Multimetallic complexes of group 10 and 11 metals based on polydentate dithiocarbamate ligands

Article abstract of DOI:10.1039/c0dt01745k

The ligands KS₂CN(Bz)CH₂CH₂N(Bz)CS ₂K (K₂L¹), N(CH₂CH ₂N(Me)CS₂Na)₃ (Na₃L²), and the new chelates {(CH₂CH₂)NCS₂Na} ₃ (Na₃L³) and {CH₂CH ₂N(CS₂Na)CH₂CH₂CH ₂NCS₂Na}₂ (Na₄L⁴), react with the gold(I) complexes [ClAu(PR₃)] (R = Me, Ph, Cy) and [ClAu(IDip)] to yield di-, tri-and tetragold compounds. Larger metal units can also be coordinated by the longer, flexible linker, K₂L¹. Thus two equivalents of cis-[PtCl₂(PEt₃)₂] react with K₂L¹ in the presence of NH₄PF ₆ to yield the bimetallic complex [L¹{Pt(PEt ₃)₂}₂](PF₆)₂. The compounds [NiCl₂(dppp)] and [MCl₂(dppf)] (M = Ni, Pd, Pt; dppp = 1,3-bis(diphenylphosphino)propane, dppf = 1,1'-bis(diphenylphosphino) ferrocene) also yield the dications, [L¹{Ni(dppp)}₂] ²⁺ and [L¹{Ni(dppf)}₂]²⁺ in an analogous fashion. In the same manner, reaction between [(L′₂) (AuCl)₂] (L′₂ = dppm, dppf; dppm = bis(diphenylphosphino)methane) and KS₂CN(Bz)CH₂CH ₂N(Bz)CS₂K yield [L¹{Au₂(L′ ₂)}₂]. The molecular structures of [L¹{M(dppf)} ₂](PF₆)₂ (M = Ni, Pd) and [L ¹{Au(PR₃)}₂] (R = Me, Ph) are reported.

Full text of DOI:10.1039/c0dt01745k

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Volume 40 | Number 22 | 14 June 2011 | Pages 5797–6056
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COVER ARTICLE
Wilton-Ely et al.
Multimetallic complexes of group 10
and 11 metals based on polydentate
dithiocarbamate ligands
1477-9226(2011)40:22;1-W

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PAPER
Multimetallic complexes of group 10 and 11 metals based on polydentate
dithiocarbamate ligands†
Katie Oliver,a Andrew J. P. White,a Graeme Hogarthb and James D. E. T. Wilton-Ely*a
Received 12th December 2010, Accepted 10th February 2011
DOI: 10.1039/c0dt01745k
The ligands KS2CN(Bz)CH2CH2N(Bz)CS2K (K2L1), N(CH2CH2N(Me)CS2Na)3 (Na3L2), and the new
chelates {(CH2CH2)NCS2Na}3 (Na3L3) and {CH2CH2N(CS2Na)CH2CH2CH2NCS2Na}2 (Na4L4),
react with the gold(I) complexes [ClAu(PR3)] (R = Me, Ph, Cy) and [ClAu(IDip)] to yield di-, tri-and
tetragold compounds. Larger metal units can also be coordinated by the longer, flexible linker, K2L1.
Thus two equivalents of cis-[PtCl2(PEt3)2] react with K2L1 in the presence of NH4PF6 to yield the
bimetallic complex [L1{Pt(PEt3)2}2](PF6)2. The compounds [NiCl2(dppp)] and [MCl2(dppf)] (M = Ni,
Pd, Pt; dppp = 1,3-bis(diphenylphosphino)propane, dppf = 1,1’-bis(diphenylphosphino)ferrocene) also
yield the dications, [L1{Ni(dppp)}2]2+ and [L1{Ni(dppf)}2]2+ in an analogous fashion. In the same
manner, reaction between [(L¢2)(AuCl)2] (L¢2 = dppm, dppf; dppm = bis(diphenylphosphino)methane)
and KS2CN(Bz)CH2CH2N(Bz)CS2K yield [L1{Au2(L¢2)}2]. The molecular structures of
[L1{M(dppf)}2](PF6)2 (M = Ni, Pd) and [L1{Au(PR3)}2] (R = Me, Ph) are reported.
(K2L1), has already been reported, offering the same number of
bonds (9) between the linked metals as the piperazine-derived,
Introduction
[S2CNC4H8NCS2]2-. K2L1 has been investigated mainly in terms
of the ligand itself7 rather than its complexation behaviour.8 This
ligand is slightly unusual in that it has two different substituents
on the nitrogen which contrasts with the symmetrical nature of
most dithiocarbamate ligands. One literature report discusses the
supramolecular contacts between the alkali metal salts of [L1]2-,7
while another explores the linking of molybdenum oxo units.8a
The remaining paper focuses on the analysis of trace heavy
metals using the ligand but does not report full spectroscopic
The area of multimetallic compounds occupies a position at the
interface between coordination and materials chemistry.1 The
structural and redox properties of these materials make them
suitable for a range of applications, such as sensing or catalysis.
Metal Organic Frameworks (MOFs) are perhaps the most high-
profile examples of these compounds.2 The incorporation of
different metal centres into the same molecular framework allows
the properties of the overall material to be tailored through the
choice of these metals (catalysis, electrochemistry, cytotoxicity,
luminescence etc.). A recent growth area within this sphere is
multisite catalysis.1a–c
The linking of transition metal units can be achieved in many
ways. Bifunctional spacers such as diamines (e.g., 4,4¢-bipyridine),3
diisocyanide,3 dicarboxylates (MOFs),2 bis(dithiocarbamates)4,5
and dixanthates6 have all been employed to link metal centres.
This is a field in which we have successfully employed bifunctional
dithiocarbamate ligands5 and, more recently, spacers with both
carboxylate and xanthate functionality.6
data for the (presumably) homoleptic complexes formed.8b
A
tris(dithiocarbamate) ligand, employed recently in the synthesis
of tin compounds,9 is N(CH2CH2N(Me)CS2Na)3 (Na3L2). This
species offers three chelation sites as well as a high degree of flexi-
bility, leading to the formation of [(L2)2(SnPh2)3] ‘sandwich’ com-
plexes. While the cyclic amines, triazacyclonane10 and cyclam11 are
well known as polydentate chelates, until now their transformation
into dithiocarbamate ligands (Na3L3 and Na4L4) has been over-
looked. While the degree of flexibility varies significantly between
the ligands employed in this work, they are related by the presence
of an ethylene bridge between the dithiocarbamate units (Chart 1).
This study is the first to explore the coordination chemistry
of the [L1]2- and [L2]3- ligands with late transition metals, while
ligands [L3]3- and [L4]4- are completely new and offer a more rigid
framework for the construction of multimetallic compounds.
This recent work on linking metals has, to date, been lim-
ited to rigid bis(dithiocarbamate) units based on piperazine.
Thus, our attention turned to more flexible linkers and those
offering more than two chelation sites. In the former category,
a suitable bis(dithiocarbamate), [S2CN(Bz)CH2CH2N(Bz)CS2]2-
aDepartment of Chemistry, Imperial College London, South Kensington
Campus, London, SW7 2AZ, UK. E-mail: j.wilton-ely@imperial.ac.uk
Results and discussion
bDepartment of Chemistry, University College London, 20 Gordon Street,
London, WC1H 0AJ, UK
Complexes with a bridging bis(dithiocarbamate) ligand
† Electronic supplementary information (ESI) available. CCDC reference
numbers 764405–764408. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c0dt01745k
Although the ligand [S2CN(Bz)CH2CH2N(Bz)CS2]2- has been
employed before, it is generally not isolated and is prepared
5852 | Dalton Trans., 2011, 40, 5852–5864
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Chart 1 The poly(dithiocarbamate) ligands used in this research.
in situ from the diamine and carbon disulfide in the presence
bis(dithiocarbamate) ligand, along with aromatic resonances
around 7.47 ppm. The CS2 unit of the dithiocarbamate was
identified in the 13C NMR spectrum as a singlet at 209.7 ppm. The
overall formulation of [L1{Pt(PEt3)2}2](PF6)2 (1) was confirmed by
a molecular ion in the electrospray mass spectrum at m/z = 1250
and good agreement of elemental analysis with calculated values
(Scheme 1).
of base. However, for greater control and ease of use, the
potassium salt of the bis(dithiocarbamate) ligand, KS2CN(Bz)-
CH2CH2N(Bz)CS2K, (K2L1), was prepared as a solid from the
reaction of HN(Bz)CH2CH2N(Bz)H and CS2 with KOH in water.
Crystals of the product precipitated from ethanol solution on
◦
1
cooling overnight at - 20 C. H NMR analysis of the ligand
revealed two singlets at 2.89 and 4.04 ppm for the ethylene
bridge and the benzyl methylene groups, respectively. These peaks
proved the most diagnostic in the metal complexes prepared
here. Aromatic resonances were also observed between 5.69 and
5.94 ppm. The potassium salt was found to be sufficiently soluble
in methanol for the reactions described.
In order to introduce metal units with diphosphines, the
series [L1{M(dppf)}2](PF6)2 (M = Ni, 2; M = Pd, 3; M = Pt,
4) was prepared in moderate to good yields using the same
1
experimental procedure employed for 1 (Scheme 1). H NMR
spectroscopic data associated with the bridging ligand were similar
to those observed for compound 1. Four resonances arising from
the substituted cyclopentadienyl rings were identified between
4.37 and 4.73 ppm indicating the subtle inequivalence of the
phosphine units caused by the unsymmetrical dithiocarbamate
ligand. This observation was reinforced by the AB system again
observed in the 31P NMR spectra of 2–4, mirroring that in
compound 1. These spectroscopic data can be compared to those
for the symmetrical piperazine-based bis(dithiocarbamate) com-
plex [(Et3P)2Pt(S2CNC4H8NCS2)Pt(PEt3)2](PF6)2,5e which dis-
plays only a singlet resonance in the 31P NMR spectrum.
