Bi- and tetrametallic complexes of the noble metals with PNP-ligands

Article abstract of DOI:10.1016/j.jorganchem.2013.05.016

Two new ligands with {(Ph₂P)₂N} functions have been synthesized and introduced into the chemistry of gold(I). The first ligand N,N-bis(diphenylphosphanyl)-4-(phenyldiazenyl)aniline (DPPPA) is a derivative of an azo dye. Reaction of DPPPA with [(tht)AuCl] (tht = tetrahydrothiophene) in CH₂CI₂ gave the dye functionalized bimetallic gold(I) complex [DPPPA(AuCl)₂] (1). The second ligand, m-N,N,N′, N′-tetrakis(diphenylphosphanyl)xylylenediamine, (DPPXA), has two {(Ph ₂P)₂N} functional groups in a xylylenediamine backbone. DPPXA was reacted with [(tht)AuCl] to give the tetrametallic gold complex [DPPXA(AuCl)₄] (2). Reaction of DPPXA with [(COD)MCl₂] (M = Pd, Pt) (COD = 1,5-cyclooctadiene) in DMSO resulted in the bimetallic palladium and platinum complexes [DPPXA(MCl₂)₂] (M= Pd (3), Pt (4)). DPPPA and all metal complexes were characterized by single crystal X-ray diffraction. The complexes demonstrate quite different photophysical properties. Whereas no photoluminescence (PL) was detected for 1 and 4, complex 2 shows red PL in methylene chloride solution as well as in the solid state. Nearinfrared emission at ～800 nm was observed for complex 3 at temperatures below ～50 K.

Full text of DOI:10.1016/j.jorganchem.2013.05.016

Accepted Manuscript
Bi- and Tetrametallic Complexes of the Noble Metals with PNP-Ligands
Christian Sarcher, Sergei Lebedkin, Manfred M. Kappes, Olaf Fuhr, Peter W. Roesky
PII:
S0022-328X(13)00395-1
10.1016/j.jorganchem.2013.05.016
JOM 18038
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 19 April 2013
Revised Date: 6 May 2013
Accepted Date: 7 May 2013
Please cite this article as: C. Sarcher, S. Lebedkin, M.M. Kappes, O. Fuhr, P.W. Roesky, Bi- and
Tetrametallic Complexes of the Noble Metals with PNP-Ligands, Journal of Organometallic Chemistry
(2013), doi: 10.1016/j.jorganchem.2013.05.016.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Bi- and Tetrametallic Complexes of the Noble Metals with PNP-
Ligands
Christian Sarcher,a Sergei Lebedkin,b Manfred M. Kappes,b,c* Olaf Fuhr,b,d* and Peter
W. Roeskya*
aInstitut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT)
Engesserstraße Geb. 30.45, 76131 Karlsruhe, Germany
bInstitut für Nanotechnologie, Karlsruhe Institute of Technology (KIT), Hermann-von-
Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)
cInstitut für Physikalische Chemie, Karlsruhe Institute of Technology (KIT), Fritz-
Haber Weg 2, 76131 Karlsruhe (Germany)
dLehn Institute of Functional Materials (LIFM), Sun Yat-Sen University (SYSU),
Xingang Road West, Guangzhou 510275, China.

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______________________________________________________________________
Two new ligands with {(Ph2P)2N} functions have been synthesized and introduced into the
chemistry of gold(I). The first ligand N,N,-bis(diphenylphosphanyl)-4-(phenyldiazenyl)aniline
(DPPPA) is a derivative of an azo dye. Reaction of DPPPA with [(tht)AuCl] (tht =
tetrahydrothiophene) in CH2Cl2 gave the dye functionalized bimetallic gold(I) complex
[DPPPA(AuCl)2]
(1).
The
second
ligand,
m-N,N,N‘,N‘-
tetrakis(diphenylphosphanyl)xylylenediamine, (DPPXA), has two {(Ph2P)2N} functional
groups in a xylylenediamine backbone. DPPXA was reacted with [(tht)AuCl] to give the
tetrametallic gold complex [DPPXA(AuCl)4] (2). Reaction of DPPXA with [(COD)MCl2] (M
= Pd, Pt) (COD = 1,5-cyclooctadiene) in DMSO resulted in the bimetallic palladium and
platinum complexes [DPPXA(MCl2)2] (M = Pd (3), Pt (4)). DPPPA and all metal complexes
were characterized by single crystal X-ray diffraction. The complexes demonstrate quite
different photophysical properties. Whereas no photoluminescence (PL) was detected for 1
and 4, complex 2 shows red PL in methylene chloride solution as well as in the solid state.
Near-infrared emission at ~800 nm was observed for complex 3 at temperatures below ~50 K.
______________________________________________________________________
Keywords: Chelates, Gold, Luminescence, Multimetallic compounds, Palladium,
Photoluminescence, Platinum, P-N-P Ligands

