bond was necessary. However, this had to be
performed under conditions which were tolerated by the
Ru(dppm)2 moieties. After attempting this transformation
unsuccessfully with tri-n-butylphosphine, we found that sodium
borohydride was able to achieve the transformation to the
corresponding thiol, [Ru(O CC H SH-4)(dppm) ]PF (3).
RESULTS AND DISCUSSION
■
Synthesis of Multimetallic Complexes. Reaction of 4-
mercaptobenzoic acid with iodine provided the disulfide
2
6
4
2
6
(
SC H CO H-4) (1) as a colorless solid in almost quantitative
However, the NMR data were found to be only slightly shifted
from those for the precursor (2) and the presence of the thiol
proton was initially difficult to identify. Mass spectrometry data
(ES, positive mode) supported the formation of the desired
product with a molecular ion at m/z 1024. The Signer
osmometry method was also employed, which estimates
molecular mass on the basis of vapor pressure values compared
6
4
2
2
1
yield. The absence of the thiol resonance observed in the H
NMR spectrum of the precursor and a slight shift in the
chemical shift values of the aryl resonances (7.52 and 7.81 ppm,
JHH = 8.0 Hz) indicated the success of the reaction. Remaining
spectroscopic and analytical data agreed with those reported for
this compound previously. Treatment of 2 equiv of the
versatile precursor cis-[RuCl (dppm) ] with 1 in the presence
10
1
1
to a known standard (Supporting Information). Data
2
2
B
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
a
Scheme 2. Synthesis of a Pentametallic Complex and Heptametallic Complexes
a
Abbreviations: R = bpyReCl(CO) , L = PPh , BTD = 2,1,3-benzothiadiazole, PPN = bis(triphenylphosphino)iminium. All metal cations are
3
3
hexafluorophosphate salts.
obtained by this method were also found to support the
monometallic formulation. Further proof was provided through
reactivity studies with gold(I) phosphine complexes. While the
In order to extend the use of gold fragments beyond
+
[AuPR ] units, the new complex [Au(SC H CO H-4)(IDip)]
3
6
4
2
(8) was prepared from the NHC precursor [AuCl(IDip)]
(IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene).
reaction of compound 2 with [AuCl(PPh )] in the presence (or
3
Compound 8 was treated with base and cis-[RuCl (dppm) ]
absence) of base was unsuccessful, treatment of 3 with the same
gold(I) reagent in the presence of base led to formation of the
complex [(dppm) Ru(O CC H S-4)Au(PPh )]PF (4). A new
2
2
to provide [(dppm) Ru(O CC H S-4)Au(IDip)]PF (9) in
2
2
6
4
6
6
2% yield (Scheme 1). The integration between the resonances
2
2
6
4
3
6
3
1
1
for the methylene protons of the dppm ligands (3.89 and 4.63
ppm) and the methyl substituents on the NHC ligand (four
doublets between 1.25 and 1.44 ppm) provided evidence for
the formulation, as well as mass spectrometry and analytical
data. Similar reactions were attempted with the complexes
resonance at 38.5 ppm in the P{ H} NMR spectrum
indicated the presence of the new triphenylphosphine ligand
in the product, as did the appearance of additional resonances
13
1
in the C{ H} NMR spectrum for the AuPPh unit. The mass
3
spectrum (ES, positive mode) showed a molecular ion at m/z
t
i
12b
[
Au(SC H CO H-4)(CNR)] (R = Bu, Pr); however, the
6 4 2
1
481. In order to further confirm the identity of the product,
12a
isocyanide ligand proved less robust than the NHC analogues
and was partially lost, leading to an intractable mixture of
products.
the known compound [Au(SC H CO H-4)(PPh )]
was
6
4
2
3
treated with cis-[RuCl (dppm) ], NaOMe, and NH PF to
2
2
4
6
provide an alternative and higher yield route to 4 (Scheme 1).
This result, and also the chemospecific nature of the reaction,
led to investigation of the reaction of other related gold(I)
precursors with cis-[RuCl (dppm) ]. The new thiolate
The homoleptic gold(I) dithiolate species [Au(SC H CO H-
6
4
2
12a
4
)2]PPN (PPN = bis(triphenylphosphine)iminium)
was
treated with cis-[RuCl (dppm) ] and base (Scheme 2) to
2
2
2
2
afford the trimetallic compound [Au{SC H CO Ru-
6
4
2
compound [Au(SC H CO H-4)(PCy )] (5) was prepared
31
1
1
6
4
2
3
(
dppm) } ]PF (10). Analysis by P{ H} and H NMR
2 2 6
from [AuCl(PCy )] and HSC H CO H-4 in the presence of
3
6
4
2
spectroscopy revealed chemical shifts displaying little difference
from those of the resonances in compound 2. Bearing in mind
the possible effect the P(III) and P(V) oxidation states could
exert on the relaxation times of the relevant phosphorus nuclei,
base. This was then used to prepare [(dppm) Ru(O CC H S-
2
2
6
4
4
)Au(PCy )]PF (6) in the same way as that employed for 4.
3 6
3
1
1
The presence of three resonances in the P{ H} NMR
31
1
spectrum at −12.1 (dppm), 8.9 (dppm) and 57.6 ppm (PCy )
3
integration of the P{ H} NMR spectrum suggested a dppm to
−
confirmed the presence of the ruthenium and gold phosphine
units at either end of the mercaptobenzoate linker. An
abundant molecular ion in the mass spectrum (ES, positive
mode) at m/z 1500 confirmed this formulation. Using the same
method, [(dppm) Ru(O CC H S-4)Au(PMe )]PF (7) was
PF6 ratio of 8:1, indicating a single counteranion for the
complex. Mass spectrometry data for the precursor [Au-
(SC H CO H-4) ]PPN revealed a molecular ion; however, in
6
4
2
2
the spectrum of 10, only an abundant fragmentation for loss of
gold was observed. The overall formulation was confirmed by
good agreement of elemental analysis with calculated values.
2
2
6
4
3
6
also synthesized from [AuCl(PMe )] (Scheme 1).
3
C
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
a
Scheme 3. Synthesis of Bi- and Trimetallic Vinyl Complexes
a
Abbreviation: BTD = 2,1,3-benzothiadiazole.
Using the known compound [dppf(AuSC H CO H-4) ]
to the formation of a new compound which gave rise to a
6
4
2
2
12a
31
1
(
dppf = 1,1′-diphenylphosphinoferrocene), the heteropenta-
singlet in the P{ H} NMR spectrum at 37.7 ppm, indicating a
mutually trans arrangement of phosphines and the highly
symmetrical nature of the complex. The coordination of the
metallic FeRu Au compound [(dppf){AuSC H CO Ru-
2
2
6
4
2
(
dppm) } ](PF ) (11) was prepared in 61% yield (Scheme
2 2 6 2
2
). The presence of the cyclopentadienyl rings was indicated by
oxygen donors in preference to the sulfur unit was provided by
1
−1
the observation of resonances at 4.24 and 4.63 ppm in the H
NMR spectrum alongside typical features for the PCH P and
aromatic protons. Support for the overall composition was
a shift in frequency for the ν
absorption from 1676 cm in
CO
1 to 1575 cm− in the product. Evidence for retention of the
1
2
1
tolylvinyl ligand was provided by resonances in the H NMR
provided by MALDI mass spectrometry (m/z 3031 for [M +
K] ) and good agreement of elemental analysis with calculated
values.
spectrum for the Hα and Hβ protons at 7.82 and 5.85 ppm,
respectively showing a mutual coupling of 15.5 Hz. In
comparison to the complexes bearing the dppm ligand, the
aromatic region was sufficiently simplified to identify the
protons of the SC H unit as an AA′BB′ system at 7.05 and
+
The Ru(dppm) unit is ideal for use in applications where a
2
1
robust terminus with characteristic spectroscopic features ( H
6
4
and 31P{ H} NMR spectroscopy) is required. However, the
potential for subsequent functionalization is mainly limited to
exchange of the counteranion. A more versatile synthetic
1
7.10 ppm (J
= 8.6 Hz). Characteristic resonances were
HH
observed for the carbonyl ligand at 202.4 ppm (t, J = 11.3
PC
13
1
Hz) and the CO unit at 176.4 ppm in the C{ H} NMR
2
1
3
starting point is provided by group 8 vinyl complexes, such as
spectrum. On the basis of these data and those from mass
spectrometry and elemental analysis measurements, the
complex was formulated as the bimetallic complex [{Ru-
(CHCHC H Me-4)(CO)(PPh ) (O CC H S-4)} ] (12).
1
4
15
[
M(CRCHR′)Cl(CO)(BTD)(PPh ) ] (M = Ru, Os;
3
2
BTD = 2,1,3-benzothiadiazole). These complexes are readily
accessible from the hydride precursors [MHCl(CO)(BTD)-
6
4
3
2
2
6
4
2
(
PPh ) ] by alkyne hydrometalation. This allows further
The osmium analogue [{Os(CHCHC H Me-4)(CO)-
(PPh ) (O CC H S-4)} ] (13) was prepared in a similar
3 2 2 6 4 2
3
2
6
4
functionality (including metal centers) to be introduced
through the choice of alkyne substituent. This has been
fashion (Scheme 3) and displayed spectroscopic data very
16
exploited to prepare bimetallic systems and to incorporate
similar to those of 12, apart from an upfield-shifted resonance
17
31
1
fluorophores for use in carbon monoxide sensing. In addition,
the resultant vinyl complexes [M(CRCHR′)Cl(CO)(BTD)-
in the P{ H} NMR spectrum at 18.5 ppm and a lower
−1
frequency νCO absorption at 1906 cm . The potential for
(
PPh ) ] possess labile ligands (BTD, chloride, phosphine)
introducing further metal fragments through the vinyl ligand
3
2
enabling the reactivity at the metal center to be exploited,
was illustrated by the use of [ReCl(CO) (bpyCCH)], which
3
18
which has been the focus of our earlier studies. This potential
has previously been used by Lang and co-workers to form
7a,9c,18h
19
8a−j
has been harnessed by us
and others to bridge such
acetylide complexes of various metals.
It appeared that its
metal centers. It was thus decided to extend the investigation of
multimetallic compound generation in this work through both
the vinyl ligand and the substitution of labile ligands.
potential in hydroosmiation reactions has been overlooked until
the preparation of [{Os{CHCH-bpyReCl(CO) }(CO)-
3
(BTD)(PPh ) ] through insertion of this alkyne into the
3
2
7a
Addition of carboxylic acids to ruthenium vinyl complexes
Os−H bond of [OsHCl(CO)(BTD)(PPh ) ]. Treatment of
2 equiv of this ReOs bimetallic product with 1 in the presence
3
2
can lead to cleavage of the organic ligand to yield the
7b
corresponding alkene. However, this can be avoided if
deprotonation is achieved prior to addition of the vinyl
complex. Treatment of [Ru(CHCHC H Me-4)Cl(CO)-
of base yielded [{Os{CHCH-bpyReCl(CO) }(CO)-
3
(PPh ) (O CC H S-4)} ] (14). The presence of the rhenium
3
2
2
6
4
2
unit was indicated by resonances at 9.36 (Hα) and 5.72 ppm
6
4
1
(
BTD)(PPh ) ] with disulfide 1 in the presence of base led
(Hβ) in the H NMR spectrum for the new vinyl ligand,
3
2
D
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 1. Molecular structure of 21. Selected bond lengths (Å) and angles (deg): Au1−S10 2.303(2), Au1−P11 2.255(2), Re1−N32 2.176(5),
Re1−N43 2.162(5), Ru1−O1 2.191(4), Ru1−O3 2.233(4), Ru1−C30 2.010(5), Ru1−P44 2.381(2), Ru1−P63 2.376(2); S10−Au1−P11
1
76.39(6), N32−Re1−N43 74.5(2), O1−Ru1−O3 59.2(2), P44−Ru1−P63 176.31(6), Ru1−C30−C31 136.0(5).
showing a mutual coupling of 16.2 Hz. The additional activity
in the solid-state infrared spectrum between 1882 and 2015
cm was attributed to the carbonyl ligands attached to the
rhenium center. The tetrametallic nature of the compound
(M = Ru, Os) and NaOMe led to formation of [(L)Au-
(SC H CO -4)M{CHCH-bpyReCl(CO) }(CO)(PPh ) ]
6
4
2
3
3 2
−1
(M = Ru, L = PPh , 21; M = Os, L = IDip, 22). While a
3
number of key features in complex 22 were obscured by peaks
(
Scheme 3) was further supported by mass spectrometry and
due to the PPh ligands, characteristic resonances for both
metal units were observed in the H NMR spectrum. These
3
1
analytical data. Spurred on by this result, we revisited the
strategy employed to prepare 11 using [{Os{CHCH-
bpyReCl(CO) }Cl(CO)(BTD)(PPh ) ] and [dppf(AuSC -
included resonances for the Hα (9.43 ppm) and Hβ (5.64
ppm) protons of the vinyl ligand and the methyl groups of the
IDip ligands at 1.30, 1.35 (both doublets) and 2.66 ppm
(septet). As before, the overall composition was supported by
elemental analysis data and the presence of a molecular ion at
m/z 1967 in the mass spectrum (ES, positive mode). To the
best of our knowledge, 22 represents the first example of a
molecular trimetallic assembly incorporating Re, Os, and Au.
Numerous attempts were made using many different
techniques (vapor diffusion, layering, slow evaporation, etc.)
and solvent combinations to obtain crystals of the key
complexes reported here. Ultimately, single crystals suitable
for structural determination were grown through slow diffusion
of ethanol into a dichloromethane solution of complex 21
(Figure 1).
3
3
2
6
H CO -4) ] in the presence of base (Scheme 2). The complex
4
2
2
formed, [(dppf){AuSC H CO Os(CHCH-bpyReCl(CO) )-
6
4
2
3
(CO)(PPh ) } ] (15), possesses seven metals (Re FeOs Au )
3 2 2 2 2 2
and was initially characterized on the basis of the highly
diagnostic H NMR spectrum. Each structural unit provided
1
characteristic resonances, including the dppf (4.30, 4.64 ppm),
SC H (6.89 and 7.25 ppm), bpy (e.g., 7.75 and 7.92 ppm), and
vinyl (5.63 and 9.38 ppm) moieties. Further support for the
structure came from the other analytical and spectroscopic
techniques employed.
6
4
12a
The complex [Au(SC H CO -4)(PPh )]
was used to
6
4
2
3
prepare the heterobimetallic complex [(Ph P)Au(SC H CO -
4
tolylvinyl ligand. The NHC compound [Au(SC H CO -
3
6
4
2
)Ru(CHCHC H Me-4)(CO)(PPh ) ] (16), bearing a
6
4
3 2
The structure of the ReRuAu trimetallic complex [(Ph P)-
6 4 2
3
4
)(IDip)] (8) was employed to prepare the NHC analogue
Au(SC H CO -4)Ru{CHCHbpyReCl(CO) }(CO)(PPh ) ]
6
4
2
3
3 2
[
(
(IDip)Au(SC H CO -4)Ru(CHCHC H Me-4)(CO)-
(21) can be discussed in relation to previously reported
6
4
2
6
4
PPh ) ] (17), in which organometallic units are present at
structural data for the individual metal units. The bond data for
3
2
either end of the carboxylate-thiolate linker. Using the five-
coordinate enynyl compound [Ru(C(CCPh)CHPh)Cl-
the common distorted-octahedral motif [ReCl(CO) (bpy)] are
3
unremarkable and are similar to those for the precursor
8
a
(
CO)(PPh ) ], an example bearing a disubstituted alkenyl
[ReCl(CO) (bpyCCH)]. There is also some disorder
3
2
3
ligand, [(Ph P)Au(SC H CO -4)Ru(C(CCPh)CHPh)-
involving the sites for the mutually trans chloride and carbonyl
ligands, which prevents further discussion. While the Au−S
distances in 21 are very similar to those found in the structure
3
6
4
2
(
CO)(PPh ) ] (18), was prepared.