In order to examine this inequivalence further, a variable
A dichloromethane solution of cis-[PtCl2(PEt3)2] was treated
with half an equivalent of K2L1 in the presence of NH4PF6 to yield
a colourless product after work up. Retention of the triethylphos-
phine ligands bonded directly to platinum was confirmed by two
new doublet resonances in the 31P NMR spectrum at 6.0 and
6.5 ppm, showing mutual coupling of 21.5 Hz. The resonances
both displayed coupling to 195Pt of 3127 and 3108 Hz, respectively.
1
The phosphine ligands gave rise to multiplets in the H NMR
spectrum at 1.28 and 2.18 ppm, while peaks at 4.20 and 5.16 ppm
were assigned to the NCH2CH2N and CH2Ph units of the bridging
Scheme 1 Routes to bi-, tetra-and hexametallic species. M = Ni (2), Pd (3), Pt (4); R = Ph (6), Me (7); X = CH2 (9), X = C5H4FeC5H4 (10). IDip =
1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene.
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◦
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Fig. 1 Molecular structure of the dication in 2. Selected bond distances (A) and angles ( ): Ni(1)–P(48) 2.2070(7), Ni(1)–P(25) 2.2119(7),
Ni(1)–S(1) 2.2143(7), Ni(1)–S(3) 2.2162(7), Ni(2)–P(84) 2.2007(7), Ni(2)–S(10) 2.2100(7), Ni(2)–P(61) 2.2213(7), Ni(2)–S(9) 2.2230(7), S(1)–C(2) 1.727(3),
C(2)–N(4) 1.316(3), C(2)–S(3) 1.711(2), N(7)–C(8) 1.314(3), C(8)–S(9) 1.713(2), C(8)–S(10) 1.718(2), S(1)–Ni(1)–S(3) 78.41(2), S(10)–Ni(2)–S(9) 78.27(2),
S(3)–C(2)–S(1) 109.07(13), S(9)–C(8)–S(10) 109.31(13).
temperature NMR experiment was conducted. A solution of 1
in deuteroaceton◦itrile (the compound is not soluble in d8-toluene)
was heated to 75 C while 31P NMR spectra were recorded at 10 ◦C
intervals. Although the chemical shift of the doublets moved closer
together, complete coalescence was not observed, indicating that
the rotational barrier of the C–N bond could not be overcome
within the temperature range investigated. Previous studies have
examined this rotational barrier using NMR methods and the
estimation is between 65 and 88 kJ mol-1 for this process at 298 K.12
The compound [L1{Ni(dppp)}2](PF6)2 (5) was prepared from
two equivalents of the 1,3-bis(diphenylphosphino)propane pre-
cursor, [NiCl2(dppp)], and K2L1 in the presence of NH4PF6.
Surprisingly, given the AB system observed for the previous
complexes, this compound gave rise only to a singlet in the 31P
NMR spectrum at room temperature. The spectral data for this
compound were otherwise comparable to those for 2–4, with the
Suitable crystals were chosen and structural studies undertaken
(Fig. 1 and Fig. 2).
The flexible nature of the bis(dithiocarbamate) ligand is clear
from its twisted appearance, allowing the metal centres to ap-
proach relatively closely. For example, the distance between palla-
˚
˚
dium centres in 3 is 6.9 A, compared to 10.8 A in the more rigid
[(dppf)Pd(S2CNC4H8NCS2)Pd(dppf)](PF6)2.5e The close proxim-
ity of the metal units is particularly significant in relation to the
potential of this linker for use in two-site catalysis. The restricted
rotation around the C–N bond explained by the contribution of
the thioureide resonance form ensures that the benzyl group is
orientated towards one phosphorus centre rendering it distinct
from the other phosphorus bonded to the same metal centre. This
effect is clearly retained in solution (31P NMR). Further discussion
of the crystal structures appears in the Structural Section.
The affinity of monovalent gold for sulfur is only matched by its
preference for phosphorus13a and cyanide donors13b and the num-
ber of known gold dithiocarbamate compounds is significant.4
Dithiocarbamate complexes of monovalent gold, such as the series
studied crystallographically, [(R3P)Au(S2CNEt2)] (R = Et,14a Cy,14b
Ph,14c p-C6H4OMe14d), typically show coordination principally
through only one sulfur donor. Recent work has revealed that
spectacularly intricate and complex supramolecular architectures
can result from gold(I) assemblies bridged by dithiocarbamate
ligands. Using the piperazine-based bis(dithiocarbamate) ligand,
KS2CNC4H8NCS2K, Yam, Li, Yu and co-workers prepared the
tetrametallic complex [{(dppm)Au2}2(S2CNC4H8NCS2)](PF6)2,15a
which exists in the solid state as an intriguing chiral, cyclic,
supramolecular structure in which 16 gold units are held to-
gether by aurophilic interactions. The same researchers have
recently reported fascinating arrangements using another flexible
bis(dithiocarbamate) ligand to prepare an Au12 cluster with D2
1
exception of the resonances in the H NMR spectrum assigned
to the propylene bridge at 2.23 and 2.71 ppm. A solution of
compound 5 in CD2Cl2 was cooled to - 90 ◦C while 31P NMR
measurements were carried out. At - 50 ◦C the original singlet
resonance split into two resonances. The chemical shift values of
the peaks proceeded to move further apart over the next 40 ◦C
decrease in temperature, however, no well-defined AB system was
observed even at - 90 ◦C. Although the continuation of the
experiment at lower temperatures was not possible (due to the
freezing point of the solvent and the insolubility of 5 in other
solvents), it was clear that, at low temperature, inequivalence
between the phosphorus nuclei could be observed. However, the
reason why compound 5 with dppp ligands should behave so
differently to the other comparable compounds is not clear.
Single crystals of 2 and 3 were grown by slow diffusion of ethanol
into a dichloromethane solution of the complex in each case.
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Fig. 2 Molecular structure of the dication in 3. Selected bond distances (A) and angles ( ): Pd(1)–P(48) 2.2923(6), Pd(1)–P(25) 2.3018(6), Pd(1)–S(3)
2.3348(6), Pd(1)–S(1) 2.3516(6), Pd(2)–P(84) 2.2906(7), Pd(2)–P(61) 2.3110(6), Pd(2)–S(10) 2.3347(6), Pd(2)–S(9) 2.3445(7), S(1)–C(2) 1.728(2),
C(2)–N(4) 1.313(3), C(2)–S(3) 1.719(2), N(7)–C(8) 1.323(3), C(8)–S(10) 1.709(2), C(8)–S(9) 1.723(2), S(3)–Pd(1)–S(1) 75.07(2), S(10)–Pd(2)–S(9) 74.98(2),
S(3)–C(2)–S(1) 111.88(14), S(10)–C(8)–S(9) 112.15(13).
symmetry15b and an unprecedented Au36 arrangement directed by
aurophilic interactions.15c
The fact that subtle differences in the nature of the bridging
ligands in these systems can cause radically different assem-
blies to organise15 led to our exploration of the coordina-
tion and structural chemistry of gold(I) units bridged by the
[S2CN(Bz)CH2CH2N(Bz)CS2]2-, [L1]2-, ligand.
The habitual starting point of gold(I) chemistry is the complex
[ClAu(PPh3)], which underwent clean and rapid reaction with
K2L1 to yield the pale yellow product [L1{Au(PPh3)}2] (6) in
62% yield. A new singlet in the 31P NMR spectrum at 36.1 ppm
indicated the formation of a new product, while the presence of
the bridging ligand was betrayed by singlet resonances at 4.26
(NCH2CH2N) and 5.25 (PhCH2) ppm in the 1H NMR spectrum,
upfield from the aromatic features. The electrospray mass spec-
trum revealed a molecular ion at m/z = 1309. The microcrystalline
nature of the compound allowed single crystals to be grown easily
from slow diffusion of ethanol into a dichloromethane solution of
the compound. A structural study was undertaken using one of
the crystals obtained (Fig. 3).
The study revealed the dithiocarbamate ligand to be bonded in
an anisobidentate mode with the Au(1)–S(3) distance measuring
◦
˚
Fig. 3 Molecular structure of 6. Selected bond distances (A) and angles ( ): Au(1)–P(13) 2.2483(10), Au(1)–S(1) 2.3290(10), Au(1)–S(3) 3.0756(10),
S(1)–C(2) 1.747(4), C(2)–N(4) 1.343(5), C(2)–S(3) 1.695(4), P(13)–Au(1)–S(1) 177.86(3), C(2)–S(1)–Au(1) 97.67(14). Atom labels with an ‘A’ after the
number are related to their counterparts without the letter by a centre of symmetry situated in the middle of the C(5)–C(5A) bond.
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Fig. 4 Molecular structure of 7. Selected bond distances (A) and angles ( ): Au(1)–P(13) 2.2440(6), Au(1)–S(1) 2.3233(5), Au(1)–S(3) 3.1196(5), S(1)–C(2)
1.7436(19), C(2)–N(4) 1.349(2), C(2)–S(3) 1.6922(19), P(13)–Au(1)–S(1) 175.07(2), C(2)–S(1)–Au(1) 99.07(6). Atom labels with an ‘A’ after the number
are related to their counterparts without the letter by a centre of symmetry situated in the middle of the C(12)–C(12A) bond.