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Introduction
Gold chemistry is currently one of the rapidly growing fields of chemistry [1-6]. The
number of publications dealing with the application of gold and gold compounds in material
and surface sciences, in heterogeneous and especially in homogenous catalysis has recently
increased dramatically. This is mirrored by a significant number of reviews dealing with
various topics of gold chemistry [1, 7-34]. Molecular gold(I) compounds with a closed shell
d10 electronic configuration show a significant attractive interaction between the gold atoms
which are in most cases linearly two-fold coordinated. This fascinating phenomenon has been
described as “aurophilicity” and “aurophilic bonding” [1]. The Au-Au distance of these intra-
and intermolecular aurophilic contacts, which are a result of strong relativistic contractions
and low coordination numbers [27, 35], usually range in the area of 2.70 Å - 3.50 Å [1]. The
energies of such Au-Au interactions lie in the range of those of hydrogen bonds [36]. Besides
their influence on structural properties, aurophilic interactions also have an influence on the
photophysical properties of gold complexes [32]. Intramolecular aurophilic bonding is often
observed when phosphorus atoms are in close proximity in the ligand scaffold, enabling
intramolecular Au-Au interactions. In this context, bis(diphenylphosphino)methane (dppm)
and its derivatives play a vital role as bridging ligands (semi-supporting according to the
classification of Schmidbaur and Schier) [34] between two gold atoms enabling
intramolecular aurophilic bonds [34, 37]. Closely related to dppm is the isoelectronic
bis(diphenylphosphino)amine, [(Ph2P)2NH]. Derivatives of this compound [(Ph2P)2NR] can
be obtained in relatively facile approach by reacting a primary amine RNH2 with Ph2PCl in
the presence of a base [38]. Nevertheless, in comparison to dppm and its derivatives only few
gold(I) compounds with bis(diphenylphosphino)amine ligands are known [38-51]. Among
these compounds only one is known with two {(Ph2P)2N} functional groups in the ligand
[50].
Specifically,
four
gold
atoms
were
coordinated
to
2,6-

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bis(bis(diphenylphosphino)amino)pyridine forming [{(ClAuPh2P)2N}2C5H3N] which is stable
in the solid state only, but decomposes slowly in solution on exposure to air/moisture [50]. To
our knowledge, no other metal complexes with this ligand have been reported.
In this contribution we report on two new bi- and tetrametallic gold(I) complexes in which
the ligands bear one or two {(Ph2P)2N} functions in the backbone, respectively. Furthermore,
the new ligand with two {(Ph2P)2N} functions was also used for the synthesis of the related
palladium and platinum compounds.
Results and Discussion
Synthesis and Characterization: For our studies we envisaged to synthesize two new
ligands with {(Ph2P)2N} functions. The first ligand has one {(Ph2P)2N} function and a 4-
(phenyldiazenyl)aniline backbone. 4-(phenyldiazenyl)aniline is a yellow azo dye also known
as “aniline yellow”. This ligand was also envisaged as it may introduce the
photoisomerisation functionality of the azobenzene group [52] to optical properties of a metal
complex. The synthesis of the {(Ph2P)2N} functionalized azo dye N,N,-
bis(diphenylphosphanyl)-4-(phenyldiazenyl)aniline (DPPPA) was achieved by reaction of 4-
(phenyldiazenyl)aniline with chlorodiphenylphosphane in a 1: 2 ratio in the presence of NEt3
which acts as a base (Scheme 1). To the best of our knowledge no similarly functionalized
dye is known. DPPPA has been characterized by standard analytical / spectroscopic
techniques and the solid-state structure was established by single crystal X-ray diffraction.

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Scheme 1. Synthesis of the ligand DPPPA.
1
The resonances of the 29 aromatic protons in the H NMR spectrum were detected in the
31
range between δ 6.89 and 7.89 ppm. One signal is seen in the P{1H} NMR at δ 69.0 ppm
which is nearly identical with the one reported for [(Ph2P)2NPh] (68.6 ppm) [53]. DPPPA
crystallizes in the triclinic space group P-1. The diazo function has E configuration. The
bonding parameters are in the expected range. Thus, the P-N bond distances of P1-N1
1.737(2) Å and P2-N1 1.732(2) Å are in the range of the corresponding distances in
[(Ph2P)2NPh] (P-N 1.7315(15) Å) [54].
Further reaction of DPPPA with [(tht)AuCl] (tht = tetrahydrothiophene) in CH2Cl2 gave the
dye functionalized bimetallic gold(I) complex [DPPPA(AuCl)2] (1) as orange crystals
(Scheme 2). Once crystallized, 1 is surprisingly poorly soluble in common organic solvents
(e.g. THF, CH2Cl2, chloroform, acetonitrile, DMSO). The signals of the 29 aromatic protons
were observed in the range between δ 7.84 and 6.46 ppm in the 1H NMR spectrum. The signal
of the lattice bound methylene chloride was detected at δ 5.33 ppm. In the 31P{1H} NMR
spectrum one signal at δ 88.3 ppm was seen which is 19.3 ppm down field with respect to the
free ligand.

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Scheme 2. Synthesis of 1.
Compound 1 crystallizes in the monoclinic space group P21/n with four molecules of 1 and
two molecules of CH2Cl2 in the unit cell (Figure 2). As observed for DPPPA the azo function
adopts E configuration. The gold atoms are in a typically linear coordination mode with bond
angles of P1-Au1-Cl1 175.04(9)° and P2-Au2-Cl2 176.15(9)°. Moreover a close Au-Au
contact of 3.0095(7) Å which is characteristic for an aurophilic interaction is observed [1].
The observed Au-Au distance is slightly shorter than in the compounds [(ClAuPh2P)2N-C6H4-
4-Br] (3.0402(5) Å) [40] and 5-[N,N-bis(diphenylphosphanyl-κP:κP’)-amino]isophthalate}-
bis[chlorogold(I)] (3.0593(7) Å) [38].
To obtain a ligand with two {(Ph2P)2N} functional groups in the scaffold we chose
xylylenediamine as rigid backbone. Using a benzyl functionalized ligand in which the
{(Ph2P)2N} functional groups are not directly attached to the benzene ring gives a system with
a better solubility. This has a significant advantages in comparison to e.g.
bis(bis(diphenylphosphino)amino)pyridine [50]. The synthesis of the new ligand m-
N,N,N‘,N‘-tetrakis(diphenylphosphanyl)xylylenediamine (DPPXA) was achieved by reacting
xylylenediamine with chlorodiphenylphosphane in a 1: 4 ratio in the presence of a base
1
13
(Scheme 3). DPPXA was characterized by H, C{1H} and 31P{1H} NMR, IR and Raman
1
spectroscopy. A characteristic triplet is observed for the benzyl protons in the H NMR