3 2
The osmium analogues [(Ph P)Au(SC H CO -4)Os(CH
3
6
4
2
12a
CHC H Me-4)(CO)(PPh ) ] (19) and [(IDip)Au-
of [Au(SC H CO H-4)(PPh )], the Au−P distance in the
6
4
3
2
6
4
2
3
(
SC H CO -4)Os(CHCHC H Me-4)(CO)(PPh ) ] (20)
monometallic compound is slightly longer (2.276(1) Å) in
comparison to the value of 2.255(2) Å found for 21. However,
the deviation from linearity of the P−Au−S linkage in 21
(176.39(6)°) is much less than that found in the literature
structure of 168.95(4)°. This is likely to be due to the presence
of short aurophilic contacts (Au···Au 3.0756(2) Å) in the
structure of [Au(SC H CO H-4)(PPh )], which, along with
6
4
2
6
4
3 2
were also prepared in a similar manner to yield two examples
of OsAu heterobimetallic complexes. These syntheses paved
the way for the preparation of two heterotrimetallic complexes
with metals drawn from groups 7, 8, and 11 of the periodic
table. Treatment of [Au(SC H CO -4)(L)] (L = PPh , IDip)
6
4
2
3
with [{M{CHCH-bpyReCl(CO) }(CO)(BTD)(PPh ) ]
3
3
2
6
4
2
3
E
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
a
Scheme 4. Synthesis of Functionalized Gold and Palladium Nanoparticles Bearing Ruthenium Surface Units
a
All metal cations have hexafluorophosphate counteranions.
Figure 2. TEM images of (a) NP1, (b) NP2, (c) NP2 detail, and (d) NP4.
probable packing effects, lead to distortion of this angle. No
such interactions between gold(I) centers is observed in the
structure of 21. The ruthenium center shows a distorted-
octahedtral geometry with cis interligand angles in the range
above, the disulfide linkage remained intact apart from when it
was specifically targeted with a strong reducing agent. This
protection represents a significant advantage in the design of
nanoparticles functionalized with metal units, as the presence of
a free thiol for attachment to the gold surface poses the risk of
59.2(2)−107.8(2)° with the smaller of these values correspon-
23
doing to the bite angle of the carboxylate chelate. This is close
to the value for the same feature in the enynyl carboxylate
complex [Ru(C(CCPh)CHPh)(O CC H N)(CO)-
reacting instead with the metal center. Strategies to overcome
this include the initial attachment of the bifunctional tether to
the metal nanoparticle through the thiol moiety followed by
2
5
4
7
d
24
(
PPh ) ]. In common with this compound, the structure of
addition of molecular metal units to the terminal donor.
3
2
2
1 displays differing ruthenium−oxygen bond lengths, with the
However, the relatively low reactivity of the disulfide moiety
allows the construction of the metal unit before the RS−SR
bond is activated by the presence of the gold surface.
With this in mind, compound 2 was used to add ruthenium
units to the surface of gold nanoparticles using two common
Ru(1)−O(3) bond trans to the vinyl ligand being longer
(2.233(4) Å) than the Ru(1)−O(1) bond distance (2.191(4)
Å) trans to the carbonyl, indicating the superior trans influence
of the former ligand over the latter. Overall, the structure of 21
does not appear to be overly congested from a steric viewpoint,
though it is worth noting that both the C H SAuPPh unit and
methods. Reduction of HAuCl with sodium borohydride using
4
25
the conditions popularized by Brust and Schiffrin followed by
addition of a methanol solution of 2 (Scheme 4) led to black
6
4
3
the (bpy)ReCl(CO) vinyl substituent are twisted with respect
3
2.9
to the plane containing the carboxylate, vinyl, and carbonyl
ligands. The respective dihedral angles across the C2−C4 and
C31−C34 bonds are 19.7(4) and 29.2(7)°.
Synthesis of Functionalized Nanoparticles. Disulfides
often require some persuasion (heat, extended reaction times)
to react with low-valent transition metals in molecular
systems. However, they are known to react readily with
gold surfaces, whether two-dimensional SAMs or gold
nanoparticles, driven by the formation of favorable Au−S
interactions. Throughout the reactions with metals described
nanoparticles, Au @[SC H CO Ru(dppm) ]PF (NP1), of
6 4 2 2 6
average diameter 2.9 nm (±0.2 nm), as determined by
transmission electron microscopy (TEM; see the Supporting
Information) (Figure 2a). The complete removal of unattached
surface units was ensured through washing with dichloro-
methane and water. Infrared spectroscopy revealed the
2
0
−1
presence of the carboxylate unit (νCO at 1575 cm ) as well
21
as typical absorptions for the dppm units and a ν absorption
PF
2
2
−1
(817 cm ) indicating the continued presence of hexafluor-
ophosphate counteranions. The material also proved suffi-
F
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
3
0
31
32
33
ciently soluble in deuterated dimethyl sulfoxide to record the
H NMR spectrum, which showed resonances for the PCH2P
protons at substantially shifted values of 4.44 and 5.76 ppm (in
containing phosphine, amine, alkyl, carboxylate, and
1
34
carbene ligands. Given their ready thermal reduction in the
35
gilding process of ceramics, it is not surprising that gold(I)
thiolate precursors (often polymeric or cyclic species) have also
been employed in the direct preparation of thiolate-capped gold
comparison to 3.88 and 5.05 ppm for 2 in dmso-d ). As in the
6
molecular complexes, the C H resonances were obscured by
6
4
36a−c
the features associated with the phenyl groups of the dppm
nanoparticles.
using e-beam lithography/thermolysis protocols.
ysis of monometallic gold(I) dithiolate complexes has been
This approach has been further developed
3
1
1
36d,e
ligands between 6.89 and 7.74 ppm. The P{ H} NMR
Thermol-
spectrum showed resonances at −18.6 and 3.2 ppm (J = 35.7
PP
37
Hz), which differ from the chemical shift values recorded for
used to generate gold nanoparticles stabilized by alkyl groups,
the precursor 2 (−12.7 and 9.3 ppm, J = 39.1 Hz in dmso-d6).
while molecular methylgold(I) precursors have been employed
in the presence of thiol surfactants to prepare thiolate-protected
gold nanoparticles by a thermal route (140 °C). We have
PP
This suggests a substantially different local environment for the
ruthenium units when they are attached to the surface. The
presence of gold and ruthenium was confirmed by energy
dispersive X-ray spectroscopy (EDS) measurements (Support-
ing Information), which also indicated the presence of sulfur,
phosphorus, oxygen, and fluorine (though this technique is less
reliable for lighter elements). Thermogravimetric analysis
3
2
2
9e
recently reported
that the metallacyclic digold complexes
= N(CH , NC ) under-
[Au (S CNR ] (NR
)
CHCH
)
2
H
4 6
2
2
2
2
2
2
2
go reduction to form gold nanoparticles with diameters of 4.0
or 4.8 nm (±0.7 nm). The presence of intramolecular and
intermolecular aurophilic interactions (probed by structural
3
8
(TGA) of a sample of NP1 revealed the loss of 42.5% of the
investigations) in these complexes offers a fascinating
31b
mass on gradual heating to 800 °C (Supporting Information).
This can be assumed to be due to loss of the lighter elements
and allows an approximate estimation of the number of surface
units to be made. This loss of mass suggests a ratio of
approximately 8.4:1 between the gold and [SC H CO Ru-
suggestion
as to the role these interactions (15−30 kJ
−
1
mol and thus comparable in strength to hydrogen bonding)
might play in facilitating the formation of nanoparticles from
such complexes. Accordingly, it was decided to explore whether
direct preparation of nanoparticles from [Au{SC
H CO Ru-
4 2
6
4
2
6
(
dppm) ]PF surface units. Inductively coupled plasma atomic
(dppm) ]PF (10) was possible either by heating or by using
2
}
2
6
2
6
emission spectroscopy (ICP-AES) was also used in an attempt
to probe the number of surface units, but complete dissolution
of the samples in the required concentration of aqua regia
proved difficult and so led to unreliable results. It has been
noted that effective measurement of ruthenium by this method
sodium borohydride as the reducing agent. However, these
attempts failed to yield nanoparticles. This showed that 10 was
sufficiently robust to withstand heating at reflux (in acetone and
1,2-dichloroethane) or the addition of a large excess of reducing
agent. In contrast, treating a solution of the monometallic
requires high-temperature fusion with NaOH−NaNO mix-
precursor PPN[Au(SC H CO H-4) ] (PPN = bis-
6 4 2 2
3
2
6
tures.
(triphenylphosphine)iminium) in acetone with excess sodium
borohydride results in darkening of the solution and the
formation of a black solid, formulated as Au@SC H CO H-4
27
The citrate route, devised originally by Turkevich, was also
used to access black nanoparticles of larger average size. The
resultant nanoparticles were found to possess a diameter of 11.9
nm (±0.9 nm), as shown in TEM images (Figure 2b,c). As with
NP1, EDS data indicated the presence of gold and ruthenium.
6
4
2
(NP3). This surface unit was also used in the
Au102(SC H CO H-4) nanoparticles structurally determined
6
4
2
44
28a
using X-ray diffraction by Kornberg and co-workers. Analysis
by TEM (Supporting Information) revealed the formation of
nanoparticles with a relatively wide size distribution (4.1 ± 0.7
nm), while the solid-state infrared spectrum displays
31
1
1
Again, P{ H} and H NMR spectroscopic data were recorded
and were found to be consistent with the formulation
1
1.9
Au @[SC H CO Ru(dppm) ]PF (NP2). The chemical
6
4
2
2
6
shift values observed in the NMR spectra were very similar
to those recorded for NP1, indicating a similarly dramatic
change in environment in comparison to the molecular
precursor 2. The stapling effect in gold nanoparticles, whereby
a gold atom is lifted from the surface and pinned between two
thiolate units, is well established and has been observed
absorptions typical of 4-mercaptobenzoic acid (ν at 1587
CO
−1
cm ). The explanation for the difference in the propensity of
PPN[Au(SC H CO H-4) ] and 10 to form nanoparticles could
6
4
2
2
be related to the presence or absence of aurophilic interactions.
Compound 10 bears two bulky Ru(dppm) units in reasonably
2
close proximity to the gold(I) center, while the precursor has a
much smaller steric profile and could indeed permit aurophilic
interactions. The structure of this compound has not been
reported, but structural data for some related dithiolate
compounds have been determined. From these reports, it
appears that the nature of the countercation exerts considerable
influence on whether short intramolecular gold−gold contacts
are observed. The structure of {K [Au(mba) ]} (H mba = 2-
2
8
29
crystallographically and modeled computationally. Poten-
tially this is a route to loss of surface units through elimination
−
of a gold(I) dithiolate unit, Au(SR) . In order to establish
2
whether this was the case with these materials, the dichloro-
methane washings were analyzed but were found to contain
only traces of unreacted [{Ru(dppm) (O CC H S-4)} ](PF )
6 2
2
2
6
4
2
(
(
1
2). The corresponding dithiolate [Au{SC H CO Ru-
6 4 2
3
2
2
2
39a
dppm) } ]PF (10) was not found to be present. Compound
mercaptobenzoic acid) displays a short separation between
2
2
6
0 contains only one hexafluorophosphate anion, whereas 2
dimeric units (3.1555(7) Å) but no additional interactions
n
possesses two of these counteranions, allowing them to be
between neighboring dimers, while the structures of [ Bu N]-
4
−
differentiated from the dppm to PF ratio provided by
[Au(SC H -R) ] (R = o-Me, o-Cl, m-Cl) show no aurophilic
6
6
4
2
3
1
1
integration of their P{ H} NMR resonances. TGA data
revealed a metallic residue of 57.5% of the original mass, and so
the remainder (42.5%) was ascribed to the mass of the surface
units (excluding ruthenium). This equates to a stoichiometry of
approximately Au (SC H CO Ru(dppm) )PF .
contacts, an observation which is attributed to the bulky nature
39b
of the countercation.
In order to broaden the study beyond attachment to gold
surfaces, the generation and functionalization of palladium
nanoparticles with 2 was investigated. The divalent palladium
precursor [PdCl (NCMe) ] was reduced by lithium triethyl-
6.8
6
4
2
2
6
Ligand-stabilized gold nanoparticles can also be obtained
2
2
through the reduction of well-defined gold(I) precursors
borohydride in the presence of the phase transfer agent
G
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
4
0
tetraoctylammonium bromide (TOAB) before addition of a
solution of compound 2. After the resultant black nanoparticles
were washed to remove TOAB and unreacted 2, the material
Pd@[SC H CO Ru(dppm) ]PF (NP4) was isolated. This
Mercury 300, Bruker AV400, and Bruker 500 Avance III HD
spectrometers in CDCl3 unless stated otherwise. All coupling
31
1
constants are given in hertz. Resonances in the P{ H} NMR
spectrum 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.
6
4
2
2
6
proved insoluble in all common deuterated solvents, preventing
NMR analysis; however, infrared spectroscopy revealed typical
features for the surface units as observed for NP1 and NP2.
TEM images showed typically small nanoparticles of only 2.2
nm (±0.2 nm) diameter (Figure 1d), while EDS analysis
indicated the presence of palladium and ruthenium as well as
the expected lighter elements. A metallic residue of 61.6%
1
Solvates were confirmed by integration of the H NMR spectra. The
procedures given provide materials of sufficient purity for synthetic
and spectroscopic purposes. TEM images and EDS data were obtained
at Imperial College using a JEOL 2010 high-resolution TEM (80−200
kV) equipped with an Oxford Instruments INCA EDS 80 mm X-Max
detector system. Thermogravimetric analysis was performed on a
Mettler Toledo DSC 1LF/UMX Thermogravimetric Analyzer, using a
platinum sample holder. ICP-AES analyses were performed using a
PerkinElmer 2000 DV ICP-OE spectrometer.
24b
(
palladium and ruthenium) was observed from TGA
investigations, with the remaining 38.4% of the mass attributed
to the rest of the elements in the surface units. This suggested
that the ratio of palladium to surface units is close to 15:1,
indicating a sparsely covered nanoparticle surface.
(
SC H CO H-4) (1). A solution of iodine (1 M in MeOH) was
6 4 2 2
added dropwise to a colorless solution of 4-mercaptobenzoic acid (450
mg, 2.92 mmol) in MeOH (60 mL) until the mixture took on a
persistent orange coloration. The cloudy mixture was stirred for a
further 30 min and then filtered. The resulting white solid was washed
several times with ethanol and dried under vacuum overnight. Yield:
CONCLUSIONS
■
In the systems described here, the significantly lower reactivity
of the disulfide linkage (in comparison to that of the
carboxylate donors) prevents unwanted reaction of the sulfur
moiety until intended. This allows chelation by the oxygen
donors to dominate initial coordination of the transition metals
employed, while allowing subsequent activation of the disulfide
through reduction or addition to a nanoparticle surface. This
strategy has been illustrated by the preparation of a series of
heterobimetallic Ru−Au complexes. An alternative route to the
same compounds is provided by the reaction of 4-
mercaptobenzoic acid with thiophilic gold(I) precursors
followed by activation (addition of base) and coordination of
the oxygen donors to ruthenium or osmium. This also allows
the preparation of pentametallic complexes containing Fe, Ru,
and Au. Exploitation of the two centers of reactivity possessed
by ruthenium and osmium vinyl complexes (i.e., the metal
center and the vinyl substituent) allows heterotrimetallic
ReOsAu, heterotetrametallic Re Os , and heteroheptametallic
4
1
7
00 mg (90%). IR (solid state): 2838, 2669, 2552, 1676 (νCO), 1591,
−1
1
423, 1323, 1292, 1181, 1116, 933, 850 cm . H NMR (dmso-d ): δ
6
.52, 7.81 (d × 2, JHH = 8.0 Hz, 2 × 4 H; C H ) ppm. The CO H
6
4
2
protons were not observed. These data agree well with literature
1
0
values.