˚
3.0756(10) A, well below the sum of the van der Waals radii of
emerged as alternative electron-rich donors to phosphines in
gold chemistry.18 Thus, two equivalents of the 1,3-bis(2,6-
diisopropylphenyl)imidazolin-2-ylidine complex, [AuCl(IDip)],
were treated with the bis(dithiocarbamate) ligand to yield
16a
˚
3.46 A for gold and sulfur. Further details are discussed in
the Structural Section. No significant Au ◊ ◊ ◊ Au intermolecular
contacts were observed, despite the relatively open environment at
the gold(I) centres. The steric profile of ligated phosphine ligands
often plays a crucial role in the formation of aurophilic contacts
between formally closed-shell d10 gold(I) centres.16b Thus, the
smallest readily available phosphine was introduced into the sys-
tem in place of PPh3, through use of [ClAu(PMe3)], which formed
[L1{Au(PMe3)}2] (7) under the same experimental conditions used
for 7. Almost identical 1H NMR spectroscopic data were obtained
apart from the features relating to the trimethylphosphine ligand
(doublet at 1.64 ppm, JHP = 10.8 Hz). Single crystals of 7 were
obtained as before and structural analysis undertaken by X-ray
diffraction (Fig. 4).
Despite the significantly smaller steric profile of the PMe3 lig-
and, no intermolecular Au ◊ ◊ ◊ Au contacts were observed, though
p-stacking was evident between the benzyl groups. This is perhaps
surprising given the relatively open region of space around the gold
centres. Either the orientation of the molecules needed for efficient
packing must preclude the formation of such interactions or an
electronic effect due to the more remote sulfur donor is responsible.
The structures of the series [(R3P)Au(S2CNEt2)] (R = Et, Cy, Ph, p-
C6H4OMe),14 do not show any intermolecular aurophilic contacts.
The trimethylphosphine complex [(L)Au(S2CNC10H25O4)] (L =
PMe3), bearing an aza-15-crown-5 dithiocarbamate ligand, does
not show Au ◊ ◊ ◊ Au contacts, while the isocyanide derivative (L =
1
[L1{Au(IDip)}2] (8). H NMR analysis revealed two doublets at
1.25 and 1.40 ppm and a septet at 2.66 ppm (mutual coupling
of JHH = 6.8 Hz) for the isopropyl groups while the meta and
para resonances of the NHC ligand were observed at 7.35 and
7.53 ppm (JHH = 7.8 Hz). The remaining peak for the HC CH unit
was obscured by the aromatic resonances of the benzyl groups. A
molecular ion in the electrospray mass spectrum (+ ve mode) at
m/z = 1562 combined with elemental analysis data confirmed the
overall formulation.
The 2005 report describing the fascinating supramolecular
arrangement of [(dppm)Au2(S2CNC4H8NCS2)Au2(dppm)](PF6)2
into a chiral Au16 ring held together by aurophilic interactions14a
prompted our investigation of the reaction of [(dppm)(AuCl)2]
with K2L1 in the presence of NH4PF6. The resulting product gave
1
rise to a resonance at 3.79 ppm for the PCH2P units in the H
NMR spectrum as well as two further peaks for the bridging
ligand at 4.42 (NCH2CH2N) and 5.25 (PhCH2) ppm. These, along
with other spectroscopic and analytical data, pointed towards
the formulation of the product being [L1{Au2(dppm)}2](PF6)2
(9), as shown in Scheme 1. The very broad resonance in the
31P NMR spectrum suggested a degree of inequivalence for the
phosphorus nuclei. Unfortunately, suitable single crystals could
not be obtained in order to probe the structure in the solid
state. The dppf analogue, [L1{Au2(dppf)}2](PF6)2 (10), was also
prepared in the same manner. Spectroscopic data were found
to be similar apart from the resonances associated with the
cyclopentadienyl groups of the diphosphine ligand, which were
observed as two broadened resonances at 4.46 and 4.54 ppm.
Attempts to grow suitable crystals of this complex for X-ray
diffraction were unsuccessful.
16c
˚
CNC6H3Me2-2,6) displays an Au ◊ ◊ ◊ Au distance of 3.565 A.
The authors do not comment on whether they believe the
difference to be steric or electronic in nature and this would
be difficult to determine without recourse to a computational
investigation.
In parallel with their introduction to ruthenium-based
catalysis,17 N-heterocyclic carbenes (NHCs) have steadily
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Scheme 2 Routes to tri-and tetrametallic species using Na3L2, Na3L3, Na4L4. L = PPh3 (11, 15, 19), PCy3 (12, 16, 20), PMe3 (13, 17, 21), IDip (14, 18);
IDip = (2,6-diisopropylphenyl)imidazol-2-ylidene.
In the light of recent reports of Au12 and Au36 assemblies
being formed from the addition of [AuCl(tht)] (tht = tetrahy-
drothiophene) to flexible bis(dithiocarbamate) compounds.14b,c
The reaction of [AuCl(tht)] with K2L1 was investigated. An initial
colour change to yellow was observed on adding two equivalents of
the gold complex to the ligand. However, the precipitate formed
was found to be insoluble in all common deuterated solvents.
This suggested that an extended polymeric arrangement had been
formed rather than a discrete Aun unit in this case. Adding four
equivalents of gold complex to one of the ligand yielded a similarly
insoluble product.
(13) was also prepared to provide further options for structural
characterisation.
Three equivalents of the compound [AuCl(IDip)] (IDip = 1,3-
bis(2,6-diisopropylphenyl)imidazol-2-ylidene) reacted with Na3L2
to yield [L2{Au(IDip)}3] (14). The doublet methyl resonances of
the IDip ligand at 1.24 and 1.37 ppm (JHH = 6.8 Hz) were found
to integrate to four times the value for the NMe resonance at
3.11 ppm, while the resonance for the isopropyl protons appeared
at the same chemical shift as those of one of the NCH2 units,
leading to a multiplet at 2.64 ppm. Further resonances (aromatic)
for the IDip ligand were observed at 7.34, 7.54 (showing mutual
coupling of 7.7 Hz) and 7.25 ppm (HC CH) alongside the
remaining triplet for the NCH2 protons of the ethylene arms at 3.72
(JHH = 7.1 Hz) ppm. The formulation (Scheme 2) was supported by
mass spectrometry (m/z = 2169) and good agreement of elemental
analysis with calculated values.
Although the coordination chemistry of [L1]2- and [L2]3- have
been explored sporadically before, there is a notable lack of rigid
poly(dithiocarbamate) ligands. Thus, it was decided to investigate
the possibility of employing cyclic amines as precursors for the
generation of such species. After unsuccessful attempts using KOH
and NEt3, deprotonation of the hydrochloride salt of triazacy-
clononane was achieved with sodium hydride. Subsequent treat-
ment by carbon disulfide yielded the new tris(dithiocarbamate)
ligand, {(CH2CH2)NCS2Na}3 (Na3L3). This was generated in situ
and used directly for subsequent additions to metal complexes. The
more rigid, cyclic nature of the central motif differs substantially
from that of Na3L2. Treatment of three equivalents of [AuCl(PPh3)]
with Na3L3 led to a colourless product, which gave rise to a
new peak at 36.0 ppm in the 31P NMR spectrum. A single
new resonance was also seen in the 1H NMR spectrum at
4.49 ppm for the equivalent protons of the triazacyclononane
ring. This is consistent with the assumed flat nature of the
ring due to the characteristic planarity of the R2NCS2 unit in
Complexes with tris-and tetrakis(dithiocarbamate) ligands
In
a
modification of the published procedure,9 tris[2-
(methylamino)ethyl]amine was treated sequentially with sodium
hydride and carbon disulfide to yield the tris(dithiocarbamate)
ligand, N(CH2CH2N(Me)CS2Na)3 (Na3L2). This was prepared in
situ for addition to the metal complexes. Reaction with three
equivalents of [AuCl(PPh3)] led to the formation of a new
compound, as demonstrated by the appearance of a new singlet in
1
the 31P NMR spectrum at 36.0 ppm. H NMR analysis revealed
a singlet for the methyl protons at 3.50 ppm and two triplet
resonances for the protons of the ethylene bridges at 3.03 and
4.07 ppm, showing a mutual coupling of 7.2 Hz. The overall
formulation was confirmed by a molecular ion in the mass
spectrum at m/z = 1792 to be [L2{Au(PPh3)}3] (11). This was
further supported by good agreement of elemental analysis with
calculated values. In order to explore the effect of changing the
steric bulk of the metal unit, [L2{Au(PCy3)}3] (12) was prepared
in the same manner. Spectroscopic data were found to be similar
apart from the features pertaining to the tricyclohexylphosphine
ligand, such as multiplets in the 1H NMR spectrum between 1.28
and 2.08 ppm. The trimethylphosphine complex [L2{Au(PMe3)}3]
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 5852–5864 | 5857
©

dithiocarbamate compounds. Integration of this peak with the
resonances attributed to the triphenylphosphine protons between
7.50 and 7.68 ppm confirmed the internal stoichiometry of
the complex. The overall formulation was confirmed as being
[L3{Au(PPh3)}3] (15) from mass spectrometry and elemental
analysis data (Scheme 2). Although space around the central
tris(dithiocarbamate) core is limited, it was decided to explore the
effect of a bulkier gold-phosphine unit. Reaction of [AuCl(PCy3)]
with Na3L3 yielded another colourless product, [L3{Au(PCy3)}3]
(16). Again, a new singlet at 55.5 ppm was observed in the
environments. In addition to typical resonances for the PPh3
protons, quintet and triplet resonances were observed in the
1H NMR spectrum for the protons of the propylene bridge,
at 2.37 and 4.18 (mutual coupling of JHH = 6.9 Hz) ppm,
respectively. In contrast, the plane of symmetry in the molecule
ensured that the protons of the ethylene bridges appeared as
a singlet at 4.38 ppm. Although no distinct molecular ion was
observed in the Fast Atom Bombardment (FAB) mass spectrum,
a diagnostic fragmentation for [M - PPh3]+ was noted at m/z =
2075. In a similar manner, the tricyclohexylphosphine analogue
[L4{Au(PCy3)}4] (20) was prepared and was found to display
similar spectroscopic data apart from the presence of multiplets
between 1.25 and 2.07 ppm (cyclohexyl CH2 protons) in the
1H NMR spectrum. In contrast, [L4{Au(PMe3)}4] (21), prepared
by the same route, showed broader resonances for all of the
ring protons, mirroring the behaviour seen in the other PMe3
complexes, 13 and 17.
