Golden crowns: Cation binding by macrocyclic gold(I) crown ether derivatives

Article abstract of DOI:10.1016/j.jorganchem.2003.10.025

The polyether bis(alkynes) α,ω-bis(O-propargyl)triethylene glycol and α,ω-bis(O-4-propargyloxyphenoxy)triethylene glycol reacted with [AuCl(SMe₂)] in the presence of base to form the corresponding oligomeric gold(I) acetylide complexes (AuCCCH₂O(CH₂CH₂O)₃ CH₂CCAu)_n and (AuCCCH₂OC₆ H₄O(CH₂CH₂O)₃C₆ H₄OCH₂CCAu)_n. These digold(I) diacetylide complexes reacted with diphosphine ligands to give macrocyclic digold(I) complexes of the type [Au₂(μ-CC) (μ-PP)], where CC is the diacetylide and PP is a diphosphine ligand. These digold(I) complexes bind the cations Li⁺, Na⁺, K⁺ and Cs⁺, as studied by electrospray mass spectrometry.

Full text of DOI:10.1016/j.jorganchem.2003.10.025

Journal of Organometallic Chemistry 689 (2004) 374–379
www.elsevier.com/locate/jorganchem
Golden crowns: cation binding by macrocyclic gold(I) crown
ether derivatives
*
Fabian Mohr, Richard J. Puddephatt
Department of Chemistry, The University of Western Ontario, Richmond Street, London, Ont., Canada N6A 5B7
Received 20 June 2003; accepted 21 October 2003
Abstract
The polyether bis(alkynes) a,x-bis(O-propargyl)triethylene glycol and a,x-bis(O-4-propargyloxyphenoxy)triethylene glycol
reacted with [AuCl(SMe2)] in the presence of base to form the corresponding oligomeric gold(I) acetylide complexes (AuC-
CCH2O(CH2CH2O)3CH2CCAu)n and (AuCCCH2OC6H4O(CH2CH2O)3C6H4OCH2CCAu)n. These digold(I) diacetylide com-
plexes reacted with diphosphine ligands to give macrocyclic digold(I) complexes of the type [Au2(l-CC)(l-PP)], where CC is the
diacetylide and PP is a diphosphine ligand. These digold(I) complexes bind the cations Liþ, Naþ, Kþ and Csþ, as studied by
electrospray mass spectrometry.
Ó 2003 Elsevier B.V. All rights reserved.
Keywords: Gold(I); Macrocycle; Crown ether; Cation binding
1. Introduction
or 4,40-C6H4C6H4), while angular diacetylides formed
24-membered rings II [13,14]. Using the diacetylides
derived from o-, m- and p-bis(propargyloxy)benzene and
the diphosphines Ph2P(CH2)nPPh2 (n ¼ 1–6) macrocy-
cles of type III containing 15–22-membered rings were
prepared [15]. Similarly, a more flexible ligand, based on
the linker group 3,3-(ethylenedioxy)diphenol, gave 23–
28-membered ring structures IV, which form interpen-
etrated dimers in the solid state [16]. Complexes of
the type V, where X ¼ O, S and OC, also form macro-
cyclic structures with diphosphine ligands but, when
X ¼ Me2C, H2C, O2S and n ¼ 3–6, the complexes un-
dergo self-assembly to give the [2]catenanes VI [17–20].
When X ¼ C6H10 and n ¼ 4, a rare doubly braided
[2]catenane was obtained [21]. A huge variety of struc-
turally diverse crown ethers with high affinities and se-
lectivities for all kinds of cations have been reported
[22–26] and there is recent interest in crown ethers
incorporating inorganic or organometallic fragments
[27,28]. This paper reports digold(I) diacetylide macro-
cycles that incorporate a flexible polyether chain to form
a ‘‘gilded’’ crown ether. It was anticipated that the large
cavity of such a macrocycle might allow catenation to
occur or that the polyether chain might enable encap-
sulation of cations.
The design of supramolecular systems containing
macrocycles or mechanically interlocked components is
of current interest, since such compounds have potential
applications in nanoscale devices [1–8]. Most known
catenanes are based on organic or inorganic molecules,
and organometallic catenanes have only been known for
ten years [9]. Entropy effects do not favour catenane
formation from simple macrocycles and so, if a catenane
is to be formed by self-assembly, the macrocycle must
incorporate functional groups to give favourable en-
thalpy effects through p–p interactions, dipole–dipole
attractions or hydrogen bonding in the catenane prod-
uct [1,4]. Linear, two-coordinate gold(I) units are useful
for the assembly of organometallic macrocycles, and
supramolecular association through aurophilic attrac-
tions can then occur to give more complex assemblies
[10–12]. Some of the known gold(I) acetylide macrocy-
cles are illustrated in Chart 1.
Rigid linear diacetylides give tetragold(I) complexes
containing 26- or 34-membered rings I (Ar ¼ 1,4-C6H4
* Corresponding author. Tel.: +5196792111; fax: +5196613022.
E-mail address: pudd@uwo.ca (R.J. Puddephatt).
0022-328X/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.10.025