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spectrum at δ 4.30 ppm. Moreover, the signals of the xylylene ring form a characteristic
3
pattern which consists of triplet (6.87 ppm, JHH = 7.6 Hz), a double doublet (6.63 ppm; 3JHH
31
= 7.7 Hz), and a singlet (6.44 ppm). One signal was detected in the P{1H} NMR at δ 59.5
ppm which is in the range of [{(Ph2P)2N}2C5H3N] (59.0 ppm) [55] but differs by about 10
ppm from the value of the corresponding phenyldiamine derivative 1,3-{(Ph2P)2N}2C6H4 [56].
Scheme 3. Synthesis of the ligand DPPXA.
DPPXA was further reacted with suitable gold(I), palladium(II), and platinum(II)
complexes. Reaction of DPPXA with [(tht)AuCl] in CH2Cl2 resulted in the desired
tetrametallic gold complex [DPPXA(AuCl)4] (2) (Scheme 4). The new complex has been
1
characterized by standard analytical/spectroscopic techniques. The H and 31P{1H} spectra
show the expected set of signals. Only broadened signals were seen in the 1H NMR spectrum
but a sharp signal at δ 78.8 ppm is observed in the 31P{1H} NMR which is about 20 ppm
downfield shifted in comparison to the free ligand DPPXA. In comparison to the diamino
pyridine based gold complex [{(ClAuPh2P)2N}2C5H3N] 2 seems to be significantly more
stable in solution [50]. In contrast to [{(ClAuPh2P)2N}2C5H3N] single crystals of 2 suitable
for X-ray diffraction could be obtained. Compound 2 crystallizes in the monoclinic space
group C2/c with four molecules of 2 and eight molecules of chloroform in the unit cell. A
crystallographic C2-axis is observed in the center of the xylylene ring along C1 and C4. As
seen in the unsubstituted P-N-P gold compound [(ClAuPh2P)2NH] [51] and in the
bromophenyl P-N-P gold compound [(ClAuPh2P)2N-C6H4-4-Br] [40] the gold atoms in 2 are
almost linearly coordinated exhibiting a twofold coordination mode typical for Au(I) (e.g. P1-

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Au1-Cl1 176.98(8)°). Moreover, an intramolecular aurophilic interaction is indicated with a
Au1-Au2 distance of 3.5257(6) Å. This distance which falls into the upper limit of an
aurophilic interaction [1] is about 0.5 Å longer than in compound 1. The chlorine atom Cl2 is
disordered. The Au-P distances are in the expected range of Au1-P1 2.225(2) Å and Au2-P2
2.230(2) Å.
Scheme 4. Synthesis of 2.
Reacting DPPXA with [(COD)PdCl2] (COD = 1,5-cyclooctadiene) in DMSO resulted in
the bimetallic palladium complex [DPPXA(PdCl2)2] (3) (Scheme 5). As expected each
{(Ph2P)2N} function coordinates in a chelating fashion to one metal atom. Although
numerous palladium complexes which are coordinated to {(Ph2P)2N} function are known
there are to the best of our knowledge only one bimetallic {(Ph2P)2N} palladium complexes
known in which the two metal atoms are bound to one rigid backbone. In this complex, [1,3-
{cis-PdCl2(PPh2)2N}2C6H4], the metal atoms are ligated by N,N,N’,N’-tetrakis-
1
(diphenylphosphanyl)-1,3-diaminobenzene [57]. In the H NMR spectrum of compound 3 a
well resolved triplet was observed for the benzyl group at δ 4.13 ppm (3JHP = 13.0 Hz). In
31
comparison to the free ligand this signal is slightly upfield shifted. In the P{1H} NMR one
signal is observed at δ 30.9 ppm. In contrast to 2 which shows a downfield shift of this signal
in comparison to DPPXA an upfield shift was seen in 3.

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Scheme 5. Synthesis of 3 and 4.
Compound 3 crystallizes in the monoclinic space group P21/n (Figure 6). In the bimetallic
compound each metal center is four-fold coordinated. Two phosphorus atoms from one
{(Ph2P)2N} function and two chlorine atoms form a square planar arrangement. This kind of
coordination mode is typically observed in comparable compounds such as
[Cl2Pd{(Ph2P)2N2C6H4-4-Br}],
[40]
[Cl2Pd{(Ph2P)2N-C6H4-2-Et}]
[58],
and
[Cl2Pd{(Ph2P)2N-benzyl}] [59]. The observed Pd-P bond length of Pd1-P1 2.1996(9) Å, Pd1-
P2 2.2214(9) Å, Pd2-P3 2.2191(9) Å, and Pd2-P4 2.2032(9) Å are in the expected range [40,
57-59].
By applying similar conditions as used for the reaction of 3, treatment of DPPXA with
[(COD)PtCl2] in DMSO resulted in the bimetallic platinum complex [DPPXA(PtCl2)2] (4)
(Scheme 5). Compound 4 was fully characterized by standard analytical /spectroscopic
1
techniques. In the H NMR spectrum the expected signals are well resolved. Most
characteristic are the singlet of the central phenyl ring at δ 5.56 and the triplet of the benzyl
group at δ 4.05 (3JHP = 13.4 Hz). The chemical shifts are in a comparable range to compound
4. As a result of the 195Pt nucleus, characteristic platinum satellites were observed in the
31P{1H} NMR spectrum at δ 16.7 ppm (1JPtP = 3282 Hz). The corresponding triplet in the 195Pt
NMR was detected at δ 4032 ppm. Single crystals of compound 4 could be obtained from the
mother liquor (Figure 5). In the solid state compound 4 which crystallizes in the monoclinic
space group P21/n is isostructural to compound 3. Thus, one square planar coordinated metal
atom is bound to each of the two {(Ph2P)2N} functions. Unfortunately, only crystals of low

