Selective formation of a two-dimensional coordination polymer based on a tridentate phospholane ligand and gold(i)

Article abstract of DOI:10.1039/c8dt03630f

The tridentate phosphine ligand 1,3,5-tris[(E)-(4-phospholano-2,6-diethyl)styryl]benzene (1) reacts with [AuCl(tht)] (tht = tetrahydrothiophene) independent of the stoichiometry employed with selective formation of a two-dimensional coordination polymer (

Full text of DOI:10.1039/c8dt03630f

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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Selective formation of a two-dimensional coordination polymer
based on a tridentate phospholane ligand and gold(I)†‡
Reinhard Hoy,a Peter Lönneckea and Evamarie Hey-Hawkinsa,*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The tridentate phosphine ligand 1,3,5-tris[(E)-(4-phospholano-2,6-diethyl)styryl]benzene (1) reacts with [AuCl(tht)]
independent of the stoichiometry employed with selective formation of a two-dimensional coordination polymer (ratio
1:1) with the gold(I) cations in a trigonal-planar [3 + 1] coordination geometry. Each of the three coordinating phosphine
units originates from another ligand, thus forming a polymeric structure.
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expected to coordinate in a similar fashion as the bidentate
Introduction
ligands, forming sandwich-type structures (Fig. 1).
P
Supramolecular Coordination Complexes (SCCs) have been
defined by Cohen as “clusters, which combine polydentate
organic ligands and transition metals to form elegant
assemblies held together by reversible metal-ligand bonds”.1
These compounds are of special interest for applications in
sensing, inclusion and transformation of small molecules as
well as catalysis.2,3 Even though extensive research has been
conducted over the past decades, examples for SCCs
containing phosphine ligands are scarce. Phosphines are prone
to oxidation and therefore require more synthetic effort and
careful handling. Furthermore, due to rotation around the P–C
bond, different orientations of the lone pairs of electrons of
the phosphines with respect to each other and to the
orientation of the ligand are possible, resulting in a lower
predictability and selectivity of the formed SCC.4 Examples for
selectively formed SCCs include macrocycles,5–9,9–20
tetrahedra,1,21,22 helicates,1,8,23,24 and polymeric structures8,25
based on phosphines and gold(I).
P
Au
P
P
Au
P
P
Au
P
Au
P
P
Au
P
ring structure
sandwich-type structure
Fig. 1 Schematic representation of a dimetallamacrocycle (left)26 and the intended
sandwich-type structure (right) based on gold(I). Counterions are omitted for clarity.
Since conjugated polyaromatic systems often suffer from
solubility issues, ethyl groups were incorporated in the
backbone. For compound 1a, a crystal structure could be
obtained (Table 1), confirming the intended geometry of an
almost perfect isosceles triangle with the bromine atoms at
the edges (distances Br(1)···Br(2) 1.67 nm, Br(2)···Br(3) 1.71
nm, Br(3) ···Br(1) 1.74 nm; Br(2)-Br(1)-Br(3) angles 57.83 to
61.80°). In order to obtain a sandwich-type structure, 1 was
reacted with [AuCl(tht)]27 in a 3:2 [M:L] molar ratio in
dichloromethane.
Br
1) NaH
2)
O
Br
Results and discussion
(EtO)2OP
PO(OEt)2
Recently, we have reported the systematic investigation of
flexible bis-phospholane ligands of different chain lengths and
the selective formation of dimetallamacrocycles, nanotubes
and polymeric chain structures.26 In order to extend the ring
structure of the dimetallamacrocycles to the third dimension,
Br
45%
PO(OEt)2
1) n-BuLi
2)
Br
P
Cl
1a
P
99%
a new tridentate ligand
1 with a semi-rigid backbone allowing
P
a certain degree of flexibility was developed (Scheme 1) and
P
P
=
a.Faculty of Chemistry and Mineralogy, Institute of Inorganic Chemistry, Leipzig
University, D-04103 Leipzig, Germany. E-mail: hey@uni-leipzig.de
† Dedicated to Professor Werner Uhl on the occasion of his 65th birthday.