1
31P NMR spectrum, while H NMR analysis revealed a singlet
in a similar position to that found in 15 for the ring protons
alongside five multiplets between 1.33 and 2.06 ppm assigned to
the cyclohexyl protons. The starting material with the smallest
commercially available phosphine is [AuCl(PMe3)], which reacts
in a similar fashion with Na3L3 to provide [L3{Au(PMe3)}3] (17) in
reasonable yield. A doublet was observed for the methyl protons of
the phosphine at 1.63 (JHH = 10.6 Hz) ppm, however, the protons
of the triazacyclononane ring appeared instead as a pair of broad
singlets at 4.27 and 4.46 ppm. This inequivalence may be connected
to the relative size of the AuPMe3 unit compared to the bulkier
AuPPh3 or AuPCy3 units and the effect of this on molecular
Attempts to introduce more bulky units led to a mixture
of products. This is likely due to the limited space available
to accommodate more sterically demanding metal units (with
diphosphines etc.) at all dithiocarbamate moieties simultaneously.
Work is currently underway to examine ligands Na3L3 and Na4L4
as the basis for extended systems.
1
motion in solution. In the H NMR spectrum of the complex
[L3{Au(IDip)}3] (18), the appearance of the NCH2 resonance
reverts to a sharp singlet (3.97 ppm), while the overall formulation
follows from FAB mass spectrum and elemental analysis data.
Cyclam has been used to complex many metals within the
macrocycle,19 however, it has not been investigated as a precursor
for dithiocarbamate ligands despite it being a secondary amine.
This may have been due to the inadequacy, for this amine, of
bases such as KOH or NEt3 typically used in the formation of
dithiocarbamate ligands. However, it was considered that depro-
tonation could be achieved if the right base were employed. Thus,
treatment of cyclam with sodium hydride in dry tetrahydrofuran
followed by addition of carbon disulfide generated a solution
of the tetrakis(dithiocarbamate) ligand Na4L4. This solution
reacted readily with [ClAu(PPh3)] to yield [L4{Au(PPh3)}4] (19)
in reasonable yield. A singlet resonance at 36.1 ppm in the 31P
NMR spectrum indicated equivalence for the four phosphine
Structural Section
The four crystal structures reported here allow
a use-
ful comparison of the structural features of the coordi-
nated [S2CN(Bz)CH2CH2N(Bz)CS2]2- ligand. The compounds
[(dppf)M(S2CNC4H8NCS2)M(dppf)](PF6)2 (M = Ni, Pd)5e can
be compared directly to compounds 2 and 3 (Table 1). The
clearest difference between these literature complexes and the
ones reported here is the flexibility of the ligand. The ethylene
bridge allows independent rotation of the dithiocarbamate units,
while the piperazine bis(dithiocarbamate) ligand is essentially
limited to boat14a and chair5a,d,e conformations. While the com-
pounds [(dppf)M(S2CNC4H8NCS2)M(dppf)]2+ display unsym-
metrical chelation to the piperazine bis(dithiocarbamate) ligand, 2
and 3 have only subtle differences in their M–C and C–S distances
˚
Table 1 Distances in A and angles in degrees
Complex
M–S
C–S
C–N
S–M–S
S–C–S
[L1{Ni(dppf)}2]2+(2)
2.2143(7)
2.2162(7)
2.2100(7)
2.2230(7)
2.212(1)
1.727(3)
1.711(2)
1.713(2)
1.718(2)
1.718(4)
1.783(4)
1.728(2)
1.719(2)
1.709(2)
1.723(2)
1.725(5)
1.728(5)
1.747(4)
1.695(4)
1.7436(19)
1.6922(19)
1.743(4)
1.690(5)
1.316(3)
1.314(3)
78.41(2)
78.27(2)
109.07(13)
109.31(13)
[(dppf)Ni(S2CNC4H8NCS2)Ni(dppf)]2+
1.311(5)
79.91(4)
110.7(2)
5e
2.272(1)
[L1{Pd(dppf)}2]2+ (3)
2.3348(6)
2.3516(6)
2.3347(6)
2.3445(7)
2.337(1)
1.313(3)
1.323(3)
75.07(2)
74.98(2)
111.88(14)
112.15(13)
[(dppf)Pd(S2CNC4H8NCS2)Pd(dppf)]2+
1.322(6)
1.343(5)
1.349(2)
1.320(5)
75.18(5)
112.1(3)
121.8(2)
121.12(11)
121.0(2)
5e
2.358(1)
[L1{Au(PPh3)}2] (6)
[L1{Au(PMe3)}2] (7)
[(Ph3P)Au(S2CNC4H8)] 20
2.3290(10)
3.0756(10)
2.3233(5)
3.1196(5)
2.3334(11)
3.0440(13)
—
—
—
5858 | Dalton Trans., 2011, 40, 5852–5864
This journal is
The Royal Society of Chemistry 2011
©

(Table 1). The S–C–S angle of the ligands are very similar in both
pairs of nickel and palladium compounds, however the S–M–S
bite angles found in 2 [78.41(2)◦ and 78.27(2)◦] are smaller than
that of 79.91(4)◦ found in [(dppf)Ni(S2CNC4H8NCS2)Ni(dppf)]2+.
The corresponding values for the palladium compounds are
comparable. The C–N bond length is similar in all group 10
complexes and, as has often been noted,4 displays some multiple
bond character reflecting the contribution of the thioureide form
of the dithiocarbamate ligand.
methods: cis-[PtCl2(PEt3)2],21 [NiCl2(dppp)],22 [MCl2(dppf)] (M =
Ni,23 Pd,24 Pt25), [ClAu(PPh3)],26 [ClAu(PMe3)],27 [ClAu(IDip)],28
[dppm(AuCl)2],29 [dppf(AuCl)2],30 [ClAu(PCy3)]31 and triazacy-
clononane HCl salt.32 The petroleum ether used is the frac-
tion boiling between 40–60 ◦C. Electrospray and Fast Atom
Bombardment (FAB) mass data were obtained using Micro-
mass LCT Premier and Autospec Q instruments, respectively.
Infrared data were obtained directly from solid samples using a
Perkin Elmer Spectrum 100 FT-IR spectrometer. Characteristic
triphenylphosphine-associated infrared data are not reported.
NMR spectroscopy was performed at 25 ◦C using a Bruker
AV400 spectrometer while variable temperature experiments were
conducted with a Bruker DRX400 spectrometer in CD3CN (1) or
CD2Cl2 (5). All couplings are in Hertz. Resonances in the 31P NMR
spectrum due to the hexafluorophosphate counteranion were
observed but are not included below. All couplings are in Hertz
and 31P NMR spectra are proton decoupled. Elemental analysis
data were obtained from London Metropolitan University. The
procedures given provide materials of sufficient purity for synthetic
and spectroscopic purposes. Samples were recrystallised from a
mixture of dichloromethane and ethanol for elemental analysis.
Solvates were confirmed by integration of the 1H NMR spectrum.
Both digold complexes show an almost linear P–Au–S arrange-
ment [177.86(3)◦ for 6 and 175.07(2)◦ for 7]. In comparison,
the piperidine dithiocarbamate complex [(Ph3P)Au(S2CNC4H8)]20
displays an angle of 173.82(4)◦. The Au–S bond lengths in 6
and 7 also correlate well to the corresponding distance in the
˚
literature compound [2.333(1) A], though it should be noted that
there is some disorder in 7 affecting the coordination of the
Au(PMe3) unit (see Supporting Information). As found also in
[(Ph3P)Au(S2CNC4H8)], the distance between the gold(I) centre
and the other, more distant, sulfur atom falls within the sum of
15
˚
the van der Waals radii for gold and sulfur (3.46 A ), leading
to an anisobidentate coordination mode. The modest deviation
from linearity in the P–Au–S linkage may also be traced, in part,
to this interaction. The weaker association of this sulfur donor is
reflected in the greater multiple bond character and hence shorter
KS2CN(Bz)CH2CH2N(Bz)CS2K (K2L1)
˚
bond length for the associated C–S distance [1.695(4) A for 6 and
˚
1.6922(19) A for 7].