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quality were obtained. Although, the X-ray data collected from 4 was poor the connectivity of
4 and its composition were deduced. However, further bonding parameters cannot be
discussed.
Figure 5 here
Photophysical Properties: The solid-state absorption spectrum of deeply colored complex
1 is closely related to those of the aniline yellow azo dye and its DPPPA derivative (Figure 6).
The onset of absorption at ~550 nm is apparently determined by the phenyldiazenyl moiety in
these compounds. In general, gold(I) complexes show moderate-to-intense
photoluminescence (PL) in particular at low (cryogenic) temperatures. In contrast, no
emission was detected for solid complex 1 at temperatures varying between 18 and 293 K.
We roughly estimate the upper limit of PL quantum yield of 1 to be less than ~10-6. The
absence of PL can be attributed to very efficient (fast) non-radiative electronic relaxation via
the phenyldiazenyl moiety. Such relaxation is well documented for azobenzene and its
derivatives and has been related to rotational motions along the azo bond [60-63]. The
photophysical properties of 1 in solution, including its possible photoisomerisation, were not
investigated because of the very poor solubility of 1 in the solvents probed (see above).
In difference to 1, complex 2 absorbs light below ~400 nm and shows PL in a methylene
chloride solution as well as in the solid state (Figure 7). The emission band A at ~470 nm is
especially prominent at temperatures below ~150 K. It decays on the time scale of
nanoseconds (upper bound estimate) and can tentatively be attributed to fluorescence of the
xylylenediamine, i.e. ligand backbone, moiety. The blue fluorescence has also been observed
for xylylenediamine polymer derivatives [64]. The red-near-infrared emission B at ~700 nm is

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relatively weak but dominates at ambient temperature. The width of band B indicates that
several emissive excited states/configurations may be involved. The emission B decays within
a few microseconds at ambient temperature and tens of microseconds at T = 18 K
(biexponential fits were used) and can be assigned to phosphorescence of the
{(ClAuPh2P)2N} core. A similar weak emission band at 650 nm is also observed for dissolved
complex 2 (Figure 7). The low energy of the emission B is likely related to Au-Au
intramolecular interaction in photoexcited 2 [65, 66].
Figures 6 and 7 here
Similar to 1, no luminescence was detected from solid Pt-complex 4 at temperatures
varying between 18 and 293 K. The photophysical properties of homologous Pd and Pt
complexes typically correlate well [67, 68]. However, in contrast to non-luminescent 4, Pd-
complex 3 shows near-infrared PL centered at ~800 nm at temperatures below ~50 K (Figure
8). The emission lifetime is about 20 µsec at T = 18K. The PL intensity is relatively weak in
comparison to complex 2 and decreases quickly by increasing the temperature above ~50 K.
Such low-energy emission might be contributed by collective (excimeric) excitations in the
solid state of 3. Its assignment requires further investigations.
Figure 8 here

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Summary
In summary, three bimetallic complexes of gold, palladium, and platinum as well as a
tetrametallic gold complex have been synthesized and structurally characterized. The
photophysical properties of all metal complexes were determined. Reaction of DPPPA, a
derivative of an azo dye, with [(tht)AuCl] gave the dye functionalized bimetallic gold(I)
complex
[DPPPA(AuCl)2]
(1).
The
second
ligand,
m-N,N,N‘,N‘-
tetrakis(diphenylphosphanyl)xylylenediamine, has two {(Ph2P)2N} functional groups in the
scaffold of a xylylenediamine backbone. Reaction of DPPXA with [(tht)AuCl] gave the
tetrametallic gold complex [DPPXA(AuCl)4] (2). Treatment of DPPXA with [(COD)MCl2]
(M = Pd, Pt) (COD = 1,5-cyclooctadiene) in DMSO resulted in the bimetallic palladium and
platinum complexes [DPPXA(MCl2)2] (M = Pd (3), Pt (4)]. In difference to 1 and 4, which
show no detectable PL, complex 2 is luminescent in solution and especially in the solid state.
Its red emission at ~650-700 nm may indicate the effect of Au-Au intramolecular interaction.
In difference to the homologous Pt-complex 4, Pd-complex 3 shows near-infrared PL at ~800
nm in the solid state at temperatures below ~50 K.
Experimental Section
Although all products are not very air sensitive all manipulations of air-sensitive materials
were performed with the rigorous exclusion of oxygen and moisture in flame-dried Schlenk-
type glassware either or in an argon-filled MBraun glove box. THF was distilled under
nitrogen from potassium benzophenone ketyl prior to use. Hydrocarbon solvents (toluene and
n-pentane) were dried using an MBraun solvent purification system (SPS-800). All solvents
for vacuum line manipulations were stored in vacuo over LiAlH4 in resealable flasks.
Deuterated solvents were obtained from Aldrich (99 atom % D) and were degassed, dried, and
stored in vacuo over Na/K alloy in resealable flasks. NMR spectra were recorded on a Bruker
Avance II 300 MHz and a Bruker Avance 500 MHz FT-NMR spectrometer. Chemical shifts