‡ Electronic Supplementary Information (ESI) available: Assigned NMR spectra of all
P
P
new compounds, crystallographic details for 1a and
measurements of . See DOI: 10.1039/x0xx00000x.
2, and TGA/DSC
1
2
Scheme 1 Synthesis of 1,3,5-tris[(E)-(4-phospholano-2,6-diethyl)styryl]benzene (1).
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Au
Au
P
Au
P
P
P
P
P
P
P
Au
Au
P
P
P
P
Au
P
Au
P
Au
P
P
P
P
P
P
Au
Au
P
P
P
P
Au
Au
P
P
P
P
P
P
P
P
Au
Au
P
P
P
P
Fig. 2 Schematic representation of the two-dimensional coordination polymer 2. Chains of different orientation (blue and green) are connected to each other by alternating
coordination of the third phospholane to the gold(I) cations in the chains in front and behind, respectively. Counterions (chloride) and the zigzag structure of the chains are
omitted for clarity.
The 31P{1H} NMR spectrum of the reaction mixture showed front and behind, respectively, thus forming a two-dimensional
two broad signals at δ = 35.4 and 33.2 ppm in a ratio of 5:1, polymer. The asymmetric unit of 2 (Fig. 3) shows a different
giving evidence for the presence of at least two species in conformation of the ligand compared to 1a (P(1)···P(2)
solution. Single crystals suitable for X-ray diffraction were 1.78 nm, P(2)···P(3) 1.63 nm, and P(3)···P(1) 1.62 nm; P(2)-P(1)-
obtained by gas diffusion of n-hexane into a saturated solution P(3) 56.98°, P(3)-P(2)-P(1) 56.53°, and P(1)-P(3)-P(2) 66.49°). A
of the product in o-difluorobenzene (Table 1). The resulting view along the crystallographic a axis shows the polymeric
structure revealed the formation of a 1:1 [M:L] complex, structure (Fig. 4).
regardless of the applied stoichiometry. In
(blue) in which gold(I) cations are bridged by two phospholane
moieties of ligand , while the third phospholane group is not
included in the formation of the chain. In
2, a chain is formed
1
Fig. 4 View of 2 along the a axis, illustrating the zigzag structure and connectivity of the
chains. Only four chains are shown. Ethyl groups and the carbon atoms of the
phospholane rings are omitted for clarity.
Gold(I) cations, phospholane moieties and the weakly
coordinating terminal chlorido ligands form the rims of the
polymeric chains, while the inner layer of 2 is composed of the
organic backbone of the ligands forming hydrophobic
1
channels (200 x 400 pm) along the b axis (Fig. 5), in which
disordered solvent molecules (o-difluorobenzene) are located.
Fig. 3 Asymmetric unit of the coordination polymer 2.
The next, parallel, chain (green) is rotated by 180° relative to
the first chain (blue). The third chain (blue) has the same
orientation as the first, and so on (Fig. 2).The phospholane
moieties, which are not included in the chain formation, are
alternatingly coordinated to the gold(I) cations of the chains in
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gold(I) by the phosphine ligands; thus, the structures should
not be discussed as distorted tetrahedral complexes. Tetra-
coordinated complexes with shorter Au–
Cl bond are known33–
42
and can be discussed as distorted tetrahedra, even though
an intermediate or trigonal [3 + 1] species could be
a
considered in some cases. An almost ideal trigonal-planar
environment has been observed for Cs8[Au(TPPTS)3]·5.25 H2O
(TPPTS = tris(meta-sulfonatophenyl)phosphine), where no
counterion is coordinated at gold(I).43 In the one-dimensional
coordination polymer [AuCl(MandyPhos)]n (MandyPhos =
(SP,S′P)-1,1′-Bis(diphenylphosphino)-2,2′-bis[(R)-α-
(dimethylamino)benzyl]ferrocene), gold(I) is coordinated in
distorted trigonal-planar fashion by bridging bidentate MandyPhos
ligands and a terminal chlorido ligand (av. Au–Cl 258.1(6) pm).44
Fig. 5 View of 2 along the b axis showing channels. Only two layers are shown. Ethyl
groups and the carbon atoms of the phospholane rings of the ligands are omitted for
clarity.