[{Ru(dppm)
RuCl (dppm) ] (263 mg, 0.280 mmol) in dichloromethane (50
(O CC H S-4)} ](PF ) (2). A solution of cis-
2 6 4 2 6 2
2
[
2
2
mL) was treated with a solution of 1 (43.0 mg, 0.140 mmol), sodium
methoxide (30.0 mg, 0.555 mmol), and ammonium hexafluorophos-
phate (91.0 mg, 0.558 mmol) in methanol (25 mL). The reaction
mixture was stirred for 2 h at room temperature. All solvent was
removed under vacuum, and the crude product was dissolved in
dichloromethane (10 mL) and filtered through Celite to remove NaCl,
NaOMe, and excess ligand. Ethanol (20 mL) was added, and the
solvent volume was slowly reduced on a rotary evaporator until the
precipitation of the yellow solid was complete. This was filtered,
washed with petroleum ether (10 mL), and dried under vacuum. Yield:
2
1
81 mg (86%). IR (solid state): 3058, 1590 (νCO), 1484, 1426, 1189,
−
1 1
097, 834 (ν ) cm . H NMR (dichloromethane-d ): δ 3.95, 4.63
PF
2
2
2
(
8
m × 2, 2 × 4H; PCH P), 6.18 (m, 8H; C H ), 6.92−7.76 (m, 72H +
2
6
5
Re FeOs Au assemblies to be prepared in a controlled,
31
1
2
2
2
H; C H + C H ) ppm. P{ H} NMR (dmso-d ): δ −12.0, 8.9
6
5
6
4
6
stepwise manner. Furthermore, the same diruthenium disulfide
complex (2), used as the starting point in the above studies,
serves as an easily prepared and versatile precursor for the
surface functionalization of gold and palladium nanoparticles.
This versatility allows the same design approach to be applied
to the assembly of both molecular and nanoscale multimetallic
assemblies.
1
(
3
pseudotriplet × 2, JPP = 39.0 Hz; dppm) ppm. H NMR (dmso-d ): δ
6
.88, 5.05 (m × 2, 2 × 4H; PCH P), 6.14 (m, 8H; C H ), 6.86−7.77
13 1
2
6
5
(m, 72H + 8H; C H + C H ) ppm. C{ H} NMR (CD Cl , 500
6 5 6 4 2 2
MHz): δ = 181.7 (s, CO ), 141.9 (s, CS), 134.9 (s, CCO ), 133.8,
2
2
132.4, 132.1 (m × 3, C
H
), 131.7 (s, o/m-C
5
H
4
), 131.3 (m, C H ),
6
6
6 5
1
1
31.1, 130.8 (s × 2, C H ), 130.4 (s, o/m-C H ), 129.6, 129.4, 129.3,
6 5 6 4
28.8 (m × 4, C H ), 126.4, 126.2 (s × 2, C H ), 43.6 (t, J = 11.5
6
5
6
5
PC
3
1
1
Hz, PCH P) ppm. P{ H} NMR (dmso-d ): δ −12.7, 9.3
2
6
(
pseudotriplet × 2, JPP = 39.1 Hz; dppm) ppm. MS (FAB + ve):
EXPERIMENTAL SECTION
+
■
m/z (%) 2044 (5) [M] . Anal. Calcd for C114
2333.97): C, 58.7; H, 4.2. Found: C, 58.6; H, 4.2.
[Ru(dppm) (O CC SH-4)]PF (3). Solid sodium borohydride
H F O P10Ru S (M =
96 12 4 2 2 w
General Comments. Unless otherwise stated, all experiments
were carried out in air and 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 complexes were prepared as described elsewhere: [AuCl-
H
6
2
2
4
6
(8.0 mg, 0.21 mmol) was added at 0 °C to a solution of 2 (115 mg,
0.049 mmol) in dichloromethane (15 mL). After it was stirred for 4 h,
the solution was adjusted to pH 4 through addition of 4 M HCl
solution. The organic layer was then washed with water (20 mL) and
41
42
43
44
45
(
[
PR )] (R = Me, Cy, Ph ), [dppf(AuCl) ], [AuCl(IDip)],
brine (20 mL) and dried over Na SO . All solvent was removed under
2 4
3
2
1
2
46
Au(SC H CO H-4) ]PPN, cis-[RuCl (dppm) ], [M(CH
vacuum, and the resulting yellow powder was washed with diethyl
ether (10 mL). This was dried under vacuum. Yield: 73 mg (64%). IR
6
4
2
2
2
2
14,17b
15
CHC H Me-4)Cl(CO)(BTD)(PPh ) ] (M = Ru,
Os ), [Ru(C-
6
4
3 2
4
7
(
(
CCPh)CHPh)(CO)(PPh ) ], and [Os{CHCH-bpyReCl-
(solid state): 3056, 1595 (νCO), 1484, 1428, 1095, 1000, 830 (νPF)
3
2
7
a
−1 1
CO) }Cl(CO)(BTD)(PPh ) ]. All glassware used for nanoparticle
cm . H NMR: δ 4.06, 4.72 (m × 2, 2 × 2H; PCH P), 6.10−6.18 (m,
3
3
2
2
31 1
preparation was washed with aqua regia and rinsed thoroughly with
ultrapure water before use. Electrospray (ES) and fast atom
bombardment (FAB) mass data were obtained using Micromass
LCT Premier and Autospec Q instruments, respectively. Infrared data
were obtained using a PerkinElmer Spectrum 100 FT-IR spectrometer,
and characteristic triphenylphosphine-associated infrared data are not
reported. NMR spectroscopy was performed at 25 °C using Varian
4H; C H ), 6.99−7.77 (m, 36H + 4H; C H + C H ) ppm. P{ H}
6
5
6
5
6
4
NMR: δ −11.9, 8.8 (pseudotriplet × 2, J = 39.0 Hz; dppm) ppm. MS
PP
+
(ES +ve): m/z (%) 1024 (50) [M + H] . Anal. Calcd for
C H F O P RuS·4CH Cl (M = 1507.72, M = 1167.99 in absence
57
49
6
2
5
2
2
w
w
of solvation): C, 48.6; H, 3.8. Found: C, 48.5; H, 4.0.
[(dppm) Ru(O CC H S-4)Au(PPh )]PF (4). A solution of [Au-
2
2
6
4
3
6
(SC H CO H-4)(PPh )] (19 mg, 0.031 mmol), sodium methoxide
6
4
2
3
H
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
−
1 1
(
0
2.7 mg, 0.050 mmol), and ammonium hexafluorophosphate (5.0 mg,
.031 mmol) in dichloromethane (5 mL) and methanol (2 mL) was
added dropwise to a stirred solution of cis-[RuCl (dppm) ] (28 mg,
1281, 1171, 1084, 936, 801, 755 cm . H NMR (acetone-d ): δ 1.28
6
(d, JHH = 6.9 Hz, 12H; CH ), 1.37 (d, J = 6.9 Hz, 12H; CH ), 2.74
(sep, JHH = 6.9 Hz, 4H; CHMe ), 6.84, 7.42 (d × 2, J = 8.2 Hz, 4H;
C H ), 7.48 (d, J = 7.8 Hz, 4H; m-C H ), 7.64 (t, J = 7.8 Hz, 2H;
6 4 HH 6 3 HH
3
HH
3
2
2
2
HH
0
.030 mmol) in dichloromethane (10 mL). After the mixture was
stirred for 4 h, all solvent was removed under vacuum. The residue was
dissolved in dichloromethane (10 mL) and filtered through Celite to
remove inorganic salts. The solvent was removed, and the resulting
yellow powder was washed with diethyl ether (10 mL). This was dried
under vacuum. Yield: 38 mg (75%). IR (solid state): 3055, 1587 (νCO),
p-C H ), 7.87 (s, 2H; NCH) ppm. MS (ES +ve): m/z (%): 739 (10)
6 3
+
[M] . Anal. Calcd for C H AuN O S (M = 738.73): C, 55.3; H, 5.6;
34
41
2
2
w
N, 3.8. Found: C, 55.2; H, 5.7; N, 3.9.
[(dppm) Ru(O CC H S-4)Au(IDip)]PF (9). Using the same
2
2
6
4
6
procedure as employed for 4, the reaction of 8 (18 mg, 0.024
mmol), sodium methoxide (1.4 mg, 0.026 mmol), ammonium
hexafluorophosphate (4.1 mg, 0.025 mmol), and cis-[RuCl (dppm) ]
−1 1
1
481, 1435, 1419, 1175, 1098, 833 (ν ), 730, 690 cm . H NMR
PF
(
dichloromethane-d ): δ 3.90, 4.62 (m × 2, 2 × 2H; PCH P), 6.15−
.20 (m, 4H; C H ), 6.99−7.80 (m, 51H + 4H; C H + C H ) ppm.
2
2
2
2
6
(24 mg, 0.026 mmol) provided a yellow solid. Yield: 28 mg (62%). IR
(solid state): 2960, 1585 (νCO), 1471, 1416, 1174, 1093, 837 (νPF),
6
5
6
5
6
4
1
3
1
C{ H} NMR (CD Cl , 500 MHz): δ 183.4 (s, CO ), 151.3 (s, CS),
2
2
2
−
1 1
1
34.5 (d, JPC = 11.0 Hz, o/m-AuPC H ), 133.9 (m, RuPC H ), 133.7
734, 692 cm . H NMR (dichloromethane-d
1.44 (d × 4, JHH = 6.9 Hz, 4 × 6H; Me), 2.77 (sep, JHH = 6.9 Hz, 4H;
CHMe ), 3.89, 4.63 (m × 2, 2 × 2 H; PCH P), 6.34 (m, 4H; C ),
6.83 (d, JHH = 8.1 Hz, 2H; C ), 7.06−7.55 (m, 28H + 2H + 4H;
+ C + m-C ), 7.64 (t, JHH = 7.8 Hz, 2H; p-C ), 7.83 (m,
4H; C ), 7.91 (s, 2H; NCH), 8.01 (m, 4H; C ) ppm. P{ H}
NMR (acetone-d ): δ −12.9, 9.0 (pseudotriplet × 2, JPP = 39.0 Hz;
dppm) ppm. MS (ES +ve): m/z (%) 1607 (100) [M] . Anal. Calcd for
RuS (M = 1752.54): C, 57.6; H, 4.8; N, 1.6.
Found: C, 57.4; H, 4.8; N, 1.6.
[Au{SC CO Ru(dppm)
[RuCl (dppm) ] (55 mg, 0.059 mmol) in dichloromethane (10 mL)
was added to [N(PPh ][Au(SC CO H) ] (30 mg, 0.029 mmol),
2
): δ 1.25, 1.33, 1.39,
6
5
6
5
(
s, CCO ), 132.4 (m, RuPC H ), 132.3 (s, RuPC H ), 132.1 (s, o/m-
2 6 5 6 5
C H ), 131.6 (s, p-AuPC H ), 131.3, 130.9 (m × 2, RuPC H ), 130.7
2
2
H
6 5
6
4
6
5
6
5
(
s, RuPC H ), 130.4 (s, o/m-C H ), 129.7 (m, o/m-AuPC H + ipso-
H
6 4
6
5
6
4
6
5
AuPC H ), 129.6, 129.4, 128.9, 128.7 (m × 4, RuPC H ), 128.2 (s,
C
6
H
5
6
H
4
6
H
3
H
6 3
6
5
6
5
3
1
1
31
1
RuPC H ), 43.6 (t, J = 13.0 Hz, PCH P) ppm. P{ H} NMR
6
H
5
H
6 5
6
5
PC
2
(
dichloromethane-d ): δ −12.1, 8.9 (pseudotriplet × 2, J = 39.0 Hz;
6
2
PP
+
+
dppm), 38.5 (s; PPh ) ppm. MS (ES +ve): m/z (%) 1481 (60) [M] .
3
Anal. Calcd for C H AuF O P RuS (M = 1626.24): C, 55.4; H, 3.9.
C
84
H
84AuF
6
N
2
O
2
P
5
w
75
63
6
2
6
w
Found: C, 55.5; H, 3.7.
Au(SC H CO H-4)(PCy )] (5). A solution of 4-mercaptobenzoic
[
6
H
4
2
} ]PF (10). A solution of cis-
2 2 6
6
4
2
3
acid (15 mg, 0.097 mmol) and sodium methoxide (6.0 mg, 0.11
mmol) in methanol (5 mL) was added dropwise to a stirred solution
2
2
)
3
H
2
6
2
2
2
of [AuCl(PCy )] (50 mg, 0.098 mmol) in dichloromethane (10 mL).
ammonium hexafluorophosphate (19 mg, 0.12 mmol), and sodium
methoxide (6.0 mg, 0.111 mmol) in a mixture of methanol (5 mL) and
dichloromethane (2 mL). The reaction mixture was stirred for 2 h at
room temperature. All solvent was removed under vacuum, and the
crude product was dissolved in dichloromethane (10 mL) and filtered
through Celite to remove NaCl, NaOMe, and excess ligand. Ethanol
(20 mL) was added, and the solvent volume was slowly reduced on a
rotary evaporator until the precipitation of the yellow product was
complete. This was filtered, washed with cold ethanol (5 mL) and
petroleum ether (10 mL), and dried under vacuum. Yield: 49 mg
(71%). IR (solid state): 1590 (νCO), 1484, 1426, 1312, 1261, 1177,
3
After the mixture was stirred for 2 h, all solvent was removed under
vacuum. The residue was dissolved in dichloromethane (10 mL) and
filtered through Celite to remove NaCl. Pentane (25 mL) was then
added, resulting in the precipitation of a colorless solid. This was
filtered and dried under vacuum. Yield: 36 mg (58%). IR (solid state):
2
920, 2852, 1446, 1348, 1293, 1265, 1174, 1113, 1004, 888, 850, 739
−1 1
cm . H NMR (acetone-d ): δ 1.30−2.84 (m, 33H; PCy ), 7.56, 7.70
6
3
31
1
(
(
d × 2, J = 8.6 Hz, 4H; C H ). P{ H} NMR (acetone-d ): δ 58.3
HH 6 4 6
+
s; PCy ) ppm. MS (ES +ve): m/z (%) 981 (60) [2 M − PCy ] .
3
3
Anal. Calcd for C H AuO PS·CH Cl (M = 715.51, M = 630.57 in
25
38
2
2
2
w
w
−1 1
absence of solvation): C, 43.6; H, 5.6. Found: C, 43.1; H, 5.6.
(dppm) Ru(O CC H S-4)Au(PCy )]PF (6). Using the same
1094, 1027, 1014, 1000, 834 (νPF) cm ; H NMR (DMSO-d
(m, 2 × 2H; PCH P), 5.01 (m, 2 × 2H; PCH P), 6.12 (m, 8H; C
6.86−7.75 (m, 72H + 8H; C + C
(DMSO-d ): δ −7.94 (pseudotriplet, JPP = 39.0 Hz; dppm), 14.02
(pseudotriplet, JPP = 39.0 Hz; dppm) ppm. MS (ES +ve): m/z (%)
6
): δ 3.88
),
H
) ppm. 31P{ H} NMR
6 4
[
2
2
H
6 5
2
2
6
4
3
6
1
procedure employed in the preparation of 4, [Au(SC H CO H-
6
H
5
6
4
2
4
)(PCy )] (22 mg, 0.035 mmol), sodium methoxide (2.0 mg, 0.037
6
3
mmol), ammonium hexafluorophosphate (5.5 mg, 0.034 mmol), and
cis-[RuCl (dppm) ] (32 mg, 0.034 mmol) provided a yellow solid.
+
2044 (100) [M − Au] . Anal. Calcd for C114
= 2385.97): C, 57.4; H, 4.1. Found: C, 57.2; H, 4.0.