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are referenced to internal solvent resonances and are reported relative to tetramethylsilane. IR
spectra were obtained on a Bruker Tensor 34 or a Perkin Elmer Spectrum GX. Raman spectra
were carried out with a Bruker MultiRAM. Mass spectra were recorded at 70 eV on a
Finnigan MAT 8200 and a Thermo Scientific DFS. Elemental analyses were carried out with
an Elementar Vario EL. [(tht)AuCl] [69, 70] (tht = tetrahydrothiophene) was prepared
according to modified standard procedures. UV-Vis spectra were obtained on a Varian Cary
50 Spectrophotometer. Solid state absorption spectra were measured using a Labsphere
integrating sphere. Photoluminescence (PL) spectra were recorded on a Horiba JobinYvon
Fluorolog-322 spectrometer equipped with Hamamatsu R9910 and R5509 photomultipliers
(PMT) as detectors for the spectral range of ~250-800 nm and ~450-1400 nm, respectively.
Solid samples were placed into a closed-cycle optical cryostat (Leybold) and measured at
temperatures varying between 293 K and 18 K. The emission spectra were corrected for the
wavelength-dependent response of the spectrometer and detector (in relative photon flux
units). PL decay traces were recorded by connecting a PMT to an oscilloscope and using a
nitrogen laser for a pulsed excitation at 337 nm (with pulses of ~2 nsec duration and ~5 µJ
energy).
Synthesis of N,N,-Bis(diphenylphosphanyl)-4-(phenyldiazenyl)aniline (DPPPA).
3.94 g (20 mmol) of 4-Aminoazobenzene were dissolved in 100 mL of toluene. Then, 5.6 mL
(40 mmol) NEt3 are added to the mixture. At 0 °C 7.2 mL (40 mmol) of freshly distilled
Ph2PCl were added dropwise. After stirring for 14 h at room temperature the resulting
colorless precipitate (HNEt4Cl) was filtered off and washed twice with 10 mL of toluene. The
filtrate was brought under reduced pressure to dryness yielding a yellow powder which was
recrystallized from toluene/-hexane (1:3). Yield 8.5 g (15 mmol, 75 %) Suitable crystals for

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X-ray structure analysis were best grown by layering a toluene solution with n-hexane. Anal.
Calcd C36H29N3P2 - C 76.45, H 5.17, N 7.43, found C 76.29, H 5.30, N 7.44.
3
1H NMR (500 MHz, CDCl3): δ 7.88 (d, 3JHH = 7.6, 2H), 7.59 (d, JHH = 8.7, 2H), 7.54-7.49
3
31
(m, 2H), 7.44-7.49 (m, 9H), 7.40-7.29 (m, 12H), 6.89 (d, JHH = 8.6, 2H). - P{1H} NMR
(202.47 MHz, CDCl3): δ 69.0. - IR (FT, KBr, cm-1): 3049 (w), 2926 (w), 2854 (w), 2499 (w),
2354 (w), 1960 (w), 1890 (w), 1635 (w), 1592 (m), 1492 (m), 1479 (m), 1435 (m), 1430 (m),
1385 (w), 1306 (w), 1281 (w), 1224 (m), 1215 (s), 1183 (w), 1152 (w), 1121 (w), 1092 (m),
1070 (w), 1026 (w), 996 (w), 951 (w), 918 (w), 896 (s), 827 (w), 770 (m), 751 (m), 741 (s),
726 (m), 694 (vs), 686 (s), 668 (w), 639 (w), 569 (w), 556 (m), 521 (w), 507 (m), 483 (w),
466 (m), 421 (w).
Synthesis
of
[N,N,-Bis(diphenylphosphanyl)
κP:κP’-4-(phenyldiazenyl)aniline-
bischlorogold(I)] ([DPPPA(AuCl)2], 1)
A solution of 0.42 g (0.75 mmol) of DPPPA in 15 mL of CH2Cl2 was added to a solution of
0.48 g (1.50 mmol) of [(tht)AuCl] in 10 mL CH2Cl2. After stirring for 1 hour the reaction
mixture was stored at +4 °C for 14 hours leading to the crystallization of orange blocks of 1 ·
½CH2Cl2. Reduction of the volume of the mother solution led to further crystals. After
filtration and washing with small amounts of dichloromethane and diethylether the product
was dried in vacuum. Single crystals were obtained from CDCl3 in a NMR tube. Yield: 0.61 g
(0.57 mmol, 76 %). Anal. Calcd C36.5H30Au2Cl3N3P2 - C 40.86, H 2.82, N 3.92, found C
40.29, H 2.73, N 3.89.
1H NMR (500 MHz, CDCl3): δ 7.84-7.80 (m, 2H), 7.74-7.67 (m, 7H), 7.60-7.55 (m, 2H),
3
3
7.52-7.44 (m, 12H), 7.36 (d, JHH = 8.6 Hz, 2H), 6.46 (d, JHH = 8.2, 2H), 5.33 (s, 1H, ½
CH2Cl2) - 31P{1H} NMR (202.47 MHz, CDCl3): δ 88.3 ppm. - IR (FT, KBr, cm-1): 3052 (w),