The gold(I) cations in
2 are coordinated in an unusual trigonal
[3 + 1] fashion (Fig. 6). The sum of P–Au–P bond angles is close
to 360°, and the gold(I) cation is located only 11 pm above the
plain formed by the three phosphorus atoms. The phospholane
rings are oriented in the shape of a bowl, in which the weakly
coordinating chlorido ligand is located (Fig. 6).
Fig. 6 Coordination environment of the gold(I) cations in 2, top view (left) and side view
(right). Ellipsoids are drawn at 50% probability; H atoms are omitted for clarity.
Selected bond lengths [pm] and angles [°]: Au(1)–P(1) 233.3(1), Au(1)–P(2) 233.7(1),
Au(1)–P(3) 235.9(1), Au(1)–Cl(1) 283.1(1), P(1)–Au(1)–P(2) 125.98(3), P(1)–Au(1)–P(3)
118.78(3), P(2)–Au(1)–P(3) 114.57(3), P(1)–Au(1)–Cl(1) 88.15(3), P(2)–Au(1)–Cl(1)
96.76(3), P(3)–Au(1)–Cl(1) 93.39(3).
Table 1 Selected crystallographic data for 1a and 2.
1a
2
Formula
Crystal system
Space group
Z
C42H45Br3
Monoclinic
C2/c
C54H69AuClP3 · 2.75 C6H4F2
Monoclinic
P21/c
Trigonal-planar [3 + 1] gold(I) complexes with other weakly
coordinating ligands than chloride are known but were not
included. Furthermore, gold(I) complexes with ambiphilic
8
4
a [pm]
b [pm]
c [pm]
2861.00(8)
1558.71(3)
1621.90(3)
96.537(2)
7.1858(3)
1800.76(2)
1336.91(2)
2686.19(3)
98.503(1)
donor-acceptor ligands and
a quasi trigonal-bipyramidal
environment have been reported,45–47 but will not be
discussed here in detail.
β [deg]
V [nm3]
6.3958(1)
After crystallisation, polymer
2 is almost completely insoluble
in common organic solvents as dichloromethane and
acetonitrile and can, therefore, be considered as the
The long Au(1)–Cl(1) 283.1(1) pm bond is almost perfectly
perpendicular to P3 triangle. A similar coordination geometry was
reported by Schmidbaur for [AuCl(PPh3)3],28 in which the Au–Cl
bond (279.6(1) pm) is slightly shorter and the sum of P–Au–P bond
thermodynamically
favoured
product.42
TGA/DSC
measurements of crystalline
2
in a range of 35–1100 °C (see
ESI) showed a first mass loss of about 20% at 100 °C
corresponding to loss of 2.75 co-crystallised o-difluorobenzene
molecules (also confirmed by mass spectrometry). The second
mass loss (about 40%) occurs at 400 °C and corresponds to
degradation of the backbone (detection of a species with m/z
26, which can be attributed to ethyne). No further degradation
is observed.
angles (355.35°) also slightly smaller than in 2
.
As this structure
covalent
was discussed as an intermediate between
a
([AuCl(PPh3)3]) and an ionic structure ([Au(PPh3)3]Cl),28 the
description as a trigonal-planar [3 + 1] coordination in 2 seems
reasonable. Only a few examples of complexes with related
AuP3Cl core structures have been reported: [Au(DHP)(PEt3)]Cl
(DHP = o-phenylenebis(diisopropylphosphane, Au
pm, sum of P Au
tert-butyl-calix[4]-(OCH2PPh2)4;
[Au(DPPP)(PPh3)]Cl (DPPP
bis(diphenylphosphino)propane, Au
Au
P bond angles 356.15(7)°),31 and [(Au2Cl)L3Cl] (L = bis(5-
diphenylphosphinopyrazol-1-yl)methane, Au Cl 284.9(4) pm
and 281.9(3) pm, sum of P Au
P bond angles 352.2(1)°)32.