An aqueous (30 mL) solution of N,N¢-Dibenzylethylenediamine
(1.00 g, 4.161 mmol) and carbon disulfide (0.75 mL, 950 mg,
12.501 mmol) was treated dropwise with an aqueous solution
(20 mL) of KOH leading to a yellow solution. The reaction was
stirred for 2 h and then left to stand overnight and the resulting
colourless crystals were filtered and washed with cold water
(30 mL) and dried. Yield: 1660 mg (85%). IR: 1631, 1603, 1493,
1451, 1381, 1364, 1307, 1292, 1192, 1145, 1072, 1030, 972, 763,
Conclusion
The ligand [S2CN(Bz)CH2CH2N(Bz)CS2]2-, [L1]2-, has been shown
to act as an excellent linker with which to join transition
metal units. The unsymmetrical nature of the bis(dithiocarbamate)
ligand is observed in the spectroscopic data, while the flexibility
of the ligand is clear from the structural studies. Conventional
bidentate coordination is observed in the group 10 compounds,
while an anisobidentate arrangement is found in the gold(I) species.
The high level of crystallinity found in the complexes, permitted
the coordination modes and conformation of the ligand to be
examined in four cases. The coordination chemistry of a similarly
flexible tris(dithiocarbamate), [L2]3-, has been extended to include
gold(I) complexes. Perhaps most significantly, two new ligand
systems based on cyclic tris-and tetrakis(dithiocarbamate) have
been prepared in a straightforward manner (but requiring NaH as
base). Their synthesis remedies the lack of such rigid polydentate
dithiocarbamate ligands in the arsenal of coordination and
supramolecular chemists.
1
743, 692 cm-1. NMR H (CD3OD): d 2.89 (s, 4H, NCH2CH2N),
4.04 (s, 4H, CH2Ph), 5.69 (t, 2H, para-C6H5, JHH = 7.3 Hz), 5.76
(t, 4H, meta-C6H5, JHH = 7.3 Hz), 5.94 (d, 4H, ortho-C6H5, JHH
=
7.2 Hz) ppm.
N(CH2CH2N(Me)CS2Na)3 (Na3L2)
A
solution of tris[2-(methylamino)ethyl]amine (0.11 mL,
0.531 mmol) in dry tetrahydrofuran (12 mL) and treated with
portions of sodium hydride (95.6 mg, 2.390 mmol, 60% in mineral
oil) under nitrogen and stirred for 1 h. Carbon disulfide (0.14 mL,
2.328 mmol) was added and the reaction stirred overnight. Excess
sodium hydride was destroyed by slow addition of water (10 mL)
by syringe. This solution was used for addition to the metal
complexes without further purification.
Work is currently underway to use metal units based on these
building blocks for extended systems and to explore the potential
of multimetallic compounds based on these ligands in catalysis.
{(CH2CH2)NCS2Na}3 (Na3L3)
Experimental
A solution of triazacyclononane hydrochloride salt (100 mg,
0.422 mmol) in dry tetrahydrofuran (10 mL) was treated with
portions of sodium hydride (151.8 mg, 3.795 mmol, 60% in mineral
oil) under nitrogen and stirred for 1 h. Carbon disulfide (0.11 mL,
1.829 mmol) was added and the reaction stirred overnight. Excess
sodium hydride was destroyed by slow addition of water (10 mL)
by syringe. This solution was used for addition to the metal
complexes without further purification.
General comments
All experiments were carried out under aerobic conditions and
the majority of the complexes appear indefinitely stable towards
the atmosphere in solution or in the solid state. Solvents and
other compounds were used as received from commercial sources
apart from the following, which were prepared by literature
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 5852–5864 | 5859
©

{CH2CH2N(CS2Na)CH2CH2CH2NCS2Na}2 (Na4L4)
6.91 (d, 4H, ortho-C6H5, JHH = 6.8 Hz), 7.08 (t, 4H, meta-C6H5,
JHH = 7.1 Hz), 7.17 (t, 2H, para-C6H5, JHH = 7.1 Hz), 7.41–7.66 (m,
40H, PC6H5) ppm. 31P: d 32.8, 33.3 (AB, dppf, 2JPP = 24.3 Hz) ppm.
Cyclam (100 mg, 0.499 mmol) was dissolved in dry tetrahydrofu-
ran (10 mL) under nitrogen and treated with portions of sodium
hydride (119.8 mg, 2.995 mmol, 60% in mineral oil) and stirred for
1 h. Carbon disulfide (0.18 mL, 2.993 mmol) was added and the
reaction stirred overnight. Excess sodium hydride was destroyed by
slow addition of water (10 mL) by syringe. This solution was used
for addition to the metal complexes without further purification.
MS (FAB + ve) m/z (%) = 1857 (62) [M + PF6 ]+. Analysis: Found
-
C, 51.6; H, 3.7; N, 1.5%. Calculated for C86H74F12Fe2N2P6Pd2S4
(Mw = 2000.0): C, 51.6; H, 3.7; N, 1.4%.
[L1{Pt(dppf)}2](PF6)2 (4)
The same procedure was employed as for complex 1 using
[PtCl2(dppf)] (80 mg, 0.098 mmol), K2L1 (22.9 mg, 0.049 mmol)
and NH4PF6 (23.8 mg, 0.146 mmol). The yellow product was
obtained in a yield of 57 mg (53%). IR: 1512, 1483, 1435, 1361,
1308, 1231, 1169, 1098, 1063, 1030, 998, 828 (nPF), 745, 692,
[L1{Pt(PEt3)2}2](PF6)2 (1)
A dichloromethane solution (15 mL) of cis-[PtCl2(PEt3)2] (100 mg,
0.200 mmol) was treated with K2L1 (46.8 mg, 0.100 mmol) and
NH4PF6 (48.8 mg, 0.300 mmol) in methanol (10 mL). The reaction
was stirred at room temperature for 2 h and then all solvent
removed under reduced pressure. The residue was dissolved in
dichloromethane (10 mL) and filtered through a plug of Celite.
Ethanol (30 mL) was added and a pale yellow product obtained
on rotary evaporation. This was filtered, washed with ethanol
(20 mL) and petroleum ether (10 mL) and dried under vacuum.
Yield: 93 mg (60%). IR: 1739, 1505, 1442, 1421, 1365, 1233, 1143,
1037, 969, 833 (nPF), 770, 744, 701, 642 cm-1. NMR (CD2Cl2)
1H: d 1.28 (m, 36H, CH3), 2.18 (m, 24H, PCH2), 4.20 (s, 4H,
1
633 cm-1. NMR (CDCl3) H: d 3.53 (s, 4H, NCH2CH2N), 4.37
(s(br), 4H + 4H, CH2Ph + C5H4), 4.50, 4.61, 4.64 (s(br) x 3, 3 ¥
4H, C5H4), 6.92 (m, 4H, ortho-C6H5), 7.12 (m, 4H, meta-C6H5),
7.20 (t, 2H, para-C6H5, JHH = 6.8 Hz), 7.49–7.66 (m, 40H, PC6H5)
2
1
ppm. 31P: d 16.0 (d, dppf, JPP = 20.6 Hz, JPtP = 3375 Hz), 16.4
2
1
(d, dppf, JPP = 20.6 Hz, JPtP = 3398 Hz) ppm. MS (FAB + ve)
m/z (%) = 2034 (28) [M + PF6 ]+, 1890 (22) [M]+. Analysis: Found
-
C, 47.5; H, 3.4; N, 1.4%. Calculated for C86H74F12Fe2N2P6Pt2S4
(Mw = 2178.1): C, 47.4; H, 3.4; N, 1.3%.
NCH2CH2N), 5.16 (s, 4H, CH2Ph), 7.47 (m, 10H, C6H5) ppm. 13
C
[L1{Ni(dppp)}2](PF6)2 (5)
2
(CD2Cl2): d 8.4 (m, CH3), 16.6 (d, PCH2, JPtC = 35.7 Hz), 45.6,
54.1 (s ¥ 2, NCH2 and PhCH2), 128.9 (s, o/m-C6H5), 129.5 (s,
p-C6H5), 129.6 (s, o/m-C6H5), 133.0 (s, ipso-C6H5), 209.7 (s, CS2,
The same procedure was employed as for complex 1 using
[NiCl2(dppp)] (100 mg, 0.184 mmol), K2L1 (43.2 mg, 0.092 mmol)
and NH4PF6 (45.1 mg, 0.276 mmol). The orange-brown product
was obtained in a yield of 108 mg (72%). IR: 1503, 1434, 1358,
1228, 1184, 1099, 1066, 998, 969, 925, 829 (nPF), 741, 691, 663 cm-1.
2JPtC = 87.3 Hz) ppm. 31P: d 6.0 (d, PEt3, JPP = 21.5 Hz, JPtP
=
2
1
3127 Hz), 6.5 (d, PEt3, 2JPP = 21.5 Hz, 1JPtP = 3108 Hz) ppm. MS
(ES + ve) m/z (%) = 1250 (2) [M]+, 1133 (12) [M - PEt3]+. MS
(FAB + ve) m/z (%) = 1397 (65) [M + PF6 ]+. Analysis: Found
-
1
NMR (CD2Cl2) H: d 2.23 (m, 4H, dppp-CCH2C), 2.71 (m, 8H,
C, 32.7 H, 5.0; N, 1.9%. Calculated for C42H78F12N2P6Pt2S4 (Mw =
dppp-PCH2), 3.49 (s, 4H, NCH2CH2N), 4.42 (s, 4H, CH2Ph), 6.93
1542.6): C, 32.7; H, 5.1; N, 1.8%.
(d, 4H, ortho-C6H5, JHH = 7.3 Hz), 7.18 (t, 4H, meta-C6H5, JHH
=
7.6 Hz), 7.29 (t, 2H, para-C6H5, JHH = 7.4 Hz), 7.33–7.69 (m, 40H,
PC6H5) ppm. 31P: d 12.5 (s, dppp) ppm. MS (FAB + ve) m/z
(%) = 1332 (20) [M]+. Analysis: Found C, 53.4; H, 4.3; N, 1.8%.