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3015 (w), 2976 (w), 2865 (w), 2199 (w), 1967 (w), 1894 (w), 1813 (w), 1774 (w), 1584 (w),
1481 (m), 1435 (m), 1334 (w), 1305 (w), 1221 (w), 1283 (w), 1263 (w), 1220 (w), 1190 (m),
1155 (m), 1101 (s), 1071 (m), 998 (m), 961 (m), 940 (s), 899 (s), 772 (m), 747 (s), 690 (w),
586 (m), 568 (m), 541 (m), 512 (m), 480 (m).
Synthesis of m-N,N,N‘,N‘-Tetrakis(diphenylphosphanyl)xylylenediamine (DPPXA)
0.66 ml (0.681 g, 5 mmol) of m-xylylenediamine and 2.8 ml (2.02 g, 20 mmol) of
triethylamine were dissolved in 50 ml of CH2Cl2. To this solution 3.6 mL (4.41 g, 20 mmol)
of chlorodiphenylphosphane in 10 mL CH2Cl2 were added dropwise under stirring at 0 °C
over a period of 30 min. A colorless precipitate was formed. After warming to ambient
temperature the reaction mixture was stirred for 16 hours. The solution was evaporated and
the remaining residue was extracted with THF (3 × 10 ml). The solvent of the extract was
evaporated and the remaining residue was subsequently dried in vacuo for 3 hours. The
product was obtained as a colorless powder. Yield: 4.06 g (93%). Anal. Calcd C56H48N2P4 -
C 77.05, H 5.54, N 3.21, found C 76.82, H 5.80, N 3.28.
1H NMR (300.13 MHz, CDCl3): δ 7.41-7.33 (m, 16H, PPh), 7.33-7.25 (m, 24H, PPh), 6.87 (t,
3JHH = 7.6 Hz, 1H, CH), 6.63 (dd, 3JHH = 7.7, 1.3 Hz, 2H, CH), 6.44 (s, 1H, CH), 4.30 (t, 3JHP
= 10.5 Hz, 4H, CH2). - 31P{1H} NMR (121.48 MHz, CDCl3): δ 59.5. - IR (ATR, cm-1): 3047
(w), 2898 (w), 2864 (w), 1586 (w), 1478 (m), 1432 (m), 1347 (w), 1308 (w), 1181 (w), 1162
(w), 1090 (m), 1034 (m), 1013 (w), 982 (m), 894 (w), 875 (m), 822 (s), 795 (m), 740 (vs), 693
(vs), 624 (w), 613 (w), 571 (w), 558 (w), 519 (m). - Raman (solid state, cm-1): 3051 (m), 1586
(m), 1180 (w), 1156 (w), 1093 (m), 1027 (m), 1000 (s), 671 (w), 618 (w), 266 (w), 218 (m),
210 (m). - EI-MS (70 eV): m/z (%) = 872 ([M]+, <1), 688 ([M - PPh2]+, <1), 386 ([N(PPh2)2]+,
75), 504 ([M - N(PPh2)2]+, 1), 183 ([M - 2(N(PPh2)2)]+, 91), 106 ([C8H9]+, 48), 77 ([Ph]+, 64).

ACCEPTED MANUSCRIPT
Synthesis
of
[m-N,N,N’,N’-Tetrakis(diphenylphosphanyl)-κP:κP’:κP’’:κP’’’-
xylylenediaminetetrakischlorogold(I)] ([DPPXA(AuCl)4], 2)
0.32 g (1.00 mmol) of chloro(tetrahydrothiophene)gold(I) were dissolved in 25 ml of CH2Cl2.
0.22 g (0.25 mmol) of m-N,N,N‘,N‘-tetrakis(diphenylphosphanyl)xylylendiamine were added
under stirring. The mixture was stirred for 1 hour at ambient temperature. The solution was
then evaporated. The remaining residue was washed with diethylether (3 × 10 ml) and
subsequently dried in vacuo. The product was obtained as a colorless powder. Yield: 0.41 g
(90 %). Anal. Calcd C56H48Au4Cl4N2P4 ·2CH2Cl2 - C 35.32, H, 2.66, N, 1.42, found C 34.93,
H 3.44, N 1.08.
1H NMR (300.13 MHz, CDCl3): δ 7.84-7.64 (br, m, 16H, Ph), 7.64-7.40 (br, m, 20H, Ph),
6.46-6.39 (br, m, 1H, Ph), 6.28-6.18 (br, m, 1H, Ph), 6.07-5.94 (br, m, 2H, Ph), 4.78-4.54 (br,
m, 4H, CH2). - 31P{1H} NMR (121.49 MHz, CDCl3): δ 78.8. - IR (ATR, cm-1): 2963 (m),
1480 (w), 1435 (m), 1310 (w), 1260 (s), 1154 (w), 1097 (vs), 1015 (vs), 878 (w), 797 (vs),
746 (m), 689 (s), 580 (w), 535 (m). - Raman (solid state, cm-1): 3056 (m), 2910 (m), 1586
(m), 1186 (w), 1161 (w), 1101 (w), 1027 (m), 1000 (s), 705 (w), 618 (w), 331 (m), 264 (m),
193 (w). - FAB-MS: m/z (%) = 1767 ([M - Cl]+, 100), 1534 ([M - (AuCl2)]+, 24), 1117 ([M -
(PPh2AuCl2)]+, 28).
Synthesis
of
[m-N,N,N’,N’-Tetrakis(diphenylphosphanyl)-κ2P,P’:κ2P’’,P’’’-
xylylenediaminetetrakisdichloropaladium(II)] ([DPPXA(PdCl2)2], 3)
0.14 g (0.5 mmol) of dichloro(1,5-cyclooctadiene)palladium(II) were dissolved in 5 ml of
DMSO. 0.22 g (0.25 mmol) of m-N,N,N‘,N‘-tetrakis(diphenylphosphanyl)xylylendiamine
were added under stirring. The mixture was heated to 100 °C and stirred for 1 hour. After