These structures indicate that an elongation of the Au Cl bond
–Cl 307.3(2)
–
–
P bond angles 354.8(1)°),29 [Au2Cl2L]n (L = p-
While a linear coordination is typically preferred in gold(I)
Au
–Cl
301.2(6)
=
pm),30
1,3-
phosphine complexes, in polymer 2, which is formed
selectively independent of the stoichiometry employed, gold(I)
exhibits an usually [3 + 1] coordination as a linear sandwich-type
arrangements is sterically hindered.
–Cl 292.8(2) pm, sum of P–
–
–
–
–
Conclusion
–
correlates with formation of a (trigonal)-planar environment of
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A straight-forward synthetic route to the tridentate phosphine phases were dried over MgSO4 and the solvent removed under
ligand 1,3,5-tris[(E)-(4-phospholano-2,6-diethyl)styryl]benzene reduced pressure.
(
1
) was developed. The complexation of gold(I) is unusual,
resulting in an almost perfect trigonal-planar coordination and 6.15; N, 6.33. Calc. for C10H14BrN: C, 52.65; H, 6.19; N, 6.14. IR:
formation of a two-dimensional polymeric structure in = 3923 (w), 3485 (s), 3402 (s), 3234 (w), 2966 (s), 2935 (m),
Yield: 36.8 g (96%), slightly brown oil. Found C, 53.06; H,
2,
νꢀ
regardless of the stoichiometry employed. Our studies indicate 2875 (s), 2732 (w), 2429 (w), 2175 (w), 1739 (m), 1622 (s),
that the ligand geometry has a significant impact on the 1578 (m), 1451 (s), 1378 (m), 1344 (m), 1303 (w), 1284 (m),
coordination properties; therefore, an extraordinary 1247 (w), 1210 (s), 1137 (w), 1056 (m), 986 (w), 970 (w), 867
coordination chemistry of other metal cations can also be (s), 853 (m), 796 (m), 759 (w), 740 (m), 723 (w), 586 (w), 548
1
expected.
(m), 523 (w), 488 (w), 413 (w) cm–1. H NMR (CDCl3): δ = 7.03
3
(s, 2H), 3.56 (s, 2H), 2.41 (q, JHH = 7.5, 4H), 1.19 ppm (t,
3JHH = 7.6, 6H). 13C{1H} NMR (CDCl3): δ = 140.7 (s), 129.6 (s),
128.4 (s), 110.1 (s), 24.1 (s), 12.7 ppm (s). MS (ESI(+), MeCN):
m/z = 228.1 [M+H]+.
Experimental section
All reactions were carried out in a nitrogen atmosphere by
using standard Schlenk techniques and anhydrous solvents,
which were purified with an MB SPS-800 solvent purification
system from MBRAUN or as mentioned in the literature. 1,3,5-
Tris[(methylene)diethylphosphonato]benzene48
[AuCl(tht)]27 were prepared according to the literature. All
other chemicals were used as purchased. NMR spectra were
5-Bromo-1,3-diethyl-2-iodobenzene. 73.0 g (320.0 mmol; 1.0
eq) 4-Bromo-2,6-diethylaniline were suspended in 1.1 l H2O,
200 ml acetonitrile and 350 ml concentrated aqueous HCl and
cooled to –10 °C. 40 g (580 mmol; 1.8 eq) NaNO2 in 200 ml H2O
were added dropwise, giving a pink precipitate, followed by
formation of a clear red solution. After the addition, the
solution was stirred for further 60 min at –10 °C, followed by
dropwise addition of a solution of 184 g (902 mmol; 2.8 eq) KI
in 300 ml H2O. The formation of a yellowish foam was
observed. Afterwards, the mixture was carefully allowed to
warm to room temperature. The mixture was stirred
overnight, heated to 60 °C for 30 min, cooled to room
temperature, and extracted with n-hexane (4 x 50 ml). The
collected organic phases were stirred over saturated aqueous
Na2SO3 solution, until the organic phase had a light yellow
colour. The organic phase was then dried over MgSO4 and the
solvent removed under reduced pressure.