[(dppf){AuSC CO Ru(dppm) ](PF (11). A solution of
[dppf(AuSC CO H-4) ] (12 mg, 0.010 mmol), sodium methoxide
H96AuF O P Ru S (M
2
2
6 4 9 2 2 w
Yield: 29 mg (52%). IR (solid state): 3057, 2925, 2852, 1706, 1586
−1 1
(
νCO), 1482, 1418, 1261, 1094, 834 (ν ), 729, 691 cm . H NMR
6
H
2
4
2
2
}
2
)
6 2
PF
(
CD Cl ): δ 1.30−2.16 (m, 33H; PCy ), 3.90, 4.63 (m × 2, 2 × 2H;
6
H
4
2
2
2
3
PCH P), 6.18 (m, 4H; C H ), 6.96−7.99 (m, 36H + 4H; C H +
(1.0 mg, 0.019 mmol), and ammonium hexafluorophosphate (4.9 mg,
0.030 mmol) in dichloromethane (5 mL) and methanol (2 mL) was
added dropwise to a stirred solution of cis-[RuCl (dppm) ] (18.8 mg,
2
6
5
6
5
31
1
C H ) ppm. P{ H} NMR (dichloromethane-d ): δ −12.1, 8.9
6
4
2
(
+
pseudotriplet × 2, JPP = 39.0 Hz; dppm), 57.6 (s; PPh ) ppm. MS (ES
3
+
2
2
ve): m/z (%) 1500 (100) [M] . Anal. Calcd for C H AuF O P RuS
0.020 mmol) in dichloromethane (10 mL). After the mixture was
stirred for 4 h, all solvent was removed under vacuum. The residue was
filtered and washed with water (10 mL) and pentane (5 mL),
providing a pale yellow powder. This was dried under vacuum. Yield:
20 mg (61%). IR (solid state): 1587 (νCO), 1483, 1435, 1173, 1099,
75
81
6
2 6
(
M = 1644.38): C, 54.8; H, 5.0. Found: C, 54.4; H, 5.2.
w
[
(dppm) Ru(O CC H S-4)Au(PMe )]PF (7). Employing the
2 2 6 4 3 6
same procedure used to prepare 4, the reaction of [Au-
(
(
0
SC H CO H-4)(PMe )] (21 mg, 0.049 mmol), sodium methoxide
6 4 2 3
−1 1
3.0 mg, 0.056 mmol), ammonium hexafluorophosphate (8.0 mg,
.049 mmol), and cis-[RuCl (dppm) ] (46 mg, 0.049 mmol) provided
1027, 835 (ν ), 731, 692 cm . H NMR (acetone-d ): δ 3.98 (m, 4
P
F
6
H; PCH P), 4.24, 4.63 (s × 2, 2 × 4H; C H ), 4.95 (m, 4 H; PCH P),
2 5 4 2
2
2
a yellow solid. Yield: 44 mg (62%). IR (solid state): 3056, 1916, 1586
6.21 (m, 4 H; C H ), 6.49, 6.63 (m × 2, 2 × 2H; C H ), 6.81−7.80
6
5
6
4
31 1
(
ν
), 1481, 1482, 1419, 1262, 1174, 1094, 960, 832 (ν ), 729, 690
(m, 76 H + 8 H; C H + C H ) ppm. P{ H} NMR: δ −13.7, 7.5
CO
PF
6
5
6
4
−
1 1
cm . H NMR (acetone-d ): δ 1.75 (d, J = 11.0 Hz, 9H; PMe3),
(pseudotriplet × 2, JPP = 39.0 Hz; dppm), 27.7 (s; dppf) ppm. MS
6
HP
+
4
.12, 5.02 (m × 2, 2 × 2H; PCH P), 6.34 (m, 4H; C H ), 7.04−8.00
(MALDI) m/z (%) 3031 (12) [M + K] . Anal. Calcd for
2
6
5
31
1
(
m, 36H + 4H; C H + C H ) ppm. P{ H} NMR (acetone-d ): δ
C148H124Au F FeO P Ru S (Mw = 3282.24): C, 54.2; H, 3.8.
6
5
6
4
6
2
12
4
12
2 2
−
12.8, 8.9 (pseudotriplet × 2, JPP = 39 Hz; dppm), 0.6 (s; PMe ) ppm.
Found: C, 54.4; H, 3.9.
3
+
MS (ES +ve): m/z (%) 1295 (100) [M] . Anal. Calcd for
C H AuF O P RuS (M = 1440.03): C, 50.0; H, 4.0. Found: C,
[{Ru(CHCHC H Me-4)(CO)(PPh ) (O CC H S-4)} ] (12).
6
4
3 2
2
6
4
2
Using the same procedure used to prepare 2, the reaction of
compound 1 (6.4 mg, 0.021 mmol), sodium methoxide (2.3 mg, 0.043
mmol), and [Ru(CHCHC H Me-4)Cl(CO)(BTD)(PPh ) ] (40
6
0
57
6
2
6
w
4
9.9; H, 4.1.
Au(SC H CO H-4)(IDip)] (8). Using the same procedure as
[
6
4
2
6
4
3 2
employed for 5, the reaction of 4-mercaptobenzoic acid (12 mg,
.078 mmol), sodium methoxide (4.5 mg, 0.083 mmol), and
AuCl(IDip)] (50 mg, 0.081 mmol) provided a colorless solid.
Yield: 50 mg (84%). IR (solid state): 2961, 1671, 1581 (νCO), 1415,
mg, 0.042 mmol) provided an orange solid. Yield: 24 mg (62%). IR
0
[
(solid state): 1917 (νCO), 1575 (νCO), 1507, 1481, 1418, 1185, 1094,
−1 1
862, 742, 691 cm . H NMR (CD Cl ): δ 2.22 (s, 6H; CH ), 5.85 (d,
2 2 3
JHH = 15.5 Hz, 2H; Hβ), 6.38, 6.82 (d × 2, JHH = 7.8 Hz, 2 × 4H;
I
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
C H Me), 7.05, 7.10 (d × 2, J = 8.6 Hz, 2 × 4H; C H S), 7.28−7.51
Hz, 4H; SC H ), 7.32−7.40, 7.46−7.63 (m × 2, 45H; C H ), 7.85 (dt,
HH HP 2 2
6
4
HH
6
4
6
4
6
5
= 15.4, J = 2.6 Hz, 1H; Hα) ppm. 13C{ H} NMR (CD Cl , 500
1
(
m, 60H; C H ), 7.82 (dt, J = 15.5 Hz, J unresolved, 2H; Hα)
J
6
5
HH
HP
13
1
ppm. C{ H} NMR (CD Cl , 400 MHz): δ 202.4 (t, J = 11.3 Hz,
MHz): δ 207.1 (t, JPC = 15.3 Hz, CO), 178.2 (s, CO ), 153.5 (t, J
=
PC
2
2
PC
2
1/4
v
CO), 176.4 (s, CO ), 152.5 (s, CS), 139.2 (t(br), J unresolved, Cα),
11.7 Hz, Cα), 147.6 (s, CS), 138.6 (s, C -C H ), 134.7 (t , J = 5.8
2
PC
6 4 PC
/4
v
1
38.1 (s, C1 -C H ), 134.3 (t , J = 5.5 Hz; o/m-C H ), 133.4 (t(br),
Hz, o/m-RuPC H ), 134.5 (d, J = 13.7 Hz, o/m-AuPC H ), 133.8
6 5 PC 6 5
6
4
PC
6
5
1
/4
v
1/4
JPC unresolved, Cβ), 132.9, 132.0, 131.9 (s × 3, C -C H ), 131.3 (t ,
JPC = 21.3 Hz; ipso-C H ), 129.8 (s, p-C H ), 128.5, 128.2 (s × 2, o/m-
(t(br), JPC unresolved, Cβ), 133.3 (s, C -C H ), 132.2 (s, p-
6
4
6 4
v
AuPC H ), 131.9 (t , J = 21.4 Hz, ipso-RuPC H ), 130.7 (s, o/m-
6 5 PC 6 5
C H ), 130.5 (s, C -C H ), 130.1 (s, p-RuPC H ), 129.7 (d, J
6
5
6
5
v
1/4
C H ), 127.9 (t , J = 3.9 Hz, o/m-C H ), 125.3, 124.5 (s × 2, o/m-
=
6
4
PC
6
5
6
4
6
4
6
5
PC
31
1
C H ), 20.6 (s, CH ) ppm. P{ H} NMR (CD Cl ): δ 37.7 (s; PPh )
11.2 Hz, o/m-AuPC H ), 129.3 (d, J = 25.3 Hz, ipso-AuPC H ),
6
4
3
2
2
3
6 5 PC 6 5
+
v
ppm. MS (ES +ve): m/z (%) 1885 (2) [M + K] , 1175 (14) [M −
128.6 (s, o/m-C H ), 128.3 (t , J = 5.6 Hz, o/m-RuPC H ), 127.9,
6 4 PC 6 5
+
31
1
vinyl − CO − 2PPh ] . Anal. Calcd for C H O P Ru S (M
=
124.5 (s × 2, o/m-C H ), 20.9 (s,CH ) ppm. P{ H} NMR
3
106 86
6
4
2
2
w
6 4 3
1
845.98): C, 69.0; H, 4.7. Found: C, 68.8; H, 4.8.
(CD Cl ): δ 37.5 (s; RuPPh ), 38.7 (s; AuPPh ). MS (ES +ve): m/
2 2 3 3
+
[
{Os(CHCHC H Me-4)(CO)(PPh ) (O CC H S-4)} ] (13).
z (%) 1405 (5) [M + Na] . Anal. Calcd for C H AuO P RuS (M =
6
4
3 2
2
6
4
2
71 58 3 3 w
Using the same procedure employed to prepare 2, the reaction of
compound 1 (5.8 mg, 0.019 mmol), sodium methoxide (2.0 mg, 0.037
mmol), and [Os(CHCHC H Me-4)Cl(CO)(BTD)(PPh ) ] (40
1382.24): C, 61.7; H, 4.2. Found: C, 61.7; H, 4.1.
[(IDip)Au(SC H CO -4)Ru(CHCHC H Me-4)(CO)(PPh ) ]
6
4
2
6
4
3 2
(17). Employing the same procedure as used for the synthesis of 4, the
reaction of [Au(SC CO H)(IDip)] (15 mg, 0.020 mmol), sodium
methoxide (1.1 mg, 0.020 mmol), and [Ru(CHCHC Me-
4)Cl(CO)(BTD)(PPh ] (20 mg, 0.020 mmol) provided a yellow
solid. Yield: 21 mg (70%). IR (solid state): 2960, 1923 (νCO), 1723,
6
4
3 2
mg, 0.039 mmol) provided a yellow solid. Yield: 26 mg (66%). IR
6
H
4
2
(
8
solid state): 1906 (νCO), 1592 (νCO), 1507, 1482, 1433, 1186, 1095,
H
6 4
−1 1
68, 742, 691 cm . H NMR (acetone-d ): δ 2.21 (s, 6H; CH ), 5.78
)
3 2
6
3
(
d, JHH = 16.0 Hz, 2H; Hβ), 6.37, 6.75 (d × 2, JHH = 7.8 Hz, 2 × 4H;
−1 1
C H Me), 7.08, 7.20 (d × 2, J = 8.6 Hz, 2 × 4H; C H S), 7.32−7.48
1587 (νCO), 1480, 1417, 1260, 1172, 1093, 801, 746, 691 cm . H
NMR (CD Cl ): δ 1.28, 1.34 (d × 2, JHH = 6.9 Hz, 2 × 12H; IDip-
CH ), 2.23 (s, 3H; tolyl-CH ), 2.65 (sep, JHH = 6.9 Hz, 4H; CHMe ),
.82 (d, JHH = 15.3 Hz, 1H; Hβ), 6.41 (d, JHH = 8.0 Hz, 2H; C H ),
6
4
HH
6
4
(
m, 60H; C H ), 8.21 (dt, J = 16.0, J = 2.1 Hz, 2H; Hα) ppm.
2
2
6
5
HH
HP
3
1
1
P{ H} NMR (acetone-d ): δ 18.5 (s; PPh ) ppm. MS (ES +ve): m/z
%) 2025 (46) [M] . Anal. Calcd for C H O Os P S (Mw
3
3
2
6
3
+
5
6
(
=
6
4
106 86
6
2 4 2
.43 (d, JHH = 8.3 Hz, 2H; C H ), 6.58 (d, J = 8.3 Hz, 2H; C H ),
2
024.30): C, 62.9; H, 4.3. Found: C, 62.8; H, 4.2.
6
4
HH
6
4
[
{Os{CHCH-bpyReCl(CO) }(CO)(PPh ) (O CC H S-4)} ] (14).
6.84 (d, JHH = 8.0 Hz, 2H; C
6
H
4
), 7.29 (s, 2H; NCH), 7.33−7.41,
+ m-C ), 7.60 (t, JHH = 7.8 Hz,
), 7.88 (dt, JHH = 15.3, JHP = 2.7 Hz, 1H; Hα) ppm.
P{ H} NMR (CD Cl ): δ 37.4 (s; PPh ). MS (ES +ve): m/z (%)
1554 (1) [M + 2Na] , 1269 (50) [M − PPh
RuS (M = 1508.54): C, 63.7; H, 5.3; N, 1.9. Found:
C, 63.5; H, 5.2; N, 2.1.
[(Ph P)Au(SC CO
(18). Employing the same procedure as used for the synthesis of 4, the
reaction of [Au(SC CO H)(PPh )] (35 mg, 0.057 mmol), sodium
methoxide (3.1 mg, 0.057 mmol), and [Ru(C(CCPh)CHPh)-
(CO)(PPh ] (50 mg, 0.057 mmol) provided a yellow solid. Yield: 57
mg (68%). IR (solid state): 2163 (νCC), 1919 (νCO), 1588 (νCO),
3
3 2
2
6
4
2
Using the same procedure used to prepare 2, the reaction of
compound 1 (5.5 mg, 0.018 mmol), sodium methoxide (2.0 mg, 0.037
mmol), and [Os{CHCH−bpyReCl(CO) }Cl(CO)(BTD)(PPh ) ]
7.48−7.52 (m × 2, 30H + 4H; C
H
6
5
H
6 3
2H; p-C
H
3
6
31
1
3
3 2
2
+
2
3
+
(
50 mg, 0.036 mmol) provided an orange solid. Yield: 44 mg (89%).
+ Na] . Anal. Calcd for
3
Recrystallization from a dichloromethane solution of 13 layered with
diethyl ether produced microcrystals, which were used for elemental
C
80
H79AuN
2
O
3
P
2
w
analysis. IR (solid state): 2015 (ν ), 1882 (νCO), 1586 (νCO), 1433,
3
6
H
4
2
-4)Ru(C(CCPh)CHPh)(CO)(PPh
) ]
3 2
CO
−
1 1
1
352, 1184, 1094, 745, 692 cm . H NMR (acetone-d ): δ 5.72 (d,
6
JHH = 16.2 Hz, 2H; Hβ), 7.14, 7.22 (d × 2, JHH = 8.4 Hz, 2 × 4H;
6
H
4
2
3
C H S), 7.30−7.46 (m, 60H + 2H; C H + bpy), 7.65 (t, J = 6.4 Hz,
6
4
6
5
HH
2
H; bpy), 8.00 (s, 2H; bpy), 8.14 (d, JHH = 8.3 Hz, 2H; bpy), 8.22 (t,
)
3 2
JHH = 7.6 Hz, 2H; bpy), 8.41 (d, JHH = 7.6 Hz, 2H; bpy), 9.01 (d, JHH
−
1
1
=
4.7 Hz, 2H; bpy), 9.36 (dt, J = 16.2 Hz, JHP unresolved, 2H; Hα)
1481, 1433, 1419, 1173, 1094, 864, 742, 690 cm . H NMR
(CD Cl ): δ 6.08 (s(br), 1H; CHPh), 6.86 (d, JHH = 8.1 Hz, 2H;
Me), 7.00, 7.10, 7.17−7.72 (m × 3, 42H; C
HH
31
1
ppm. P{ H} NMR (acetone-d ): δ 19.4 (s; PPh ) ppm. MS
2
2
6
3
+
(
MALDI) m/z (%) 1867 (40) [M − 3PPh − 4CO] . Anal. Calcd for
C
6
H
4
6
H
4
Me + CC
) ppm. 13C{ H} NMR (CD
H Cl , 500 MHz): δ 207.4 (t, JPC
6 5 2 2
6
H
5
+
=
3
1
C1 H Cl N O Os P Re S ·5CH Cl (M = 3188.43, M = 2763.77
PC
15.0 Hz, CO), 178.0 (s, CO
18
86
2
4
12
2
4
2
2
2
2
w
w
in absence of solvation): C, 46.3; H, 3.0; N, 1.8. Found: C, 46.5; H,
.9; N, 2.2.