Calculated for C72H70F12N2Ni2P6S4 (Mw = 1620.1): C, 53.3; H, 4.4;
N, 1.7%.
[L1{Ni(dppf)}2](PF6)2 (2)
The same procedure was employed as for complex 1 using
[NiCl2(dppf)] (100 mg, 0.146 mmol), K2L1 (34.3 mg, 0.073 mmol)
and NH4PF6 (35.7 mg, 0.219 mmol). The red product was obtained
in 76.3 mg (55%) yield. IR: 1520, 1481, 1434, 1390, 1361, 1344,
1308, 1233, 1168, 1124, 1093, 1030, 999, 976, 826 (nPF), 743, 692,
[L1{Au(PPh3)}2] (6)
632 cm-1. NMR (CDCl3) H: d 3.49 (s, 4H, NCH2CH2N), 4.17
1
The same procedure was employed as for complex 1 using
[AuCl(PPh3)] (100 mg, 0.202 mmol), and K2L1 (47.4 mg,
0.101 mmol). The pale yellow product was obtained in 82 mg
(62%) yield. IR: 1464, 1396, 1356, 1310, 1198, 1137, 980, 952,
(s, 4H, CH2Ph), 4.48, 4.56, 4.63, 4.73 (s(br) x 4, 4 ¥ 4H, C5H4),
6.89 (m, 4H, ortho-C6H5) 7.16 (m, 4H, meta-C6H5) 7.23 (m, 2H,
para-C6H5), 7.39–7.83 (m, 40H, PC6H5) ppm. 31P: d 32.0, 32.6 (AB,
dppf, 2JPP = 46.3 Hz) ppm. MS (ES + ve) m/z (%) = 1761 (18) [M +
1
888 cm-1. NMR (CD2Cl2) H: d 4.26 (s, 4H, NCH2CH2N), 5.25
PF6 ]+, 1616 (16) [M]+. Analysis: Found C, 54.3; H, 3.8; N, 1.5%.
-
(s, 4H, CH2Ph), 7.30–7.39 (m, 6H, CC6H5), 7.48–7.69 (m, 30H +
4H, PC6H5 + CC6H5) ppm. 31P: d 36.1 (s, PPh3) ppm. MS (ES +
ve) m/z (%) = 1309 (2) [M]+. Analysis: Found C, 49.5; H, 3.6; N,
2.3%. Calculated for C54H48Au2N2P2S4 (Mw = 1308.0): C, 49.5; H,
3.7; N, 2.1%.
Calculated for C86H74F12Fe2N2Ni2P6S4 (Mw = 1904.0): C, 54.2; H,
3.9; N, 1.5%.
[L1{Pd(dppf)}2](PF6)2 (3)
The same procedure was employed as for complex 1 using
[PdCl2(dppf)] (80 mg, 0.109 mmol), K2L1 (25.6 mg, 0.055 mmol)
and NH4PF6 (26.7 mg, 0.164 mmol). The orange product was
obtained in a yield of 60 mg (55%). IR: 1513, 1484, 1435, 1344,
1310, 1200, 1168, 1126, 1094, 1028, 978, 827 (nPF), 743, 692,
[L1{Au(PMe3)}2] (7)
The same procedure was employed as for complex 1 us-
ing [AuCl(PMe3)] (30 mg, 0.097 mmol) and K2L1 (22.8 mg,
0.049 mmol). The pale yellow product was obtained in a yield of
23.4 mg (51%). IR: 1494, 1462, 1402, 1358, 1312, 1286, 1207, 1150,
1033, 950, 888, 853, 773, 729, 694, 681, 651 cm-1. NMR (CD2Cl2)
1
631 cm-1. NMR (CDCl3) H: d 3.58 (s, 4H, NCH2CH2N), 4.39
(s, 4H, CH2Ph), 4.43, 4.49, 4.64, 4.66 (s(br) x 4, 4 ¥ 4H, C5H4),
5860 | Dalton Trans., 2011, 40, 5852–5864
This journal is
The Royal Society of Chemistry 2011
©

1H: d 1.64 (d, 18H, CH3, JHP = 10.8 Hz), 4.20 (s, 4H, NCH2CH2N),
5.21 (s, 4H, CH2Ph), 7.31–7.44 (m, 10H, C6H5) ppm. 31P: d - 7.2
(s, PMe3) ppm. MS (ES + ve) m/z (%) = 937 (50) [M]+. Analysis:
Found C, 30.7; H, 3.8; N, 2.9%. Calculated for C24H36Au2N2P2S4
(Mw = 936.0): C, 30.8; H, 3.9; N, 3.0%.
petroleum ether (10 mL) and dried under vacuum. Yield: 44 mg
(72%). IR: 1479, 1435, 1380, 1258, 1225, 1152, 1099, 1028, 974,
1
846, 744 cm-1. NMR (CD2Cl2) H: d 3.03 (t, 6H, CH2, JHH
=
7.1 Hz), 3.50 (s, 9H, NCH3), 4.07 (t, 6H, CH2, JHH = 7.2 Hz), 7.50–
7.67 (m, 45H, C6H5) ppm. 31P: d 36.0 (s, PPh3) ppm. MS (ES +
ve) m/z (%) = 1792 (1) [M]+. Analysis: Found C, 44.2 H, 3.7; N,
3.2%. Calculated for C66H66Au3N4P3S6 (Mw = 1791.5): C, 44.3; H,
3.7; N, 3.1%.
[L1{Au(IDip)}2] (8)
The same procedure was employed as for complex 1 us-
ing [AuCl(IDip)] (30 mg, 0.048 mmol) and K2L1 (11.3 mg,
0.024 mmol). The pale yellow product was obtained in a yield of
12 mg (32%). IR: 1594, 1459, 1399, 1385, 1353, 1329, 1294, 1195,
1146, 1118, 1060, 1080, 991, 946, 802, 756, 742, 699, 637 cm-1.
NMR 1H (CD2Cl2): d 1.25 (d, 24H, CH3, JHH = 6.9 Hz), 1.40 (d,
24H, CH3, JHH = 6.8 Hz), 2.66 (sept., 8H, CHMe2, JHH = 6.8 Hz),
3.89 (s, 4H, NCH2CH2N), 4.97 (s, 4H, CH2Ph), 7.13–7.28 (m,
[L2{Au(PCy3)}3] (12)
The same procedure was employed as for complex 11 using
[AuCl(PCy3)] (50 mg, 0.098 mmol) and Na3L2 (0.033 mmol) to
yield 35 mg (57%) of the pale yellow product. IR: 2921, 2848,
1710, 1444, 1389, 1346, 1295, 1268, 1243, 1201, 1159, 1112, 1070,
1002, 967, 915, 888, 851, 819, 754, 739 cm-1. NMR (CD2Cl2) 1H: d
1.28–2.08 (m ¥ 5, 99H, Cy), 2.97 (t, 6H, CH2, JHH = 7.3 Hz), 3.46
(s, 9H, NCH3), 4.04 (t, 6H, CH2, JHH = 7.3 Hz) ppm. 31P: d 55.5 (s,
PCy3) ppm. MS (ES + ve) m/z (%) = 1846 (3) [M]+, 1367 (5) [M
- AuPCy3]+. Analysis: Found C, 43.1 H, 6.5; N, 3.2%. Calculated
for C66H120Au3N4P3S6 (Mw = 1845.9): C, 42.9; H, 6.6; N, 3.0%.
10H + 4H, C6H5 + HC CH), 7.35 (d, meta-C6H3, 8H, JHH
=
7.8 Hz), 7.53 (t, para-C6H3, 4H, JHH = 7.8 Hz) ppm. MS (ES +
ve) m/z (%) = 1562 (76) [M]+. Analysis: Found C, 54.0; H, 4.4; N,
5.3%. Calculated for C72H90Au2N6S4 (Mw = 1561.0): C, 55.4; H,
5.8; N, 5.4%.
[L1{Au2(dppm)}2](PF6)2 (9)
[L2{Au(PMe3)}3] (13)
The same procedure was employed as for complex 1 using
[(dppm)(AuCl)2] (50 mg, 0.059 mmol), K2L1 (13.8 mg, 0.029 mmol)
and NH4PF6 (14.4 mg, 0.088 mmol). The bright yellow crystalline
solid was obtained in 45 mg (69%) yield. IR: 1742, 1465, 1405,
1358, 1310, 1286, 1208, 1150, 1102, 1032, 952, 832 (nPF), 775, 729,
690 cm-1. NMR (CD2Cl2) 1H: d 3.79 (s(br), 4H, PCH2P), 4.42 (s,
4H, NCH2CH2N), 5.25 (s, 4H, CH2Ph), 7.31–7.54 (m, 40H + 10H,
PC6H5 + C6H5) ppm. 31P: d 32.3 (s(br), dppm) ppm. MS (ES + ve)
m/z (%) = 1945 (100) [M]+. Analysis: Found C, 36.3; H, 2.5; N,
1.3%. Calculated for C68H62Au4F12N2P6S4 (Mw = 2236.1): C, 36.5;
H, 2.8; N, 1.3%.