and
recorded at 298 K with
a Bruker AVANCE DRX 400
spectrometer. The chemical shifts δ of 1H, 13C, 31P are reported
in parts per million (ppm) at 400.12, 100.63 and 162.02 MHz,
respectively, with tetramethylsilane as an internal standard
and referencing to the unified scale. Coupling constants J are
given in Hz. NMR spectra with detailed signal assignment are
given in the ESI. FTIR spectra were recorded between
400 and 4000 cm–1 with a PerkinElmer Spectrum 2000 FTIR
spectrometer by using KBr pellets, and ATR spectra were
recorded on
a
THERMOFISCHER NICOLET iS5 ATR
spectrometer. Mass spectra were recorded on a BRUKER-
DALTONICS ESQUIRE 3000 Plus spectrometer (ESI) and on a
THERMO FISCHER SCIENTIFIC MAT 8230 spectrometer (EI).
Elemental analyses were carried out with a Heraeus VARIO EL
oven. Melting points were measured in sealed capillaries by
using a variable heater from Gallenkamp.
Yield: 100.0 g (92%), slightly yellow oil. Found C, 35.97; H,
3.55. Calc. for C10H12BrI: C, 35.46; H, 3.57. IR (KBr): νꢀ = 2968
(s), 2931 (m), 2873 (m), 2382 (w), 2347 (w), 1734 (w), 1558
(m), 1460 (s), 1427 (m), 1417 (m), 1397 (w), 1373 (m), 1327
(m), 1271 (w), 1241 (m), 1128 (m), 1075 (w), 1051 (m), 1004
(s), 862 (s), 813 (m), 784 (w), 726 (w), 709 (w), 661 (w), 600
Crystallographic data for compounds 1a and
2 were collected
1
(w), 568 (w), 530 (w), 421 (w) cm−1. H NMR (CDCl3): δ = 7.15
with an Oxford Diffraction CCD Xcalibur-S diffractometer (data
reduction with CrysAlis Pro,49 including the program SCALE3
ABSPACK50 for empirical absorption correction) by using MoKα
irradiation (λ = 71.073 pm) and ω-scan rotation. The structure
3
3
(s, 2H), 2.73 (q, JHH = 7.5, 4H), 1.18 ppm (t, JHH = 7.4, 6H).
13C{1H} NMR (CDCl3): δ = 148.8 (s), 128.7 (s), 122.6 (s), 105.4
(s), 35.3 (s), 14.5 ppm (s). MS (ESI(+), CH2Cl2/MeOH): m/z =
374.9 [C10H10BrI+K]+.
solution was performed with SHELXS-201351
201452 ). Refinement was performed with SHELXL-201853.
Figures were drawn with Mercury. CCDC 1861124 (1a) and
1860064 ( ) contain the supplementary crystallographic data
(1a) and SHELXT-
4-Bromo-2,6-diethylbenzaldehyde. 10.0 g (29.5 mmol; 1.0
eq) 5-Bromo-1,3-diethyl-2-iodobenzene were dissolved in
100 ml diethyl ether and cooled to –78 °C. 21.9 ml (33.9 mmol;
1.1 eq) of a 1.55 M n-butyllithium solution in n-hexane were
added in one portion and the solution stirred for 90 min at a
temperature below –45 °C. A white precipitate was formed.
Afterwards, 10.3 ml (132.8 mmol; 4.5 eq) dimethylformamide
were added dropwise and the precipitate dissolved. The
mixture was allowed to warm to room temperature and was
stirred overnight, resulting in a white precipitate. 20 ml of an
aqueous NH4Cl solution were added carefully, and then the
mixture was extracted with diethyl ether (2 x 25 ml). The
collected organic phase was dried over MgSO4 and the solvent
removed using a rotary evaporator. The raw product was
(
2
2
for this paper.