(dppf){AuSC H CO Os(CHCH-bpyReCl(CO) )(CO)(PPh ) } ]
2
), 147.6 (s, CS), 140.4 (t(br), JPC
unresolved, Cα), 134.9 (t , JPC = 5.9 Hz, o/m-RuPC ), 134.5 (d, JPC
= 13.6 Hz, o/m-AuPC ), 132.2 (s, p-AuPC ), 131.7 (s, o/m-
C H ), 131.2 (t , J = 21.6 Hz, ipso-RuPC H ), 130.6 (s, o/m-C H ),
v
2
H
6 5
[
6
H
5
6 5
H
6
4
2
3
3 2 2
v
(
15). Using the same procedure employed to prepare 11, the reaction
6
4
PC
6
5
6
4
of [dppf(AuSC H CO H) ] (23 mg, 0.018 mmol), sodium methoxide
130.1 (s, p-RuPC H ), 129.7 (d, J = 25.7 Hz, ipso-AuPC H ), 129.6
6
4
2
2
6
5
PC
6
5
(
(
4
1
2.0 mg, 0.037 mmol), and [Os{CHCH-bpyReCl(CO) }Cl(CO)-
(d, JPC = 11.2 Hz, o/m-AuPC H ), 128.9 (s, quaternary-C), 128.5 (s,
3
6 5
v
BTD)(PPh ) ] (50 mg, 0.036 mmol) provided an orange solid. Yield:
CC H ), 128.1 (t , J = 5.0 Hz, o/m-RuPC H ), 127.8, 127.4 (s × 2,
6 5 PC 6 5
3
2
7 mg (70%). IR (solid state): 2016 (νCO), 1886 (νCO), 1586 (νCO),
CC H ), 127.3 (s, quaternary-C), 126.6 (t(br), J unresolved, Cβ),
6
5
P
C
−1
1
31
1
534, 1469, 1420, 1355, 1168, 1095, 869, 744, 692 cm . H NMR
CD Cl ): δ 4.30, 4.64 (s(br) × 2, 2 × 4H; C H ), 5.63 (d, J = 15.8
124.9 (s, CC H ) ppm. P{ H} NMR (CD Cl ): δ 37.5 (s; RuPPh ),
6 5 2 2 3
+
(
37.1 (s; AuPPh ). MS (ES +ve): m/z (%) 1469 (6) [M] . Anal. Calcd
2
2
5
4
HH
3
Hz, 2H; Hβ), 6.89 (d × 2, JHH = 8.4 Hz, 4H; C H ), 6.96 (dd, J
=
for C H AuO P RuS (M = 1468.33): C, 63.8; H, 4.1. Found: C,
6
4
HH
78 60
3
3
w
8
7
7
9
.6, 1.9 Hz, 2H; bpy), 7.25 (d × 2, JHH = 8.4 Hz, 4H; C H ), 7.30−
63.7; H, 4.0.
6
4
.62 (m, 80H + 4H; C H + bpy), 7.75 (d, J = 8.6 Hz, 2H; bpy),
[(Ph P)Au(SC H CO -4)Os(CHCHC H Me-4)(CO)(PPh ) ]
6
5
HH
3
6
4
2
6
4
3 2
.92 (s, 2H; bpy), 8.01 (m, 4H; bpy), 8.95 (d, JHH = 5.5 Hz, 2H; bpy),
(19). Using the same procedure as employed to prepare 4, the reaction
of [Au(SC CO H)(PPh )] (15 mg, 0.025 mmol), sodium
methoxide (1.4 mg, 0.026 mmol), and [Os(CHCHC Me-
4)Cl(CO)(BTD)(PPh ] (25 mg, 0.024 mmol) provided a yellow
solid. Yield: 27 mg (77%). IR (solid state): 1893 (νCO), 1586 (νCO),
.38 (dt, JHH = 15.8 Hz, JHP = 1.8 Hz, 2H; Hα) ppm. 31P{ H} NMR
1
H
6
4
2
3
(
CD Cl ): δ 19.0 (s; PPh ), 32.5 (s(br); dppf) ppm. MS (MALDI) m/
H
6 4
2
2
3
+
z (%) 3537 (100) [M − Cl − 5CO] . Anal. Calcd for
C
3
)
3 2
H
52 114
Au Cl FeN O Os P Re S (M = 3712.08): C, 49.2; H,
1
2
2
4
12
2
6
2
2
w
−
1 1
.1; N, 1.5. Found: C, 49.2; H, 3.2; N, 1.6.
(Ph P)Au(SC H CO -4)Ru(CHCHC H Me-4)(CO)(PPh ) ]
1480, 1430, 1176, 1096, 868, 742, 692 cm . H NMR (CD
2.22 (s, 3H; CH
Hz, 2H; C H Me), 6.81 (d, J = 8.3 Hz, 2H; SC H ), 6.82 (d, J
HH
2
Cl
2
): δ
[
3
), 5.69 (d, JHH = 15.9 Hz, 1H; Hβ), 6.38 (d, JHH = 8.0
3
6
4
2
6
4
3 2
(16). Using the same procedure as employed for the preparation of 4,
=
6
4
HH
6
4
the reaction of [Au(SC H CO H)(PPh )] (15 mg, 0.025 mmol),
8.0 Hz, 2H; C H Me), 7.22 (d, J = 8.3 Hz, 2H; SC H ), 7.33−7.63
6
4
2
3
6
4
HH
6
4
sodium methoxide (1.4 mg, 0.026 mmol) and [Ru(CHCHC H Me-
(m, 45H; C H ), 8.21 (dt, J = 15.9 Hz, J = 1.9 Hz, 1H; Hα) ppm.
6
4
6 5 HH HH
31
1
4
)Cl(CO)(BTD)(PPh ) ] (23 mg, 0.025 mmol) provided a light
P{ H} NMR (CD Cl ): δ 18.3 (s; OsPPh ), 38.8 (s; AuPPh ). MS
2 2 3 3
3
2
+
yellow solid. Yield: 22 mg (64%). IR (solid state): 1908 (νCO), 1586
(ES +ve): m/z (%) 1471 (2) [M] . Anal. Calcd for C H AuO OsP S
71 58 3 3
−
1
1
(
(
6
νCO), 1481, 1425, 1175, 1095, 863, 742, 692 cm . H NMR
(M = 1471.40): C, 58.0; H, 4.0. Found: C, 57.9; H, 3.9.
w
CD Cl ): δ 2.23 (s, 3H; CH ), 5.83 (d, J = 15.4, 1H; Hβ), 6.39,
.83 (d × 2, JHH = 8.0 Hz, 4H; C H Me), 6.85, 7.20 (d × 2, J = 8.3
[(IDip)Au(SC H CO -4)Os(CHCHC H Me-4)(CO)(PPh ) ]
2
2
3
HH
6
4
2
6
4
3 2
(20). Employing the same procedure used to synthesize 4, the reaction
6
4
HH
J
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
of [Au(SC H CO H)(IDip)] (15 mg, 0.020 mmol), sodium
sulfur, phosphorus, oxygen, and fluorine. TGA: 37.8% surface units,
6
4
2
methoxide (1.1 mg, 0.020 mmol), and [Os(CHCHC H Me-
62.2% gold and ruthenium (Au (SC H CO Ru(dppm) )PF ).
6
4
8.4
6
4
2
2
6
11.9
4
)Cl(CO)(BTD)(PPh ) ] (21 mg, 0.020 mmol) provided a pale
Au @[SC H CO Ru(dppm) ]PF (NP2). Tetrachloroauric acid
3
2
6 4 2 2 6
yellow solid. Yield: 17 mg (53%). IR (solid state): 2959, 1891 (ν ),
trihydrate (20 mg, 0.051 mmol) was dissolved in ultrapure water (60
mL). The solution was heated to reflux for 20 min. A preheated
aqueous solution (4 mL) of trisodium citrate (52.7 mg, 0.204 mmol)
was added. The heating source was quickly removed, and the stirred
solution was cooled to room temperature. A mixture of a methanol
and acetonitrile solution (3 mL) of 2 (179 mg, 0.077 mmol) was
added, and the mixture was stirred for 3 h at room temperature, after
which it was stored at 4 °C overnight in order to allow the
nanoparticles formed to settle. The supernatant was removed, and the
nanoparticles were washed with water (3 × 10 mL) and centrifuged.
Methanol (3 × 10 mL) and dichloromethane (10 mL) washes were
employed to remove unattached surface units. The resulting dark blue
solid (112 mg) isolated was dried under vacuum and stored under
nitrogen. IR (solid state): 1586 (νCO), 1485, 1436, 1098, 1000, 834
CO
−
1 1
1
587 (νCO), 1479, 1419, 1174, 1095, 868, 803, 745, 693 cm . H
NMR (CD Cl ): δ 1.28, 1.34 (d × 2, J = 6.8 Hz, 2 × 12H; IDip-
2
2
HH
CH ), 2.22 (s, 3H; tolyl-CH ), 2.64 (sep, J = 6.9 Hz, 4H; CHMe2),
3
3
HH
5
6
.68 (d, JHH = 15.9 Hz, 1H; Hβ), 6.40 (d, JHH = 7.8 Hz, 2H; C H Me),
6 4
.45, 6.53 (d × 2, JHH = 8.3 Hz, 2 × 2H; SC H ), 6.82 (d, J = 7.8
6
4
HH
Hz, 2H; C H Me), 7.29 (s, 2H; NCH), 7.33−7.51 (m, 30H + 4H;
6
4
C H + m-C H ), 7.60 (t, J = 7.8 Hz, 2H; p-C H ), 8.23 (dt, J =
6
5
6
3
HH
6
3
HH
31
1
1
(
5.9 Hz, JHP = 2.0 Hz, 1H; Hα) ppm. P{ H} NMR (CD Cl ): δ 18.0
s; PPh ) ppm. MS (ES +ve): m/z (%) 1599 (27) [M + H] . Anal.
2 2
+
3
Calcd for C H AuN O OsP S (M = 1597.71): C, 60.1; H, 5.0; N,
80
79
2
3
2
w
1
.8. Found: C, 59.9; H, 4.9; N, 1.8.
(Ph P)Au(SC H CO -4)Ru{CHCH-bpyReCl(CO) }(CO)-
PPh ) ] (21). Employing the same procedure used to synthesize 4,
3 2
[
3
6
4
2
3
(
−1 1
the reaction of [Au(SC H CO H)(PPh )] (23 mg, 0.038 mmol),
(ν ), 735, 698 cm . H NMR (dmso-d , 500 MHz): δ 4.43, 5.74 (m
PF 6
6
4
2
3
sodium methoxide (2.1 mg, 0.039 mmol), and [Ru{CHCH-
× 2, 2 × 2H; PCH
2
P), 6.61 (m, 4H; C
+ C H ) ppm. P{ H} NMR (dmso-
6 4
6 5
H ), 7.10, 7.26, 7.38, 7.54, 7.72,
31
1
bpyReCl(CO) }Cl(CO)(BTD)(PPh ) ] (50 mg, 0.038 mmol)
7.94 (m × 6, 36H + 4H; C
6
H
5
3
3 2
provided an orange solid. Yield: 61 mg (92%). IR (solid state):
d , 500 MHz): δ −18.6, −3.2 (pseudotriplet × 2, JPP = 35.6 Hz; dppm)
6
2
1
016 (νCO), 1909 (νCO), 1885 (νCO), 1587 (νCO), 1535, 1481, 1434,
ppm. TEM analysis of over 200 nanoparticles gave a size of 11.9 ± 0.9
nm. EDS confirmed the presence of gold and ruthenium and indicated
the presence of sulfur, phosphorus, oxygen, and fluorine. TGA: 42.5%
−1 1
419, 1176, 1095, 862, 744, 692 cm . H NMR (CD Cl ): δ 5.78 (d,
2
2
JHH = 15.6 Hz, 1H; Hβ), 6.92 (d, JHH = 8.5 Hz, 2H; SC H ), 6.98 (dd,
6
4
JHH = 8.6, 2.0 Hz, 1H; bpy), 7.21 (d, JHH = 8.5 Hz, 2H; SC H ), 7.36−
surface units, 57.5% gold and ruthenium (Au6.8(SC
(dppm) )PF ).
Au@[SC
6
H
4
CO
CO H-4) ]
2
2
Ru-
6
4
7
1
1
.61 (m, 45H; C H ), 7.78 (d, J = 8.5 Hz, 2H; bpy), 7.92 (s(br),
2
6
H
6
5
HH
H; bpy), 8.02 (m, 2H; bpy), 8.92 (dt, JHH = 15.6 Hz, J = 2.5 Hz,
6
4
CO
2
H] (NP3). Heating PPN[Au(SC
6
H
4
2
HH
H; Hα), 8.97 (d, JHH = 5.4 Hz, 1H; bpy) ppm. 31P{ H} NMR
1
(PPN = bis(triphenylphosphine)iminium; 25 mg, 0.024 mmol) in
acetone (5 mL) with excess sodium borohydride (18 mg, 0.476 mmol)
resulted in the darkening of the solution and the formation of a fine
black solid, which was washed with water (3 × 10 mL) and methanol
(2 × 10 mL) and centrifuged. The resulting black solid (11 mg) was
dried under vacuum. IR (solid state): 1587 (νCO), 1482, 1436, 1096
(
(
CD Cl ): δ 37.9 (s; RuPPh ), 38.0 (s; AuPPh ). MS (ES +ve): m/z
%) 1753 (22) [M] , 1793 (62) [M + K] . Anal. Calcd for
2 2 3 3
+
+
C H AuClN O P ReRuS (M = 1751.98): C, 52.8; H, 3.3; N, 1.6.
7
7
58
2
6
3
w
Found: C, 52.6; H, 3.4; N, 1.7.
(IDip)Au(SC H CO -4)Os{CHCH-bpyReCl(CO) }(CO)-
[
6
4
2
3
−1 1
(
PPh ) ] (22). Using the same procedure employed for the
cm . H NMR (dmso-d ): δ 7.45, 7.56 (m(br) × 2, 4H; C H ) ppm.
6
6
4
3
2
preparation of 4, the reaction of [Au(SC H CO H)(IDip)] (13 mg,
TEM analysis of over 100 nanoparticles gave a size of 4.1 ± 0.7 nm.
EDS confirmed the presence of gold and sulfur.