ACCEPTED MANUSCRIPT
cooling down to ambient temperature the product was obtained as yellow crystals. Yield: 0.23
g (75 %). Anal. Calcd C56H48Cl4N2P4Pd2· 1.5C2H6OS - C 52.70, H 4.27, N 2.08, S 3.58, found
C 52.40, H 4.18, N 2.07, S 2.97.
1H NMR (300.13 MHz, DMSO): δ 7.77-7.62 (m, 24H, Ph), 7.61-7.51 (m, 16H, Ph), 6.00 (t,
3JHH = 7.6 Hz, 1H, CH), 5.78 (d, 3JHH = 9.2 Hz, 2H, CH), 5.58 (s, 1H, CH), 4.13 (t, 3JHP = 13.0
Hz, 4H, CH2). - 31P{1H} NMR (121.49 MHz, DMSO): δ (ppm) = 30.9. - IR (ATR, cm-1):
3057 (w), 3001 (w), 2913 (w), 1480 (m), 1434 (s), 1306 (m), 1184 (w), 1162 (m), 1098 (vs),
1053 (s), 1023 (m), 991 (s), 894 (m), 842 (m), 801 (s), 749 (s), 720 (m), 690 (vs), 659 (m),
567 (m), 509 (s). - FAB-MS: m/z (%) = 1193 ([M - Cl]+, 100), 1156 ([M - 2Cl]+, 62), 1120
([M - 3Cl]+, 50).
Synthesis
of
[m-N,N,N’,N’-Tetrakis(diphenylphosphanyl)-κ2P,P’:κ2P’’,P’’’-
xylylenediaminetetrakisdichloroplatinum(II)] ([DPPXA(PtCl2)2], 4)
0.11g (0.3 mmol) of dichloro(1,5-cyclooctadiene)platinum(II) were dissolved in 3 ml of
DMSO. 0.13 g (0.15 mmol) of m-N,N,N‘,N‘-tetrakis(diphenylphosphanyl)xylylendiamine
were added under stirring. The mixture was heated to 100 °C and stirred for 1 hour. After
cooling down to ambient temperature the product was obtained as pale yellow crystals. Yield:
0.15 g (70 %). Anal. Calcd C56H48Cl4N2P4Pt2 ·1.5C2H6OS - C 46.56, H 3.77, N 1.84, S 3.16,
found C 46.54, H 3.68, N 1.84, S 2.61.
1H NMR (300.13 MHz, DMSO): δ 7.74-7.59 (m, 24H, Ph), 7.58-7.51 (m, 16H, Ph), 5.97 (t,
3JHH = 7.6 Hz, 1H, CH), 5.76 (d, 3JHH = 7.6 Hz, 2H, CH), 5.56 (s, 1H, CH), 4.05 (t, 3JHP = 13.4
31
1
Hz, 4H, CH2) - P{1H} NMR (121.49 MHz, DMSO): δ (ppm) = 16.7 (s and d, JPtP = 3282
1
Hz). - 195Pt NMR (86.02 MHz, DMSO): δ (ppm) = 4032 (t, JPtP = 3282 Hz). - IR (ATR, cm-
1): 3058 (w), 2921 (m), 2852 (m), 1480 (w), 1457 (w), 1434 (s), 1306 (m), 1264 (w), 1183

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(w), 1162 (m), 1100 (vs), 1053 (s), 1024 (m), 990 (s), 950 (w), 893 (m), 839 (s), 798 (s), 748
(s), 721 (s), 691 (vs), 661 (s), 574 (s), 518 (s). - Raman (solid state, cm-1): 3060 (s), 3006 (w),
2909 (m), 1587 (s), 1186 (w), 1161 (w), 1101 (m), 1027 (m), 1000 (vs), 617 (w), 580 (w), 331
(w) 302 (m), 270 (w), 232 (w), 217 (m), 193 (m). - FAB-MS: m/z (%) = 1405 ([M]+, 5), 1370
([M - Cl]+, 100).
X-ray Crystallographic studies of DPPPA and 1-3: Single crystals were grown as
described in the synthetic procedures of each compound. Suitable crystals were covered in
mineral oil (Aldrich) and mounted onto a glass fiber. Data were collected on diffractometer
equipped with a STOE imaging plate detector system IPDS2 using MoKα radiation with
graphite monochromatization (λ = 0.71073 Å) at low temperatures. Subsequent computations
were carried out on an Intel Core2Quad. Structure solution was performed by direct methods;
full-matrix-least squares refinement against F2 using SHELXS-97 and SHELXL-97 software
[71]. Figures 1-5 were generated using the program Diamond3.2 [72].
Crystal data for DPPPA: C36H29N3P2, M = 565.56, triclinic, a = 11.1761(6) Å, b = 11.1965(6)
Å, c = 14.1318(7) Å, α = 99.258(4)°, β = 103.902(4)°, γ = 115.270(4)°, V = 1480.74(13) Å3, T
= 180(2) K, space group P-1, Z = 2, ꢀ(MoKα) = 0.177 mm-1, 10061 reflections measured,
5216 independent reflections (Rint = 0.1397). The final R1 values were 0.0575 (I > 2σ(I)). The
final wR(F2) values were 0.2036 (all data). The goodness of fit on F2 was 1.168.
Crystal data for 1: C36.50H30Au2Cl3N3P2, M = 1072.86, monoclinic, a = 10.177(2) Å, b =
26.446(5) Å, c = 13.202(3) Å, β = 96.31(3)°, V = 3531.7(12) Å3, T = 120(2) K, space group
P21/n, Z = 4, ꢀ(MoKα) = 8.647 mm-1, 16400 reflections measured, 6522 independent
reflections (Rint = 0.0701). The final R1 values were 0.0470 (I > 2σ(I)). The final wR(F2)
values were 0.0768 (all data). The goodness of fit on F2 was 0.989.