Synthesis and characterisation
4-Bromo-2,6-diethylaniline. 25 g (167.5 mmol; 1.0 eq) 2,6-
Diethylaniline were dissolved in 200 ml dimethyl sulfoxide and
cooled to 0 °C. 200 ml of an aqueous HBr solution (40%) was
added and the mixture was allowed to warm to room
temperature. The mixture was stirred for 7 days at room
temperature, neutralised with aqueous NaOH solution and
extracted with diethyl ether (3 x 80 ml). The collected organic
4 | J. Name., 2012, 00, 1-3
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filtered over silica using n-hexane/EtOH (20:1; Rf = 0.7) and 687 (m), 668 (m), 600 (m), 533 (m), 465 (w) cm−1. 1H
3
subsequently distilled at 2.6·10–2 mbar and 100 °C.
Yield: 6.2 g (87%), colourless oil. Found C, 54.82; H,
NMR (CDCl3): δ = 7.42 (s, 3H), 7.15 (d, JHH = 16.8, 3H), 7.05 (d,
5.57. 3JHP = 6.8, 6H), 6.56 (d, 3JHH = 16.8, 3H), 2.66 (q, 3JHH = 7.5, 12H),
= 3373 (w), 1.97 – 1.68 (m, 24H), 1.40 ppm (t, 3JHH = 7.5, 18H). 13C{1H} NMR
Calc. for C11H13BrO: C, 54.79;
H, 5.43. IR (KBr): νꢀ
2970 (s), 2934 (m), 2874 (m), 2767 (m), 1740 (m), 1695 (s), (CDCl3): δ = 142.1 (d, 3JCP = 5.2), 140.7 (d, 1JCP = 21.9), 138.3 (s),
2
1574 (s), 1457 (s), 1401 (m), 1377 (m), 1324 (w), 1298 (w), 135.2 (s), 133.4 (s), 128.1 (d, JCP = 15.6), 127.0 (s), 123.3 (s),
1264 (m), 1234 (s), 1184 (m), 1158 (m), 1114 (s), 1061 (m), 968 27.9 (d, JCP = 3.5), 27.1 – 27.0 (m), 15.4 ppm (s). 31P{1H} NMR
2
(w), 893 (m), 867 (s), 844 (s), 799 (w), 737 (m), 590 (w), 442 (CDCl3): δ = –16.8 ppm (s). MS (EI): m/z = 693.6 (100.0%) [M–
1
(m) cm−1. H NMR (CDCl3): δ = 10.52 (s, 1H), 7.28 (s, 2H), 2.93 (C4H8)P–C2H6]+, 723.7 (44.1%) [M–(C4H8)P]+, 810.7 (5.1%) [M]+.
3
3
(q, JHH = 7.5, 4H), 1.24 ppm (t, JHH = 7.6, 6H). 13C{1H} NMR
Poly[μ-1,3,5-tris[(E)-(4-phospholano-2,6-diethyl)styryl]-
(CDCl3): δ = 192.3 (s), 149.1 (s), 131.0 (s), 130.3 (s), 127.8 (s), benzene-κ3P,P´,P´´]gold(I) chloride (2). 164 mg (202 μmol;
26.4 (s), 16.1 ppm (s). MS (ESI(+), MeCN): m/z = 298.3.
1,3,5-Tris[(E)-(4-bromo-2,6-diethyl)styryl]benzene
1.0 eq)
1,3,5-Tris[(E)-(4-phospholano-2,6-diethyl)styryl]ben-
(1a). zene were dissolved in 10 ml dichloromethane followed by the
1.00 g (1.89 mmol; 1.0 eq) 1,3,5-Tris[(methylene)diethylphos- dropwise addition of 65 mg (202 μmol; 1.0 eq) [AuCl(tht)] in
phonato]benzene were dissolved in 25 ml of tetrahydrofuran. 5 ml dichloromethane, resulting in the formation of a white
0.15 g NaH in mineral-oil (60%, 3.8 mmol; 2.0 eq) were added, precipitate, which dissolved again, after the addition was
the mixture was stirred for 3 h and subsequently 0.59 g completed. The mixture was stirred for 30 min at room
(2.46 mmol; 1.3 eq) 4-bromo-2,6-diethylbenzaldehyde in 10 ml temperature, filtered and all volatiles were removed in vacuo.