6
4
2
0
.018 mmol), sodium methoxide (1.0 mg, 0.019 mmol), and
[
Os{CHCH-bpyReCl(CO) }Cl(CO)(BTD)(PPh ) ] (24 mg,
Pd@[SC H CO Ru(dppm) ]PF (NP4). [PdCl (NCMe) ] (13 mg,
6 4 2 2 6 2 2
3
3 2
0
2
1
1
.017 mmol) provided an orange solid. Yield: 23 mg (69%). IR:
0.050 mmol) and tetraoctylammonium bromide (109 mg, 0.200
mmol) were dissolved in dry tetrahydrofuran (10 mL) under an inert
atmosphere. After 10 min of stirring, lithium triethylborohydride (1 M
tetrahydrofuran solution, 0.15 mL, 3 equiv) was added with vigorous
stirring. The solution faded from red to black, indicating the formation
of nanoparticles. After 30 min, a solution of 2 (117 mg, 0.050 mmol)
in a 2/1 mixture of dry tetrahydrofuran and dry acetonitrile was added
(3 mL). The mixture was stirred overnight at room temperature. The
mixture was then centrifuged and the supernatant removed. The
remaining solid was washed with methanol (2 × 10 mL) and acetone
(2 × 10 mL). The resultant black solid (16.5 mg) was dried under
vacuum and stored under nitrogen. It was found to be insoluble in all
available deuterated solvents; therefore, no NMR data could be
964, 2014 (νCO), 1882 (νCO), 1586 (ν ), 1532, 1469, 1434, 1418,
CO
−
1 1
239, 1168, 1094, 802, 744, 692 cm . H NMR (CD Cl ): δ 1.30,
2
2
.35 (d × 2, JHH = 6.8 Hz, 2 × 12H; IDip-CH ), 2.66 (sep, J = 6.9
3
HH
Hz, 4H; CHMe ), 5.64 (d, J = 15.7 Hz, 1H; Hβ), 6.47, 6.59 (d × 2,
2
HH
JHH = 8.4 Hz, 2 × 2H; SC H ), 6.98 (dd, J = 8.6, 1.8 Hz, 1H; bpy),
6
4
HH
7
+
.31 (s, 2H; NCH), 7.27−7.50 (m, 30H + 4H + 1H; C H + m-C H
6
5
6
3
bpy), 7.64 (t, J = 8.6 Hz, 2H; p-C H ), 7.77 (d, J = 8.6 Hz, 1H;
HH 6 3 HH
bpy), 7.95 (s, 1H; bpy), 8.02 (m, 2H; bpy), 8.96 (d, JHH = 5.6 Hz, 1H;
bpy), 9.43 (dt, JHH = 15.7 Hz, JHP = 1.8 Hz, 1H; Hα) ppm. 31P{ H}
NMR (CD Cl ): δ 18.9 (s, PPh ) ppm. MS (ES +ve): m/z (%) 1967
1
2
2
3
+
(
2) [M] . Anal. Calcd for C H AuClN O OsP ReS.CH Cl (M =
86 79 4 6 2 2 2 w
2
2
052.37, M = 1967.44 in absence of solvation): C, 50.9; H, 4.0; N,
w
recorded. IR (solid state): 1585 (ν ), 1485, 1435, 1098, 828 (νPF)
.7. Found: C, 50.6; H, 3.8; N, 2.8.
CO
−1
2.9
cm . TEM analysis of over 200 nanoparticles gave a size of 2.2 ± 0.2
nm. EDS confirmed the presence of palladium and ruthenium and
indicated the presence of sulfur, phosphorus, oxygen, and fluorine.
TGA: 38.4% surface units, 61.6% palladium and ruthenium
Au @[SC H CO Ru(dppm) ]PF (NP1). A solution of tetra-
6
4
2
2
6
chloroauric acid trihydrate (50.0 mg, 0.127 mmol) in methanol (10
mL) was added to a solution of 2 (149 mg, 0.064 mmol) in methanol
(
5 mL). The mixture was stirred for 30 min at room temperature and
then cooled to 4 °C. A fresh solution of sodium borohydride (40.4 mg,
.063 mmol) in water (3 mL) was then added dropwise. The solution
(
Pd15.1(SC H CO Ru(dppm) )PF ).
6 4 2 2 6
1
changed from yellow to dark brown, indicating the formation of
nanoparticles. The mixture was stirred for a further 3 h at 10 °C. The
supernatant was removed by centrifugation, and the brown solid was
washed with water (3 × 10 mL) and dichloromethane (10 mL) to
remove unattached surface units. The black nanoparticles (40 mg)
were dried under vacuum and stored under nitrogen. IR (solid state):
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.6b02409.
■
*
S
−1 1
1
575 (ν
), 1483, 1435, 1096, 999, 817 (ν ), 724, 685 cm ; H
CO
PF
NMR (dmso-d , 500 MHz): δ 4.44, 5.76 (m × 2, 2 × 2H; PCH P),
TEM, EDS, and TGA data for NP1−NP4, selected
NMR spectra, details of the Signer molecular mass
determination apparatus, and crystallographic data for 21
6
2
6
.59 (m, 4H; C H ), 7.08, 7.24, 7.37, 7.53, 7.70, 7.93 (m × 6, 36 H + 4
6 5
31 1
H; C H + C H ) ppm. P{ H} NMR (dmso-d , 500 MHz): δ −18.6,
6
5
6
4
6
−
3.2 (pseudoquartet × 2, JPP = 35.7 Hz; dppm) ppm. TEM: Analysis
(PDF)
of over 200 nanoparticles gave a size of 2.9 ± 0.2 nm. EDS confirmed
the presence of gold and ruthenium and indicated the presence of
Crystallographic data for 21 (CIF)
K
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
functionalized gold nanoparticles based on a combination of d- and f-
AUTHOR INFORMATION
■
elements. Inorg. Chem. 2014, 53, 1989−2005.
Corresponding Author
E-mail for J.D.E.T.W.-E.: j.wilton-ely@imperial.ac.uk.
(3) (a) Shibasaki, M.; Kanai, M.; Matsunaga, S.; Kumagai, N. Recent
*
progress in asymmetric bifunctional catalysis using multimetallic
systems. Acc. Chem. Res. 2009, 42, 1117−1127. (b) Weber, M.;
Klein, J. E. M. N.; Miehlich, B.; Frey, W.; Peters, R. Monomeric
ferrocene bis-imidazoline bis-palladacycles: Variation of Pd−Pd
distances by an interplay of metallophilic, dispersive, and coulombic
interactions. Organometallics 2013, 32, 5810−5817. (c) Sasai, H.;
Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. Basic character of rare earth
metal alkoxides. Utilization in catalytic carbon-carbon bond-forming
reactions and catalytic asymmetric nitroaldol reactions. J. Am. Chem.
Soc. 1992, 114, 4418−4420. (d) Ho, J. H. H.; Wagler, J.; Willis, A. C.;
Messerle, B. A. Synthesis and structures of homo- and heterobimetallic
rhodium(I) and/or iridium(I) complexes of binucleating bis(1-
pyrazolyl)methane ligands. Dalton Trans. 2011, 40, 11031−11042.
ORCID
James D. E. T. Wilton-Ely: 0000-0002-5192-3038
Author Contributions
These authors contributed equally.
§
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the Wellcome Trust for the award of a
Networks of Excellence award (M.N.W.). F.G.d.R. thanks the
Ministerio de Ciencia e Innovacion of Spain for provision of
́
funding (grants CTQ2009-12520 and CTQ2010-15292). K.A.J.
is grateful to the Ministry of Higher Education of Malaysia for a
scholarship on the IPTA Academic Training Scheme and for an
Academic Staff Scholarship from the Universiti Teknologi
MARA, Malaysia. We thank Dr. Ecaterina Ware for the TEM
and EDS data.
(
e) Lee, W.-Z.; Wang, T.-L.; Chang, H.-C.; Chen, Y.-T.; Kuo, T.-S. A
II
III
bioinspired Zn /Fe heterobimetallic catalyst for thia-michael
addition. Organometallics 2012, 31, 4106−4109. (f) Yamaguchi, Y.;
3
Yamanishi, K.; Kondo, M.; Tsukada, N. Synthesis of dinuclear (μ- η -
allyl)palladium(I) and -platinum(I) complexes supported by chelate-
bridging ligands. Organometallics 2013, 32, 4837−4842. (g) Wu, B.;
Gallucci, J. C.; Parquette, J. R.; RajanBabu, T. V. Bimetallic catalysis in
the highly enantioselective ring−opening reactions of aziridines. Chem.
Sci. 2014, 5, 1102−1117.
REFERENCES
(4) Jabri, E.; Carr, M. B.; Hausinger, R. P.; Karplus, P. A. The crystal
structure of urease from Klebsiella aerogenes. Science 1995, 268, 998−
■
(
1) (a) He, X.; Herranz, F.; Cheng, E. C.-C.; Vilar, R.; Yam, V. W.-W.
1
004.
Design, synthesis, photophysics, and anion-binding studies of
bis(dicyclohexylphosphino)methane-containing dinuclear gold(I) thi-
olate complexes with urea receptors. Chem. - Eur. J. 2010, 16, 9123−
(5) Low, P. J. Twists and turns: Studies of the complexes and
properties of bimetallic complexes featuring phenylene ethynylene and
related bridging ligands. Low, P. J. Coord. Chem. Rev. 2013, 257,
9
131. (b) Mendy, J. S.; Saeed, M. A.; Fronczek, F. R.; Powell, D. R.;
1
(
507−1532.
Hossain, Md. A. Anion recognition and sensing by a new macrocyclic
dinuclear copper(II) complex: A selective receptor for iodide. Inorg.
Chem. 2010, 49, 7223−7225. (c) Saeed, M. A.; Powell, D. R.; Hossain,
M. A. Fluorescent detection of phosphate anion by a highly selective
chemosensor in water. Tetrahedron Lett. 2010, 51, 4904−4907.
6) (a) Yaghi, O. M.; Li, H.; Eddaoudi, M.; O’Keeffe, M. Design and
synthesis of an exceptionally stable and highly porous metal-organic
framework. Nature 1999, 402, 276−279. (b) Long, J. R.; Yaghi, O. M.
The pervasive chemistry of metal−organic frameworks. Chem. Soc. Rev.
2
009, 38, 1213−1214 and subsequent reviews in the same issue.
(
́
2) (a) Livramento, J. B.; Toth, E.; Sour, A.; Borel, A.; Merbach, A.
E.; Ruloff, R. High relaxivity confined to a small molecular space: A
(c) Janiak, C.; Vieth, J. K. MOFs, MILs and more: concepts, properties
and applications for porous coordination networks (PCNs). New J.
Chem. 2010, 34, 2366−2388. (d) Janiak, C. Engineering coordination
polymers towards applications. Dalton Trans. 2003, 2781−2804.
(e) Arora, H.; Mukherjee, R. Coordination polymers using (2-
pyridyl)alkylamine-appended carboxylates: magnetic properties. New J.
Chem. 2010, 34, 2357−2365.
metallostar-based, potential MRI contrast agent. Angew. Chem., Int. Ed.
2
005, 44, 1480−1484. (b) Livramento, J. B.; Sour, A.; Borel, A.;
Merbach, A. E.; Toth, E. A starburst-shaped heterometallic compound
incorporating six densely packed Gd ions. Chem. - Eur. J. 2006, 12,
́
3+
9
89−1003. (c) Moriggi, L.; Aebischer, A.; Cannizzo, C.; Sour, A.;
Borel, A.; Bunzli, J.-C. G.; Helm, L. A ruthenium-based metallostar:
synthesis, sensitized luminescence and H relaxivity. Dalton Trans.
1
(7) (a) Toscani, A.; Heliovaara, E. K.; Hena, J. B.; White, A. J. P.;
̈
Wilton-Ely, J. D. E. T. Multimetallic alkenyl complexes bearing
macrocyclic dithiocarbamate ligands. Organometallics 2015, 34, 494−
2
009, 2088−2095. (d) Kasala, D.; Lin, T.-S.; Chen, C.-Y.; Liu, G.-C.;
2
‑
Kao, C.-L.; Cheng, T.-L.; Wang, Y.-M. [Gd(Try-TTDA)(H O)] : A
2
5
̀
05. (b) Lin, Y. H.; Duclaux, L.; Gonzalez de Rivera, F.; Thompson, A.
new MRI contrast agent for copper ion sensing. Dalton Trans. 2011,
L.; Wilton-Ely, J. D. E. T. The pentynoate ligand as a building block
4
0, 5018−5025. (e) Mieville, P.; Jaccard, H.; Reviriego, F.; Tripier, R.;
for multimetallic systems. Eur. J. Inorg. Chem. 2014, 2014, 2065−2072.
Helm, L. Synthesis, complexation and NMR relaxation properties of
3+
(c) Hurtubise, V. L.; McArdle, J. M.; Naeem, S.; Toscani, A.; White, A.
Gd complexes of Mes(DO3A) . Dalton Trans. 2011, 40, 4260−4267.
3
J. P.; Long, N. J.; Wilton-Ely, J. D. E. T. Multimetallic complexes and
functionalized nanoparticles based on unsymmetrical dithiocarbamate
ligands with allyl and propargyl functionality. Inorg. Chem. 2014, 53,
11740−11748. (d) Naeem, S.; Ribes, A.; White, A. J. P.; Haque, M. N.;
Holt, K. B.; Wilton-Ely, J. D. E. T. Multimetallic complexes and
functionalized nanoparticles based on oxygen-and nitrogen-donor
combinations. Inorg. Chem. 2013, 52, 4700−4713. (e) Lin, Y. H.;
Leung, N. H.; Holt, K. B.; Thompson, A. L.; Wilton-Ely, J. D. E. T.
Bimetallic complexes based on carboxylate and xanthate ligands:
Synthesis and electrochemical investigations. Dalton Trans. 2009,
(
f) Dehaen, G.; Verwilst, P.; Eliseeva, S. V.; Laurent, S.; Vander Elst,
L.; Muller, R. N.; De Borggraeve, W. M.; Binnemans, K.; Parac-Vogt,
T. N. A heterobimetallic ruthenium−gadolinium complex as a
potential agent for bimodal imaging. Inorg. Chem. 2011, 50, 10005−
1
0014. (g) Dehaen, G.; Eliseeva, S. V.; Kimpe, K.; Laurent, S.; Vander
Elst, L.; Muller, R. N.; Dehaen, W.; Binnemans, K.; Parac-Vogt, T. N.
A self-assembled complex with a titanium(IV) catecholate core as a
potential bimodal contrast agent. Chem. - Eur. J. 2012, 18, 293−302.
(
h) Verwilst, P.; Eliseeva, S. V.; Vander Elst, L.; Burtea, C.; Laurent, S.;
Petoud, S.; Muller, R. N.; Parac-Vogt, T. N.; De Borggraeve, W. M. A
tripodal ruthenium−gadolinium metallostar as a potential α β integrin
̀
7891−7901. (f) Sherwood, R.; Gonzalez de Rivera, F.; Wan, J. H.;
v
3
specific bimodal imaging contrast agent. Inorg. Chem. 2012, 51, 6405−
Zhang, Q.; White, A. J. P.; Rossell, O.; Hogarth, G.; Wilton-Ely, J. D.
E. T. Multimetallic complexes based on a diphosphine-dithiocarbamate
“Janus” ligand. Inorg. Chem. 2015, 54, 4222−4230.
6
411. (i) Dehaen, G.; Eliseeva, S. V.; Verwilst, P.; Laurent, S.; Vander
Elst, L.; Muller, R. N.; De Borggraeve, W.; Binnemans, K.; Parac-Vogt,
T. N. Tetranuclear d-f metallostars: Synthesis, relaxometric, and
luminescent properties. Inorg. Chem. 2012, 51, 8775−8783. (j) Sung,
S.; Holmes, H.; Wainwright, L.; Toscani, A.; Stasiuk, G. J.; White, A. J.
P.; Bell, J. D.; Wilton-Ely, J. D. E. T. Multimetallic complexes and
̈
(8) (a) Packheiser, R.; Ecorchard, P.; Ruffer, T.; Walfort, B.; Lang, H.
Mixed heterotri- to heteropentametallic transition-metal complexes:
Synthesis, characterization and electrochemical behavior. Eur. J. Inorg.
Chem. 2008, 2008, 4152−4165. (b) Packheiser, R.; Jakob, A.;
L
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Ecorchard, P.; Walfort, B.; Lang, H. Diphenylphosphinoferrocene
gold(I) acetylides: Synthesis of heterotri-and heterotetrametallic
transition metal complexes. Organometallics 2008, 27, 1214−1226.