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Crystal data for 2: C58H50Au4Cl10N2P4, M = 2041.25, monoclinic, a = 19.742(4) Å, b =
18.125(4) Å, c = 20.570(4) Å, β = 112.74(3)°, V = 6788(2) Å3, T = 200(2) K, space group
C2/c, Z = 4, ꢀ(MoKα) = 9.143 mm-1, 21679 reflections measured, 6243 independent
reflections (Rint = 0.0673). The final R1 values were 0.0416 (I > 2σ(I)). The final wR(F2)
values were 0.1092 (all data). The goodness of fit on F2 was 1.044.
Crystal data for 3: C58H54Cl4N2OP4Pd2S, M = 1305.57, monoclinic, a = 17.1159(7) Å, b =
16.2598(5) Å, c = 20.7904(8) Å, β = 96.553(3)°, V = 5748.2(4) Å3, T = 150(2) K, space group
P21/n, Z = 4, ꢀ(MoKα) = 1.000 mm-1, 65134 reflections measured, 12547 independent
reflections (Rint = 0.0831). The final R1 values were 0.0447 (I > 2σ(I)). The final wR(F2)
values were 0.0978 (all data). The goodness of fit on F2 was 1.037.
Crystallographic data (excluding structure factors) for the structures reported in this paper
have been deposited with the Cambridge Crystallographic Data Centre as a supplementary
publication no. CCDC-927333 (DPPPA), 927334 (1), 927335 (2), 927336 (3). Copies of the
data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge
CB21EZ, UK (fax: (+(44)1223-336-033; email: deposit@ccdc.cam.ac.uk).
Acknowledgements
This work was supported by the DFG-funded transregional collaborative research center
SFB/TRR 88 “Cooperative effects in homo- and hetero-metallic complexes (3MET)”. C.S.
thanks the Konrad-Adenauer-Stiftung for a doctoral fellowship. O.F. is grateful to Sven Stahl
for his assistance with the analytics.
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Figure Captions
Figure 1. Solid-state structure of DPPPA, omitting hydrogen atoms [72]. Selected bond
lengths [Å] and angles [°]: P1-N1 1.737(2), P2-N1 1.732(2), N2-N3 1.247(3); P1-N1-P1
120.72(11).
Figure 2. Solid-state structure of 1, omitting hydrogen atoms [72]. Selected bond lengths [Å]
and angles [°]: Au1-P1 2.236(3), Au1-Cl1 2.290(2), Au1-Au2 3.0095(7), Au2-P2 2.235(2),
Au2-Cl2 2.285(2), P1-N1 1.696(8), P2-N1 1.712(7), N2-N3 1.270(11); P1-Au1-Cl1
175.04(9), P1-Au1-Au2 85.60(6), Cl1-Au1-Au2 99.12(7), P2-Au2-Cl2 176.15(9), P2-Au2-
Au1 85.58(6), Cl2-Au2-Au1 98.09(7), P1-N1-P2 123.4(4).
Figure 3. Solid-state structure of 2, omitting hydrogen atoms [72]. Selected bond lengths [Å],
angles [°] or torsion angles [°]: Au1-Cl1 2.288(2), Au2-Cl2B 2.323(6), Au1-P1 2.225(2),
Au2-P2 2.230(2), N-P1 1.703(6), N-P2 1.717(6), Au1-Au2 3.5257(6); P1-Au1-Cl1 176.98(8),
N-P1-Au1 109.0(2), N-P2-Au2 112.4(2), P1-N-P2 115.7(3), Cl1-Au1-Au2 106.68(6), P1-
Au1-Au2 75.69(6), P2-Au2-Au1 65.70(4); P1-Au1-Au2-P2 58.08(2).
Figure 4. Solid-state structure of 3, omitting hydrogen atoms [72]. Selected bond lengths [Å],
angles [°] or torsion angles [°]: Pd1-Cl1 2.3627(11), Pd1-Cl2 2.3464(9), Pd2-Cl3 2.3610(9),
Pd2-Cl4 2.3706(9), Pd1-P1 2.1996(9), Pd1-P2 2.2214(9), Pd2-P3 2.2191(9), Pd2-P4

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2.2032(9), N1-P1 1.699(3), N1-P2 1.696(3), N2-P3 1.698(3), N2-P4 1.692(3); Cl1-Pd1-Cl2
96.33(4), Cl3-Pd2-Cl4 96.57(3), P1-Pd1-P2 71.92(3), P3-Pd2-P4 71.43(3), Cl1-Pd1-P1
94.77(3), Cl2-Pd1-P2 97.24(4), Cl3-Pd2-P3 96.01(3), Cl4-Pd2-P4 96.38(3), Cl1-Pd1-P2
166.09(3), Cl2-Pd1-P1 168.29(4), Cl3-Pd2-P4 166.78(3), Cl4-Pd2-P3 166.05(3), Pd1-P1-N1
94.40(10), Pd1-P2-N1 93.70(10), Pd2-P3-N2 94.29(10), Pd2-P4-N2 95.02(10), P1-N1-P2
99.74(15), P3-N2-P4 99.19(14).
Figure 5. Solid-state structure of 4, omitting hydrogen atoms. As result of the low quality of
the collected data no bond lengths and angles are given.
Figure 6. UV-Vis solid state absorption spectra of aniline yellow, DPPPA and complex 1.
The spectra are vertically shifted for clarity.
Figure 7. Photoluminescence excitation (PLE) and emission (PL) spectra of 2 in the (a)
methylene chloride solution and (b) solid (polycrystalline) state. The PL and PLE spectra
were excited and recorded at 300 and 650 nm and 300 and 800 nm in (a) and (b), respectively.
The low-temperature PL of solid 2 is relatively bright and was recorded with the excitation
and emission monochromator slits set to 2 nm spectral width.
Figure 8. Photoluminescence excitation (PLE) and emission (PL) spectra of solid complex 3
cooled to 18 K. The PL and PLE spectra were excited and recorded at 350 and 750 nm,
respectively

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ACCEPTED MANUSCRIPT
Synthesis of ligands with one or two {(Ph2P)2N} functions in the backbone
Synthesis of bi- and tetrametallic gold complexes
Synthesis of bimetallic palladium and platinum complexes