The same procedure was employed as for complex 11 using
[AuCl(PMe3)] (50 mg, 0.162 mmol) and Na3L2 (0.054 mmol) to
provide a pale yellow product in 43 mg (65%) yield. IR: 1617,
1479, 1418, 1376, 1287, 1257, 1225, 1150, 1087, 1043, 954, 855,
1
747, 682 cm-1. NMR (CD2Cl2) H: d 1.62 (d, 27H, PCH3, JHH
=
10.7 Hz), 2.95 (t, 6H, CH2, JHH = unresolved), 3.45, 3.44 (s ¥ 2,
9H, NCH3), 4.00 (t, 6H, CH2, JHH = unresolved) ppm. 31P: d - 6.7
(s, PMe3) ppm. MS (ES + ve) m/z (%) = 1233 (3) [M]+, 1157 (5)
[M - PMe3]+. Analysis: Found C, 20.4 H, 3.6; N, 4.2%. Calculated
for C21H48Au3N4P3S6 (Mw = 1232.9): C, 20.6; H, 3.9; N, 4.6%.
[L2{Au(IDip)}3] (14)
[L1{Au2(dppf)}2](PF6)2 (10)
The same procedure was employed as for complex 11 using
[AuCl(IDip)] (40 mg, 0.064 mmol) and Na3L2 (0.021 mmol) to
yield 33 mg (72%) of the pale yellow product. IR: 2960, 2926,
2866, 1594, 1554, 1469, 1415, 1364, 1347, 1290, 1257, 1214, 1150,
1088, 1059, 1044, 984, 946, 802, 757, 744, 701 cm-1. NMR (CD2Cl2)
1H: d 1.24, 1.37 (d ¥ 2, MeIDip, 2 ¥ 36H, JHH = 6.8 Hz), 2.64 (m,
CHMeIDip + NCH2, 12H + 6H), 3.11 (s, 9H, NCH3), 3.72 (t, 6H,
CH2, JHH = 7.1 Hz), 7.25 (s, 6H, HC CHIDip), 7.34 (d, 12H, meta-
C6H3, JHH = 7.7 Hz), 7.54 (t, 6H, para-C6H3, JHH = 7.7 Hz) ppm.
MS (ES + ve) m/z (%) = 2169 (22) [M]+. Analysis: Found C, 51.4
H, 6.2; N, 6.4%. Calculated for C93H129Au3N10S6 (Mw = 2170.4): C,
51.5; H, 6.0; N, 6.5%.
The same procedure was employed as for complex 1 using
[(dppf)(AuCl)2] (50 mg, 0.049 mmol), K2L1 (11.5 mg, 0.025 mmol)
and NH4PF6 (12 mg, 0.074 mmol). A pale yellow product was
obtained in a yield of 42 mg (66%). IR: 1481, 1434, 1355, 1311,
1218, 1173, 1101, 1030, 999, 964, 829 (nPF), 744, 692, 626 cm-1.
1
NMR (d6-acetone) H: d 4.46, 4.54 (s(br) x 2, 2 ¥ 8H, C5H4),
4.87 (s, 4H, NCH2CH2N), 5.69 (s, 4H, CH2Ph), 7.40–7.52 (m,
10H, C6H5), 7.63–7.77 (m, 40H, dppf) ppm. 31P: d 30.9 (s, dppf)
ppm. MS (FAB + ve) m/z (%) = 2431 (32) [M + PF6]+, 2287 (3)
[M]+. Analysis: Found C, 39.9; H, 2.9; N, 1.2%. Calculated for
C86H74Au4F12Fe2N2P6S4 (Mw = 2576.0): C, 40.1; H, 2.9; N, 1.1%.
[L2{Au(PPh3)}3] (11)
[L3{Au(PPh3)}3] (15)
A dichloromethane solution (15 mL) of [AuCl(PPh3)] (50 mg,
0.101 mmol) was treated with a solution of Na3L2 (0.034 mmol)
and methanol (10 mL) added. The reaction was stirred at room
temperature for 1 h and then all solvent removed under reduced
pressure. The residue was dissolved in dichloromethane (10 mL)
and filtered through a plug of Celite to remove NaCl. Methanol
(30 mL) was added and a pale yellow product obtained on rotary
evaporation. This was filtered, washed with methanol (20 mL),
A dichloromethane solution (15 mL) of [AuCl(PPh3)] (50 mg,
0.101 mmol) was treated with a solution of Na3L3 (0.034 mmol)
and methanol (10 mL) added. The reaction was stirred at room
temperature for 1 h and then all solvent removed under reduced
pressure. The residue was dissolved in dichloromethane (10 mL)
and filtered through a plug of Celite to remove NaCl. Methanol
(30 mL) was added and a pale yellow product obtained on rotary
evaporation. This was filtered, washed with methanol (20 mL),
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 5852–5864 | 5861
©

petroleum ether (10 mL) and dried under vacuum. Yield: 42 mg
(71%). The complex is moderately soluble in methanol, allowing a
second crop to be obtained from the filtrate on standing overnight
at - 20 ◦C. IR: 1710, 1444, 1389, 1347, 1295, 1268, 1243, 1202,
1158, 1101, 1071, 1001, 967, 915, 888, 851, 820, 741 cm-1. NMR
temperature for 1 h and then all solvent removed under reduced
pressure. The residue was dissolved in dichloromethane (10 mL)
and filtered through a plug of Celite to remove NaCl. Methanol
(30 mL) was added and a pale yellow product obtained on rotary
evaporation. This was filtered, washed with methanol (20 mL),
petroleum ether (10 mL) and dried under vacuum. Yield: 45 mg
(77%). The complex is moderately soluble in methanol, allowing a
second crop to be obtained from the filtrate on standing overnight
at - 20 ◦C. IR: 2926, 2851, 1707, 1462, 1435, 1401, 1360, 1272,
1184, 1133, 1098, 957, 892, 852, 744, 691 cm-1. NMR (CD2Cl2) 1H:
d 2.37 (quintet, 4H, NCH2CH2CH2N, JHH = 6.9 Hz), 4.18 (t, 8H,
NCH2CH2CH2N, JHH = 6.9 Hz), 4.38 (s, 8H, NCH2CH2N), 7.50–
7.67 (m, 60H, C6H5) ppm. 31P: d 36.1 (s, PPh3) ppm. MS (ES + ve)
m/z (%) = 2075 (5) [M - PPh3]+, 1813 (2) [M - 2PPh3]+. Analysis:
Found C, 44.0 H, 3.4; N, 2.5%. Calculated for C86H80Au4N4P4S8
(Mw = 2337.9): C, 44.2; H, 3.5; N, 2.4%.
1
(CD2Cl2) H: d 4.49 (s, 12H, CH2), 7.50–7.68 (m, 45H, C6H5)
ppm. 31P: d 36.0 (s, PPh3) ppm. MS (ES + ve) m/z (%) = 1732
(2) [M]+. Analysis: Found C, 43.6 H, 3.2; N, 2.4%. Calculated for
C63H57Au3N3P3S6 (Mw = 1731.1): C, 43.7; H, 3.3; N, 2.4%.
[L3{Au(PCy3)}3] (16)
The same procedure was employed as for complex 15 using
[AuCl(PCy3)] (50 mg, 0.097 mmol) and Na3L3 (0.033 mmol)
to yield 16 mg (27%) of pale yellow product. The complex is
moderately soluble in methanol, allowing a second crop to be
◦
obtained from the filtrate on standing overnight at - 20 C. IR:
2922, 2848, 1444, 1391, 1345, 1296, 1270, 1242, 1201, 1167, 1113,
1070, 1003, 967, 916, 888, 852, 821, 754, 743 cm-1. NMR (CD2Cl2)
1H: d 1.33–2.06 (m ¥ 5, 99H, Cy), 4.40 (s, 12H, CH2) ppm.
31P: d 55.5 (s, PCy3) ppm. MS (ES + ve) m/z (%) = 1786 (2)
[M]+. Analysis: Found C, 40.6 H, 5.3; N, 2.3%. Calculated for
C63H111Au3N3P3S6·CH2Cl2 (Mw = 1785.5): C, 41.1; H, 6.1; N 2.3%.
[L4{Au(PCy3)}4] (20)
The same procedure was employed as for complex 19 using
[AuCl(PCy3)] (50 mg, 0.098 mmol) and Na4L4 (0.024 mmol) to
provide a pale yellow product in 30 mg (52%) yield. IR: 2924,
2848, 1706, 1461, 1402, 1360, 1283, 1183, 1132, 1096, 1052, 951,
890, 852, 742 cm-1. NMR (CD2Cl2) 1H: d 1.25–2.07 (m ¥ 5, 132H,
Cy), 2.28 (quintet, 4H, NCH2CH2CH2N, JHH = 7.0 Hz), 4.11 (t,
8H, NCH2CH2CH2N, JHH = 7.2 Hz), 4.30 (s, 8H, NCH2CH2N)
ppm. 31P: d 55.6 (s, PCy3) ppm. MS (ES + ve) m/z (%) = 2409
(1) [M]+. Analysis: Found C, 42.8 H, 6.2; N, 2.4%. Calculated for
C86H152Au4N4P4S8 (Mw = 2410.4): C, 42.9; H, 6.4; N, 2.3%.
[L3{Au(PMe3)}3] (17)
The same procedure was employed as for complex 15 using
[AuCl(PMe3)] (50 mg, 0.162 mmol) and Na3L3 (0.054 mmol) to
yield 43 mg (68%) of the pale yellow product. The complex is
moderately soluble in methanol, allowing a second crop to be
◦
obtained from the filtrate on standing overnight at - 20 C. IR:
1707, 1479, 1418, 1375, 1287, 1258, 1221, 1150, 1087, 1043, 954,
[L4{Au(PMe3)}4] (21)
1
856, 747 cm-1. NMR (CD2Cl2) H: d 1.63 (d, 27H, PCH3, JHH
=
10.6 Hz), 4.27, 4.46 (m ¥ 2, 12H, CH2) ppm. 31P: d - 6.0 (s,
PMe3) ppm. MS (ES + ve) m/z (%) = 1353 (10) [M + Na +
nitrobenzylalcohol matrix]+. Analysis: Found C, 18.6 H, 3.5; N,
3.3%. Calculated for C18H39Au3N3P3S6 (Mw = 1173.0): C, 18.4; H,
3.4; N, 3.6%.