2010, 39, 4080−4089. (j) Bedford, R. B.; Hill, A. F.; Jones, C.; White,
A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T. Co-ordinative activation
of phosphaalkynes: methyl neopentylidene phosphorane complexes of
t
(
c) Packheiser, R.; Ecorchard, P.; Ru
̈
ffer, T.; Lang, H. Mixed-
ruthenium(II); crystal structure of [Ru(MePCHBu )Cl(I)(CO)-
transition-metal acetylides: Synthesis and characterization of com-
plexes with up to six different transition metals connected by carbon-
rich bridging units. Chem. - Eur. J. 2008, 14, 4948−4960.
(PPh ) ]. J. Chem. Soc., Dalton Trans. 1997, 139−140.
3
2
(10) (a) Guerrini, L.; Pazos, E.; Penas, C.; Vazquez, M. E.;
Mascarenas, J. L.; Alvarez-Puebla, R. A. Highly sensitive SERS
quantification of the oncogenic protein c-Jun in cellular extracts. J.
Am. Chem. Soc. 2013, 135, 10314−10317. (b) Rowland, C. E.; Belai,
N.; Knope, K. E.; Cahill, C. L. Hydrothermal synthesis of disulfide-
containing uranyl compounds: in situ ligand synthesis versus direct
assembly. Cryst. Growth Des. 2010, 10, 1390−1398.
(
d) Packheiser, R.; Ecorchard, P.; Walfort, B.; Lang, H. Hetero-
trimetallic and heterotetrametallic transition metal complexes. J.
Organomet. Chem. 2008, 693, 933−946. (e) Packheiser, R.;
Ecorchard, P.; Ruffer, T.; Lohan, M.; Brauer, B.; Justaud, F.;
̈
̈
Lapinte, C.; Lang, H. Heterotrimetallic M−M′−M″ transition metal
complexes based on 1,3,5-triethynylbenzene: Synthesis, solid state
structure, and electrochemical and UV−Vis characterization. EPR
analysis of the in situ generated associated radical cations. Organo-
metallics 2008, 27, 3444−3457. (f) Packheiser, R.; Ecorchard, P.;
̈
(11) (a) Signer, R. Uber eine Aban
̈
derung der Molekulargewichtbes-
ber hochpolymere
timmungsmethode nach Barger. 34. Mitteilung u
̈
Verbindungen. Annalen 1930, 478, 246. (b) Clark, E. P. Signer method
for determining molecular weights. Ind. Eng. Chem., Anal. Ed. 1941, 13,
820. (c) Patel, P.; Naeem, S.; White, A. J. P.; Wilton-Ely, J. D. E. T.
Synthesis and reactivity of dialkyldithiophosphate complexes of
ruthenium(II). RSC Adv. 2012, 2, 999−1008.
Ru
based on unsymmetrical platinum (II) bis-acetylides. Organometallics
P.; Klaib, S.; del Villar,
̈
ffer, T.; Lang, H. Heteromultimetallic transition metal complexes
2
008, 27, 3534−3546. (g) Lang, H.; Zoufala,
́
A.; Rheinwald, G. Synthesis of di-, tri- and tetranuclear platinum(II)
(12) (a) Wilton-Ely, J. D. E. T.; Schier, A.; Mitzel, N. W.;
Schmidbaur, H. Structural diversity in gold(I) complexes of 4-
sulfanylbenzoic acid. J. Chem. Soc., Dalton Trans. 2001, 1058−1062.
(b) Wilton-Ely, J. D. E. T.; Ehlich, H.; Schier, A.; Schmidbaur, H. The
effect of hard and soft donors on structural motifs in (isocyanide)-
gold(I) complexes. Helv. Chim. Acta 2001, 84, 3216−3232.
(13) For an overview of alkenyl chemistry of ruthenium(II), see:
(a) Whittlesey, M. K. In Comprehensive Organometallic Chemistry III;
Crabtree, R. H., Mingos, D. M. P., Bruce, M. I.; Eds.; Elsevier: Oxford,
U.K., 2006; Vol. 6. (b) Hill, A. F. In Comprehensive Organometallic
Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G.; Eds.;
Pergamon Press: Oxford, U.K., 1995; Vol. 7.
and copper(I) acetylide complexes. J. Organomet. Chem. 2007, 692,
4
168−4176. (h) Packheiser, R.; Lang, H. The first heterohexametallic
transition-metal complex. Eur. J. Inorg. Chem. 2007, 2007, 3786−3788.
i) Packheiser, R.; Walfort, B.; Lang, H. Heterobi-and heterotrimetallic
(
transition metal complexes with carbon-rich bridging units. Organo-
metallics 2006, 25, 4579−4587. (j) Maurer, J.; Sarkar, B.; Kaim, W.;
̌
Winter, R. F.; Zaìlis, S. Towards new organometallic wires:
Tetraruthenium complexes bridged by phenylenevinylene and vinyl-
pyridine ligands. Chem. - Eur. J. 2007, 13, 10257−10272.
(
k) Koutsantonis, G. A.; Low, P. J.; Mackenzie, C. F. R.; Skelton, B.
W.; Yufit, D. S. Coordinating Tectons: Bimetallic Complexes from
Bipyridyl Terminated Group 8 Alkynyl Complexes. Organometallics
(14) Prepared using 2,1,3-benzothiadiazole (BTD) in place of 2,1,3-
benzoselenadiazole (BSD) following the procedure reported by:
Harris, M. C. J.; Hill, A. F. Reactions of ruthenium complex
[RuHCl(CO)(BSD)(PPh ) ] (BSD = benzo-2,1,3-selenadiazole)
2
(
014, 33, 4911−4922.
9) (a) Wilton-Ely, J. D. E. T.; Solanki, D.; Hogarth, G.
Multifunctional dithiocarbamates as ligands towards the rational
synthesis of polymetallic arrays: An example based on a piperizine-
derived dithiocarbamate. Eur. J. Inorg. Chem. 2005, 2005, 4027−4030.
3
2
with alkynes. Organometallics 1991, 10, 3903−3906.
(15) Hill, A. F.; Wilton-Ely, J. D. E. T. Alkenyl and alkynyl complexes
of osmium(II) derived from [OsH(Cl)(CO)(BTD)(PPh ) ] (BTD =
(
b) Wilton-Ely, J. D. E. T.; Solanki, D.; Knight, E. R.; Holt, K. B.;
3
2
Thompson, A. L.; Hogarth, G. Multimetallic assemblies using
piperazine-based dithiocarbamate building blocks. Inorg. Chem. 2008,
2,1,3-benzothiadiazole). J. Chem. Soc., Dalton Trans. 1998, 3501−3510.
(16) (a) Santos, A.; Lopez, J.; Montoya, J.; Noheda, P.; Romero, A.;
́
4
7, 9642−9653. (c) Macgregor, M. J.; Hogarth, G.; Thompson, A. L.;
Echavarren, A. M. Synthesis of new ruthenium (II) carbonyl hydrido,
alkenyl, and alkynyl complexes with chelating diphosphines. Organo-
metallics 1994, 13, 3605−3615. (b) Maurer, J.; Winter, R. F.; Sarkar,
Wilton-Ely, J. D. E. T. Multimetallic arrays: Symmetrical and
unsymmetrical bi-, tri-, and tetrametallic organometallic complexes of
ruthenium(II) and osmium(II). Organometallics 2009, 28, 197−208.
̌
B.; Fiedler, J.; Zaìlis, S. Bridge dominated oxidation of a diruthenium 1,
(
d) Knight, E. R.; Cowley, A. R.; Hogarth, G.; Wilton-Ely, J. D. E. T.
3-divinylphenylene complex. Chem. Commun. 2004, 1900−1901.
Bifunctional dithiocarbamates: a bridge between coordination
(c) Maurer, J.; Linseis, M.; Sarkar, B.; Schwederski, B.; Niemeyer,
chemistry and nanoscale materials. Dalton Trans. 2009, 607−609.
̌
M.; Kaim, W.; Zaìlis, S.; Anson, C.; Zabel, M.; Winter, R. F.
(
e) Knight, E. R.; Leung, N. H.; Lin, Y. H.; Cowley, A. R.; Watkin, D.
Ruthenium complexes with vinyl, styryl, and vinylpyrenyl ligands: A
case of non-innocence in organometallic chemistry. J. Am. Chem. Soc.
2008, 130, 259−268. (d) Scheerer, S.; Rotthowe, N.; Abdel-Rahman,
O. S.; He, X.; Rigaut, S.; Kvapilova, H.; Zalis, S.; Winter, R. F. Vinyl
ruthenium-modified biphenyl and 2, 2′-bipyridines. Inorg. Chem. 2015,
54, 3387−3402.
J.; Thompson, A. L.; Hogarth, G.; Wilton-Ely, J. D. E. T. Multimetallic
arrays: Symmetrical bi-, tri- and tetrametallic complexes based on the
group 10 metals and the functionalisation of gold nanoparticles with
nickel-phosphine surface units. Dalton Trans. 2009, 3688−3697.
(
f) Knight, E. R.; Leung, N. H.; Thompson, A. L.; Hogarth, G.;
Wilton-Ely, J. D. E. T. Multimetallic arrays: Bi-, tri-, tetra-, and
hexametallic complexes based on gold(I) and gold(III) and the surface
functionalization of gold nanoparticles with transition metals. Inorg.
Chem. 2009, 48, 3866−3874. (g) Oliver, K.; White, A. J. P.; Hogarth,
G.; Wilton-Ely, J. D. E. T. Multimetallic complexes of group 10 and 11
metals based on polydentate dithiocarbamate ligands. Dalton Trans.
(17) (a) Moragues, M. E.; Toscani, A.; Sancenon
́
, F.; Martínez-
Manez, R.; White, A. J. P.; Wilton-Ely, J. D. E. T. A chromo-
̃
fluorogenic synthetic “canary” for CO detection based on a
pyrenylvinyl ruthenium(II) complex. J. Am. Chem. Soc. 2014, 136,
11930−11933. (b) Toscani, A.; Marín-Hernan
́
dez, C.; Moragues, M.
ez, R.;
E.; Sancenon, F.; Dingwall, P.; Brown, N. J.; Martínez-Man
́
̃
2
011, 40, 5852−5864. (h) Hogarth, G.; Rainford-Brent, E.-J. C.-R. C.
White, A. J. P.; Wilton-Ely, J. D. E. T. Ruthenium(II) and osmium(II)
vinyl complexes as highly sensitive and selective chromogenic and
fluorogenic probes for the sensing of carbon monoxide in air. Chem. -
R.; Kabir, S. E.; Richards, I.; Wilton-Ely, J. D. E. T.; Zhang, Q.
Functionalised dithiocarbamate complexes: Synthesis and molecular
structures of 2-diethylaminoethyl and 3-dimethylaminopropyl dithio-
carbamate complexes [M{S CN(CH CH NEt ) } ] and [M{S CN-
Eur. J. 2015, 21, 14529−14538. (c) Marín-Hernan
́
dez, C.; Toscani, A.;
ez, R. Chromo-
Sancenon, F.; Wilton-Ely, J. D. E. T.; Martínez-Man
́
̃
2
2
2
2
2
n
2
(
CH CH CH NMe ) } ] (n = 2, M = Ni, Cu, Zn, Pd;n = 3, M = Co).
fluorogenic probes for carbon monoxide detection. Chem. Commun.
2016, 52, 5902−5911.
(18) (a) Cannadine, J. C.; Hill, A. F.; White, A. J. P.; Williams, D. J.;
Wilton-Ely, J. D. E. T. Organometallic macrocycle chemistry. 5. σ-
Vinyl and σ-aryl complexes of ruthenium(II) ligated by 1,4,7-
2
2
2
2 2 n
Inorg. Chim. Acta 2009, 362, 2020−2026. (i) Naeem, S.; Ogilvie, E.;
White, A. J. P.; Hogarth, G.; Wilton-Ely, J. D. E. T. The
functionalisation of ruthenium(II) and osmium(II) alkenyl complexes
with amine- and alkoxy-terminated dithiocarbamates. Dalton Trans.
M
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
trithiacyclononane: X-ray crystal structure of [Ru(CHCH )(CO)-
Beer, P. D. Anion sensing porphyrin functionalized nanoparticles. J.
Inorg. Organomet. Polym. Mater. 2008, 18, 32−40.
(23) (a) Lewis, D. J.; Pikramenou, Z. Lanthanide-coated gold
nanoparticles for biomedical applications. Coord. Chem. Rev. 2014,
273-274, 213−225. (b) Beloglazkina, E. K.; Majouga, A. G.;
Romashkina, R. B.; Zyk, N. V.; Zefirov, N. S. Gold nanoparticles
modified with coordination compounds of metals: synthesis and
2
(
PPh )([9]aneS )]PF ·2CH Cl . Organometallics 1996, 15, 5409−
3
3
6
2
2
5
415. (c) Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E.
T. Polyazolyl chelate chemistry 8. Organometallic dihydrido bis-
pyrazol-1-yl) borato complexes of ruthenium(II). Organometallics
998, 17, 4249−4258. (d) Wilton-Ely, J. D. E. T.; Pogorzelec, P. J.;
(
1
Honarkhah, S. J.; Tocher, D. A. Mixed-donor ligands: Pyrrolecarbal-
dehyde and pyrrolecarbothioaldehyde σ-organyl complexes of
ruthenium (II) and osmium (II). Organometallics 2005, 24, 2862−
̀
application. Russ. Chem. Rev. 2012, 81, 65−90. (c) Roy, S.; Pericas, M.
A. Functionalized nanoparticles as catalysts for enantioselective
processes. Org. Biomol. Chem. 2009, 7, 2669−2677. (d) Wilton-Ely,
J. D. E. T. The surface functionalisation of gold nanoparticles with
metal complexes. Dalton Trans. 2008, 25−29.
2
874. (e) Wilton-Ely, J. D. E. T.; Honarkhah, S. J.; Wang, M.; Tocher,
D. A. σ-Organyl complexes of ruthenium and osmium supported by a
mixed-donor ligand. Dalton Trans. 2005, 1930−1939. (f) Wilton-Ely, J.
D. E. T.; Wang, M.; Honarkhah, S. J.; Tocher, D. A. Ruthenium
hydride and vinyl complexes supported by nitrogen−oxygen mixed-
donor ligands. Inorg. Chim. Acta 2005, 358, 3218−3226. (g) Wilton-
Ely, J. D. E. T.; Wang, M.; Benoit, D.; Tocher, D. A. Spectroscopic,
Structural and Theoretical Investigation of Alkenyl Ruthenium
Complexes Supported by Sulfur−Nitrogen Mixed-Donor Ligands.
Eur. J. Inorg. Chem. 2006, 2006, 3068−3078. (h) Cowley, A. R.;
Hector, A. L.; Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J.
D. E. T. Synthesis and reactions of five-coordinate mono-and binuclear
thiocarbonyl-alkenyl and thioacyl complexes of ruthenium(II).
Organometallics 2007, 26, 6114−6125. (i) Cowley, A. R.; Hector, A.
L.; Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T.
Synthesis and reactions of five-coordinate mono-and binuclear
thiocarbonyl-alkenyl and thioacyl complexes of ruthenium(II).
Organometallics 2007, 26, 6114−6125. (j) Hill, A. F.; Jones, C.;
White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T.
Mercuriophosphaalkene-P complexes: Crystal structure of [Ru{P(
̀
(24) (a) Gonzalez de Rivera, F.; Angurell, I.; Rossell, O.; Seco, M.;
Llorca, J. Organometallic surface functionalization of gold nano-
particles. J. Organomet. Chem. 2012, 715, 13−18. (b) Friederici, M.;
Angurell, I.; Rossell, O.; Seco, M.; Divins, N. J.; Llorca, J. Facile
synthesis of palladium nanoparticles protected with alkanethiolates
functionalized with organometallic fragments. Organometallics 2012,
3
1, 722−728. (c) Friederici, M.; Angurell, I.; Rossell, O.; Seco, M.;
Muller, G. Exploring palladium nanoparticles protected with
alkanethiolates functionalized with organometallic units as potential
catalysts for sequential reactions. J. Mol. Catal. A: Chem. 2013, 376, 7−
1
(
2.