n-hexane were added. The mixture was stirred for 3 h at room Suitable crystals of
2 for single-crystal X-ray crystallography
temperature and the addition sequence was repeated twice, were obtained by dissolving the solid in 30 ml o-
followed by stirring overnight. 5 ml H2O were added carefully difluorobenzene, followed by filtration and subsequent gas
and all volatiles were removed in vacuo. The remaining solid diffusion of n-hexane into the solution at room temperature.
was dissolved in 30 ml dichloromethane, washed with brine 1H NMR and 31P{1H} NMR and mass spectra were recorded of
and water (15 ml each) and dried over MgSO4. The raw the solid before crystallisation, while IR spectra and elemental
product was purified via column chromatography using n- analysis were obtained from crystalline
hexane (Rf = 0,4). Found C, 61.91; H, 6.19. Calc. for C54H69AuClP3 · 2.5 C6H4F2: C,
Yield: 0.67 g (45%), white solid. Mp = 133 °C. Found C, 63.89; 62.37; H, 5.99. IR (ATR): ν = 3336 (w), 2962 (s), 2931 (s), 2870
H, 5.91. Calc. for C42H45Br3: C, 63.89; H, 5.74. IR (KBr): ν (s), 2361 (w), 1617 (w), 1587 (m), 1505 (s), 1455 (m), 1414 (w),
2.
ꢀ
ꢀ
=
3021 (m), 2964 (s), 2930 (s), 2871 (s), 1782 (w), 1735 (w), 1637 1265 (s), 1192 (w), 1101 (m), 1059 (m), 1024 (m), 969 (m), 875
(m), 1588 (s), 1574 (s), 1455 (s), 1407 (m), 1372 (m), 1329 (s), (w), 842 (m), 753 (s), 687 (m) cm–1. 1H NMR (CD2Cl2):
3
1266 (m), 1239 (m), 1187 (m), 1164 (w), 1115 (w), 1058 (m), δ = 7.53 (s, 3H), 7.40 (d, JHP = 13.2, 6H), 7.27 (d, JHH = 16.7,
3
3
971 (s), 862 (s), 839 (m), 822 (m), 797 (s), 766 (m), 726 (w), 684 3H), 6.67 (d, JHH = 16.6, 3H), 2.79 (q, JHH = 7.5, 12H), 2.54 –
3
1
3
(s), 629 (w), 594 (w), 549 (w), 418 (w) cm−1. H NMR (CDCl3): 2.02 (m, 24H), 1.22 ppm (t, JHH = 7.5, 18H). 31P{1H} NMR
3
δ = 7.53 (s, 3H), 7.25 (s, 6H), 7.16 (d, JHH = 16.0, 3H), 6.62 (d, (CD2Cl2): δ = 26.5 ppm (s). MS (ESI(+), CH2Cl2): L = C54H69P3,
3JHH = 16.0, 3H), 2.70 (q, 3JHH = 8.0, 12H), 1.20 ppm (t, 3JHH = 8.0, m/z = 1471.3 [Au3Cl2L]+, 1705.2 [Au4Cl3L]+, 1937.2 [Au5Cl4L]+.
18H). 13C{1H} NMR (CDCl3): δ = 144.6 (s), 138.1 (s), 135.0 (s), Details for TGA/DSC measurements of
133.9 (s), 128.8 (s), 126.5 (s), 123.6 (s), 121.2 (s), 26.8 (s), 15.9
2 are given in the ESI.
ppm (s). MS (ESI(–), CH2Cl2/MeOH): m/z = 825.0 [M+Cl]–.
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