The same procedure was employed as for complex 19 using
[AuCl(PMe3)] (50 mg, 0.162 mmol) and Na4L4 (0.041 mmol) to
provide 17 mg (26%) of the pale yellow product. The complex
is moderately soluble in methanol, allowing a second cro◦p to be
obtained from the filtrate on standing overnight at - 20 C. IR:
2898, 1464, 1405, 1362, 1285, 1184, 1134, 1097, 1054, 955, 891, 853,
[L3{Au(IDip)}3] (18)
1
744, 680 cm-1. NMR (CD2Cl2) H: d 1.62 (d, 36H, PCH3, JHH
=
10.7 Hz), 2.26 (quintet, 4H, NCH2CH2CH2N, JHH = 7.7 Hz), 4.10
(t, 8H, NCH2CH2CH2N, JHH = 7.7 Hz), 4.3 (s, 8H, NCH2CH2N)
ppm. 31P: d - 6.3 (s, PMe3) ppm. MS (ES + ve) m/z (%) = 1163
(10) [M - Au - 3PMe3]+. Analysis: Found C, 19.7 H, 3.4; N, 3.6%.
Calculated for C26H56 Au4N4P4S8 (Mw = 1593.0): C, 19.6; H, 3.5;
N, 3.5%.
The same procedure was employed as for complex 15 using
[AuCl(IDip3)] (50 mg, 0.081 mmol) and Na3L3 (0.027 mmol) to
provide a pale yellow product 46 mg (81%) yield. The complex
is moderately soluble in methanol, allowing a second cro◦p to be
obtained from the filtrate on standing overnight at - 20 C. IR:
2960, 2926, 2867, 1594, 1554, 1457, 1415, 1385, 1293, 1243, 1203,
1182, 1162, 1060, 971, 801, 756, 739, 699 cm-1. NMR (CD2Cl2)
1H: d 1.24, 1.37 (d ¥ 2, MeIDip, 2 ¥ 36H, JHH = 6.9 Hz), 2.65 (septet,
12H, CHMeIDip, JHH = 6.9 Hz), 3.97 (s, 12H, NCH2), 7.24 (s, 6H,
HC CHIDip), 7.34 (d, 12H, meta-C6H3, JHH = 7.8 Hz), 7.54 (t,
6H, para-C6H3, JHH = 7.8 Hz) ppm. MS (ES + ve) m/z (%) = 2111
(15) [M]+. Analysis: Found C, 51.3 H, 5.7; N, 5.8%. Calculated for
C90H120Au3N9S6 (Mw = 2111.3): C, 51.2; H, 5.7; N, 6.0%.
Crystallographic section
Crystal data for 2. [C86H74Fe2N2Ni2P4S4](PF6)2·CH2Cl2, M =
¯
1991.58, triclinic, P1(no. 2), a = 13.5263(2), b = 17.6262(3), c ◦=
˚
19.4449(4) A, a = 96.8975(15), b = 97.5228(15), g = 107.7830(15) ,
V = 4313.12(14) A , Z = 2, Dc = 1.534 g cm-3, m(Cu-Ka) =
3
˚
6.276 mm-1, T = 173 K, red platy needles, Oxford Diffraction
Xcalibur PX Ultra diffractometer; 50144 measured reflections,
16955 independent reflections (Rint = 0.0220), F2 refinement,
R1(obs) = 0.0409, wR2(all) = 0.1168, 14825 independent observed
absorption-corrected reflections [|Fo| > 4s(|Fo|), 2qmax = 145◦],
1095 parameters. CCDC 764405.
[L4{Au(PPh3)}4] (19)
A dichloromethane solution (15 mL) of [AuCl(PPh3)] (50 mg,
0.101 mmol) was treated with a solution of Na4L4 (0.025 mmol)
and methanol (10 mL) added. The reaction was stirred at room
5862 | Dalton Trans., 2011, 40, 5852–5864
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The Royal Society of Chemistry 2011
©

Crystaldatafor3. [C86H74Fe2N2P4Pd2S4](PF6)2·CH2Cl2·EtOH,
Trans., 2009, 607–609; (e) E. R. Knight, N. H. Leung, Y. H. Lin, A. R.
Cowley, D. J. Watkin, A. L. Thompson, G. Hogarth and J. D. E. T.
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¯
M = 2133.03, triclinic, P1(no. 2), a = 13.8220(2), b = 17.8518(3),
˚
c = 19.3592◦(3) A, a = 98.2051(14), b = 96.9952(14), g
=
3
-3
˚
108.4619(17) , V = 4413.11(13) A , Z = 2, Dc = 1.605 g cm ,
m(Mo-Ka) = 1.061 mm-1, T = 173 K, orange blocks, Oxford
Diffraction Xcalibur 3 diffractometer; 46924 measured reflections,
28689 independent reflections (Rint = 0.0193), F2 refinement,
R1(obs) = 0.0379, wR2(all) = 0.1072, 19906 independent observed
absorption-corrected reflections [|Fo| > 4s(|Fo|), 2qmax = 65◦],
1151 parameters. CCDC 764406.
Crystal data for 6. C54H48Au2N2P2S4·2CH2Cl2·0.5EtOH, M =
9 R. Reyes-Mart´ınez, P. Garc´ıa, y Garc´ıa, M. Lo´pez-Cardoso, H. Ho¨pfl
and H. Tlahuext, Dalton Trans., 2008, 6624–6627.
¯
1501.94, triclinic, P1 (no. 2), a = 9.0346(3), b = 12.1805(3), c ◦=
˚
14.0257(4) A, a = 93.738(2), b = 105.979(3), g = 102.402(3) ,
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and B. Konig, Curr. Org. Synth., 2007, 4, 390–412; (d) X. Y. Liang and
P. J. Sadler, Chem. Soc. Rev., 2004, 33, 246–266.
3
-3
˚
V = 1436.45(8) A , Z = 1 [Ci symmetry], Dc = 1.736 g cm ,
m(Mo-Ka) = 5.528 mm-1, T = 173 K, colourless plates, Oxford
Diffraction Xcalibur 3 diffractometer; 16291 measured reflections,
9388 independent reflections (Rint = 0.0296), F2 refinement,
R1(obs) = 0.0344, wR2(all) = 0.0833, 7186 independent observed
absorption-corrected reflections [|Fo| > 4s(|Fo|), 2qmax = 66◦],
341 parameters. CCDC 764407.
12 P. J. Heard, K. Kite, J. S. Nielsen and D. A. Tocher, J. Chem. Soc.,
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Cronje, in Gold-Progress in Chemistry Biochemistry and Technology
Ed. H. Schmidbaur, John Wiley & Sons Inc.New York, 1999; (c).
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2005, 220, 342–344; (b) S. Y. Ho and E. R. T. Tiekink, Acta Crystallogr.,
Sect. E: Struct. Rep. Online, 2001, 57, m603–m604; (c) J. G. Wijnhoven,
W. P. J. H. Bosman and P. T. Beurskens, J. Cryst. Mol. Struct., 1972,
2, 7–15; (d) S. Y. Ho and E. R. T. Tiekink, Acta Crystallogr., Sect. E:
Struct. Rep. Online, 2002, 58, m86–m87.
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H.-P. Huang and R. Zhang, J. Am. Chem. Soc., 2005, 127, 17994–
17995; (b) Q.-F. Sun, T. K.-M. Lee, P.-Z. Li, L.-Y. Yao, J.-J. Huang, J.
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E. C.-C. Cheng, Y.-Z. Li and V. W.-W. Yam, Angew. Chem., Int. Ed.,
2008, 47, 4551–4554; (d) J. D. E. T. Wilton-Ely, A. Schier, N. W. Mitzel
and H. Schmidbaur, Inorg. Chem., 2001, 40, 6266–6271; (e) J. D. E. T.
Wilton-Ely, H. Ehlich, A. Schier and H. Schmidbaur, Helv. Chim. Acta,
2001, 84, 3216–3232; (f) J. D. E. T. Wilton-Ely, A. Schier, N. W. Mitzel,
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313–323.
Crystal data for 7. C24H36Au2N2P2S4, M = 936.66, monoclinic,
˚
P21/n (no. 14), a = 6.41819(12), b = 23.1984(4), c = 10.39421(17) A,
◦
3
˚
b = 94.3353(16) , V = 1543.18(5) A , Z = 2 [Ci symmetry],
Dc = 2.016 g cm-3, m(Mo-Ka) = 9.887 mm-1, T = 173 K,
colourless blocks, Oxford Diffraction Xcalibur 3 diffractometer;
16525 measured reflections, 5174 independent reflections (Rint
=
0.0215), F2 refinement, R1(obs) = 0.0184, wR2(all) = 0.0340, 4032
independent observed absorption-corrected reflections [|Fo| >
4s(|Fo|), 2qmax = 65◦], 176 parameters. CCDC 764408.
The structures were refined based using the SHELXTL and
SHELX-97 program systems.33 Further details can be found in
the Supporting Information.†
Acknowledgements
We thank Johnson Matthey Ltd for a generous loan of hydrogen
tetrachloroaurate.
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