25) (a) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman,
R. Synthesis of thiol-derivatised gold nanoparticles in a two-phase
liquid−liquid system. J. Chem. Soc., Chem. Commun. 1994, 0, 801−802.
(b) Brust, M.; Fink, J.; Bethell, D.; Schiffrin, D. J.; Kiely, C. Synthesis
and reactions of functionalised gold nanoparticles. J. Chem. Soc., Chem.
Commun. 1995, 1655−1656.
t
̈ ̈ ̈
(26) Suoranta, T.; Niemela, M.; Peramaki, P. Comparison of
CHBu )HgC H Fe(η-C H )}Cl (CO)(PPh ) ]. J. Chem. Soc., Dalton
5
4
5
5
2
3 2
digestion methods for the determination of ruthenium in catalyst
Trans. 1998, 1419−1420. (k) Bedford, R. B.; Hill, A. F.; Jones, C.;
White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T. Phosphaalkyne
hydrometalation: Synthesis and reactivity of the complexes [Ru(P
CHCMe )Cl(CA)(PPh ) ](A= O, S). Organometallics 1998, 17,
materials. Talanta 2014, 119, 425−429.
(27) (a) Turkevich, J.; Stevenson, P. C.; Hillier, J. A study of the
nucleation and growth processes in the synthesis of colloidal gold.
Discuss. Faraday Soc. 1951, 11, 55−75. (b) Grabar, K. C.; Freeman, R.
G.; Hommer, M. B.; Natan, M. J. Preparation and characterization of
Au colloid monolayers. Anal. Chem. 1995, 67, 735−743. (c) Kimling,
J.; Mier, M.; Okenve, B.; Kotaidis, V.; Ballot, H.; Plech, A. Turkevich
method for gold nanoparticle synthesis revisited. J. Phys. Chem. B
3
3 2
4
(
744−4753.
19) Jia, G.; Wu, W. F.; Yeung, R. C. Y.; Xia, H. P. Dimeric and
polymeric ruthenium complexes with Ru-vinyl linkages. J. Organomet.
Chem. 1997, 539, 53−59.
(
20) (a) Aucott, S. M.; Milton, H. L.; Robertson, S. D.; Slawin, A. M.
2
(
006, 110, 15700−15707.
Z.; Woollins, J. D. The preparation and characterisation of bimetallic
iridium(II) complexes containing derivatised bridging naphthalene-
28) (a) Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.;
Kornberg, R. D. Structure of a thiol monolayer-protected gold
1
2
,8-disulfur or 4,5-dithiolato acephenanthrylene ligands. Dalton Trans.
004, 3347−3352. (b) Lang, R. F.; Ju, T. D.; Kiss, G.; Hoff, C. D.;
nanoparticle at 1.1 Å resolution. Science 2007, 318, 430−433.
(b) Heaven, M. W.; Dass, A.; White, P. S.; Holt, K. M.; Murray, R.
Bryan, J. C.; Kubas, G. J. Oxidative addition of disulfides to the
W. Crystal structure of the gold nanoparticle [N(C H ) ]-
8
17
4
complex W(CO) (phen)(EtCN). Synthesis, structure, and reactivity
3
[Au (SCH CH Ph) ]. J. Am. Chem. Soc. 2008, 130, 3754−3755.
25
2
2
18
t
of W(CO) (phen)(SR) (R = Ph, Me, CH Ph, Bu; phen = 1,10-
2
2
2
(29) (a) Akola, J.; Walter, M.; Whetten, R. L.; Hak
Gro
Soc. 2008, 130, 3756−3757. (b) Jiang, D.; Luo, W.; Tiago, M. L.; Dai,
S. In search of a structural model for a thiolate-protected Au cluster.
̈
kinen, H.;
Phenanthroline) coordinatively unsaturated complexes of tungsten(II)
that reversibly bind CO and other ligands. Inorg. Chem. 1994, 33,
̈
nbeck, H. On the structure of thiolate-protected Au . J. Am. Chem.
25
3
899−3907. (c) Jessop, P. G.; Rettig, S. J.; Lee, C.-L.; James, B. R.
3
8
Hydrido thiolato and thiolato complexes of ruthenium (II) carbonyl
phosphines. Inorg. Chem. 1991, 30, 4617−4627. (d) Markham, S. J.;
Chung, Y. L.; Branum, G. D.; Blake, D. M. Reactions of iridium (I)
compounds with oxidized derivatives of organic disulfides and with
thionyl chloride. J. Organomet. Chem. 1976, 107, 121−127.
J. Phys. Chem. C 2008, 112, 13905−13910. (c) Qian, H.; Eckenhoff, W.
T.; Zhu, Y.; Pintauer, T.; Jin, R. Total structure determination of
thiolate-protected Au38 nanoparticles. J. Am. Chem. Soc. 2010, 132,
8
280−8281. (d) Rojas-Cervellera, V.; Giralt, E.; Rovira, C. Staple
motifs, initial steps in the formation of thiolate-protected gold
(
21) (a) Nuzzo, R. G.; Allara, D. L. Adsorption of bifunctional
organic disulfides on gold surfaces. J. Am. Chem. Soc. 1983, 105, 4481−
483. (b) Nuzzo, R. G.; Fusco, F. A.; Allara, D. L. Spontaneously
nanoparticles: how do they form? Inorg. Chem. 2012, 51, 11422−
1
1429. (e) Naeem, S.; Serapian, S. A.; Toscani, A.; White, A. J. P.;
4
Hogarth, G.; Wilton-Ely, J. D. E. T. Ring-closing metathesis and
nanoparticle formation based on diallyldithiocarbamate complexes of
gold(I): Synthetic, structural, and computational studies. Inorg. Chem.
2014, 53, 2404−2416.
organized molecular assemblies. 3. Preparation and properties of
solution adsorbed monolayers of organic disulfides on gold surfaces. J.
Am. Chem. Soc. 1987, 109, 2358−2368. (c) Chinwangso, P.; Jamison,
A. C.; Lee, T. R. Multidentate adsorbates for self-assembled monolayer
films. Acc. Chem. Res. 2011, 44, 511−519.
(30) (a) Schmid, G.; Pfeil, R.; Boese, R.; Bandermann, F.; Meyer, S.;
Calis, G. H. M.; Van der Velden, J. W. A. Au [P(C H ) ] Cl - ein
55
6
5
3
12
6
(
22) (a) Daniel, M.-C.; Astruc, D. Gold nanoparticles: assembly,
̈ ̈
Goldcluster ungewohnlicher Große. Chem. Ber. 1981, 114, 3634−
supramolecular chemistry, quantum-size-related properties, and
applications toward biology, catalysis, and nanotechnology. Chem.
Rev. 2004, 104, 293−346. (b) Beer, P. D.; Cormode, D. P.; Davis, J. J.
Zinc metalloporphyrin-functionalised nanoparticle anion sensors.
Chem. Commun. 2004, 414−415. (c) Cormode, D. P.; Davis, J. J.;
3642. (b) Schmid, G. Large clusters and colloids. Metals in the
embryonic state. Chem. Rev. 1992, 92, 1709−1727. (c) Weare, W. W.;
Reed, S. M.; Warner, M. G.; Hutchison, J. E. Improved synthesis of
small (dcore ≈ 1.5 nm) phosphine-stabilized gold nanoparticles. J. Am.
Chem. Soc. 2000, 122, 12890−12891.
N
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(
31) (a) Lu, X. M.; Yavuz, M. S.; Tuan, H. Y.; Korgel, B. A.; Xia, Y.
complexes containing Group 5 donor ligands: Crystal and molecular
N. Ultrathin gold nanowires can be obtained by reducing polymeric
strands of oleylamine−AuCl complexes formed via aurophilic
interaction. J. Am. Chem. Soc. 2008, 130, 8900−8901. (b) Ma, Y.;
Zeng, J.; Li, W.; McKiernan, M.; Xie, Z.; Xia, Y. Seed-mediated
synthesis of truncated gold decahedrons with a AuCl/oleylamine
complex as precursor. Adv. Mater. 2010, 22, 1930−1934. (c) Gomez,
S.; Philippot, K.; Colliere, V.; Chaudret, B.; Senocq, F.; Lecante, P.
Gold nanoparticles from self-assembledgold(I) amine precursors.
Chem. Commun. 2000, 1945−1946. (d) Leff, D. V.; Brandt, L.;
Heath, J. R. Synthesis and characterization of hydrophobic, organically-
soluble gold nanocrystals functionalized with primary amines.
Langmuir 1996, 12, 4723−4730.
structures of Au(C C F )(PPh ). Aust. J. Chem. 1984, 37, 1163−1170.
2
6
5
3
(42) Bailey, J. Tricyclohexylphosphinegold compounds. J. Inorg. Nucl.
Chem. 1973, 35, 1921−1924.
(43) Schmidbaur, H.; Wohlleben, A.; Wagner, F.; Orama, O.;
Huttner, G. Gold-Komplexe von Diphosphinomethanen, I. Synthese
und Kristallstruktur zweikerniger Gold (I)-Verbindungen. Chem. Ber.
1
(
977, 110, 1748−1754.
44) Hill, D. T.; Girard, G. R.; McCabe, F. L.; Johnson, R. K.; Stupik,
P. D.; Zhang, J. H.; Reiff, W. M.; Eggleston, D. S. [μ-1,1′-
Bis(diphenylphosphino)ferrocene]bis(chlorogold): Synthesis, iron-57
and gold-197 Moessbauer spectroscopy, x-ray crystal structure, and
antitumor activity. Inorg. Chem. 1989, 28, 3529−3533.
(45) de Fremont, P.; Scott, N. M.; Stevens, E. D.; Nolan, S. P.
(
32) (a) Selvam, T.; Chi, K.-M. Synthesis of hydrophobic gold
Synthesis and structural characterization of N-heterocyclic carbene
nanoclusters: growth mechanism study, luminescence property and
gold (I) complexes. Organometallics 2005, 24, 2411−2418.
catalytic application. J. Nanopart. Res. 2011, 13, 1769−1780.
(46) (a) Sullivan, B. P.; Meyer, T. J. Comparisons of the physical and
(
b) Selvam, T.; Chi, K.-M.; Chiang, C.-M. Organic-phase synthesis
chemical properties of isomeric pairs. Photochemical, thermal and
electrochemical cis-trans isomerizations of M(Ph PCH PPh ) Cl (M
of self-assembled gold nanosheets. J. Nanopart. Res. 2011, 13, 3275−
286.
33) Tuchscherer, A.; Schaarschmidt, D.; Schulze, S.; Hietschold, M.;
2
2
2
2
2
3
(
II
II
=
Ru , Os ). Inorg. Chem. 1982, 21, 1037−1040. (b) Keller, A.;
Jasionka, B.; Glowiak, T.; Ershov, A.; Matusiak, R. Cyclic oxycarbene
and vinylidene complexes of ruthenium with (P∧P) and (N∧N) type
ligands. Inorg. Chim. Acta 2003, 344, 49−60.
Lang, H. Simple and efficient: Gold nanoparticles from triphenyl-
phosphane gold (I) carboxylates without addition of any further
stabilizing and reducing agent. Inorg. Chem. Commun. 2011, 14, 676−
(47) (a) Hill, A. F.; Melling, R. P. Diyne coordination chemistry:
6
(
78.
34) (a) Vignolle, J.; Tilley, T. D. N-Heterocyclic carbene-stabilized
Reactions of [RuClH(CO)(PPh ) ] with diphenylbutadiyne and
3
3
bis(phenylethynyl)mercury. J. Organomet. Chem. 1990, 396, C22−
C24. (b) Alcock, N. W.; Hill, A. F.; Melling, R. P. Polyazolyl chelate
chemistry 3. (Sigma-organyl)[tris(pyrazol-1-yl)borato]ruthenium
complexes. Organometallics 1991, 10, 3898−3903.
gold nanoparticles and their assembly into 3D superlattices. Chem.
Commun. 2009, 7230−7232. (b) Collinson, J.-M.; Wilton-Ely, J. D. E.
T.; Díez-Gonzalez, S. Reusable and highly active supported copper
́
(
1
I)−NHC catalysts for Click chemistry. Chem. Commun. 2013, 49,
1358−11360.
35) Landgraf, G. In Gold-Progress in Chemistry, Biochemistry and
Technology; Schmidbaur, H., Ed.; Wiley: Chichester, U.K., 1999.
36) (a) Corbierre, M. K.; Lennox, R. B. Preparation of thiol-capped
(
(
gold nanoparticles by chemical reduction of soluble Au (I)-thiolates.
Chem. Mater. 2005, 17, 5691−5696. (b) Goulet, P. J. G.; Lennox, R. B.
New insights into Brust− Schiffrin metal nanoparticle synthesis. J. Am.
Chem. Soc. 2010, 132, 9582−9584. (c) Simpson, C. A.; Farrow, C. L.;
Tian, P.; Billinge, S. J. L.; Huffman, B. J.; Harkness, K. M.; Cliffel, D. E.
Tiopronin gold nanoparticle precursor forms aurophilic ring tetramer.
Inorg. Chem. 2010, 49, 10858−10866. (d) Corbierre, M. K.; Beerens,
J.; Lennox, R. B. Gold nanoparticles generated by electron beam
lithography of gold(I)-thiolate thin films. Chem. Mater. 2005, 17,
5
774−5779. (e) Corbierre, M. K.; Beerens, J.; Beauvais, J.; Lennox, R.
B. Uniform one-dimensional arrays of tunable gold nanoparticles with
tunable interparticle distances. Chem. Mater. 2006, 18, 2628−2631.
(
37) (a) Nakamoto, M.; Yamamoto, M.; Fukusumi, M. Thermolysis
of gold(I) thiolate complexes producing novel gold nanoparticles
passivated by alkyl groups. Chem. Commun. 2002, 1622−1623.
(
b) Nakamoto, M.; Kashiwagi, Y.; Yamamoto, M. Synthesis and size
regulation of gold nanoparticles by controlled thermolysis of
ammonium gold(I) thiolate in the absence or presence of amines.
Inorg. Chim. Acta 2005, 358, 4229−4236.
(
38) Schmidbaur, H.; Schier, A. A briefing on aurophilicity. Chem.
Soc. Rev. 2008, 37, 1931−1951.
39) (a) Nomiya, K.; Noguchi, R.; Sakurai, T. Synthesis and Crystal
Structure of a Water-soluble Gold(I) Complex, {K [Au(mba) ]}
2
(
3
2
Formed by 2-Mercaptobenzoic Acid (H mba), with Aurophilic
2
Interaction in the Solid-State. Chem. Lett. 2000, 29, 274−275.
(
b) Watase, S.; Nakamoto, M.; Kitamura, T.; Kanehisa, N.; Kai, Y.;
Yanagida, S. Solid-state luminescence and crystal structures of novel
gold(I) benzenethiolate complexes. J. Chem. Soc., Dalton Trans. 2000,
3
(
585−3590.
40) Quiros, I.; Yamada, M.; Kubo, K.; Mizutani, J.; Kurihara, M.;
Nishihara, H. Preparation of alkanethiolate-protected palladium
nanoparticles and their size dependence on synthetic conditions.
Langmuir 2002, 18, 1413−1418.
(
41) Bruce, M. I.; Horn, E.; Matisons, J. G.; Snow, M. R. Chemistry
of the Group 1B metals. XVII. Preparation of some gold(I) acetylide
O
DOI: 10.1021/acs.inorgchem.6b02409
Inorg. Chem. XXXX, XXX, XXX−XXX