F. Mohr, R.J. Puddephatt / Journal of Organometallic Chemistry 689 (2004) 374–379
375
Au
P
Au
Au
Ar
Au
Au
P
P
P
P
O
Au
Ar
Au
P
I
(CH2)n
P
O
Au
Au
Au
III
O
O
O
O
II
P
Au
P
P
Au
P
IV
O
O
Au
P
O
O
Au
Au
P
O
P
Au
X
X
X
Au
P
Au
P
P
V
O
Chart 1. Some known gold(I) macrocycles.
2. Results and discussion
the diphosphine ligands Ph2PZPPh2 [Z ¼ (CH2)n,
n ¼ 1–5; CC] to form the beige or pale yellow gold(I)
macrocyclic complexes (3a–3f and 6a–6f) as shown in
Schemes 1 and 2.
2.1. Ligand and gold(I) macrocycle syntheses
The bis(alkyne) with an oligoether spacer group, a,x-
bis(O-propargyl)triethylene glycol, HCCCH2O(CH2
CH2O)3CH2CCH, 1, was prepared by the literature
method [29], and the related bis(alkyne) HCCCH2O
C6H4O(CH2CH2O)3C6H4OCH2CCH, 4, having two
extra oxyphenylene spacer groups, was prepared by re-
acting 4,40-{ethylenebis(oxyethyleneoxy)} diphenol with
propargyl bromide in the presence of potassium car-
bonate. The new bis(alkyne) was characterized by its
1H, 13C NMR and IR spectra and by the high resolution
mass spectrum (see Section 3). Treatment of these
bis(alkynes) with two equivalents of [AuCl(SMe2)] and
Et3N gave the yellow solid products (AuCCCH2O
(CH2CH2O)3CH2CCAu)n, 2, and (AuCCCH2O C6H4O
(CH2CH2O)3C6H4OCH2CCAu)n, 5, which were insol-
uble in common organic solvents. These compounds,
like other gold(I) acetylide complexes, are oligomeric or
polymeric, and are characterized in the IR spectra by
m(CC) values [1993 cmꢀ1 in 2 and 2003 cmꢀ1 in 5] that
are lower by ca. 100 cmꢀ1 than in the parent bis(alkyne),
as a result of p-bonding between gold and the alkynyl
groups [30]. The digold(I) oligomers 2 and 5 react with
O
O
O
O
H
H
O
O
O
O
Au
Au
[AuCl(SMe2)]
Et3N
(1)
(2)
Ph2PZPPh2
O
O
O
O
Au PPh2
Z
(3a), Z = CH2
(3b), Z = (CH2)2
(3c), Z = (CH2)3
(3d), Z = (CH2)4
(3e), Z = (CH2)5
(3f), Z = CC
Au
Scheme 1.

376
F. Mohr, R.J. Puddephatt / Journal of Organometallic Chemistry 689 (2004) 374–379
O
O
O
O
O
O
O
H
H
Au
Au
O
O
O
[AuCl(SMe2)]
Et3N
O
O
(4)
(5)
Ph2PZPPh2
O
O
O
O
O
Au
(6a), Z = CH2
PPh2
(6b), Z = (CH2)2
(6c), Z = (CH2)3
(6d), Z = (CH2)4
(6e), Z = (CH2)5
(6f), Z = CC
Z
PPh2
Au
Scheme 2.
The new gold complexes did not form crystals
2.2. Cation binding studies
suitable for X-ray structure determination, so they
were characterized spectroscopically. For example,
complex 3a gave a singlet in the 31P NMR spectrum
The observation of intense peaks in the electrospray
mass spectra due to Csþ adducts of the macrocycles
prompted an examination of the cation binding ability
of these complexes in more detail. Samples of the gold(I)
macrocycles (complexes 3a, 3c, 3e and 6a, 6c, 6e) were
treated with solutions containing equimolar amounts of
cation pairs (Liþ/Naþ; Naþ/Kþ; Kþ/Csþ), the ES mass
spectra were recorded, and the relative amounts of the
macrocycle-cation adducts in the gas phase were deter-
mined from the relative abundance of each in the ES-
MS. The results are shown in Table 1. It is most useful
to examine trends since the gas phase abundances will
not generally be the same as those in solution, due to
solvation and ionization effects [31].
1
at d 32.89 and, in the H NMR spectrum, there was a
single resonance for the PCH2P protons at d 3.63 (t,
2JPH ¼ 11 Hz) and for the OCH2C protons of the
propargyl group at d 4.36, indicating the presence of a
single complex. However, these data do not distin-
guish between ring and [2]catenane structures. The ES-
MS, obtained from a solution containing CsCl to aid
ionization, gave a peak at m=z ¼ 1134 [M + Cs]þ for
the simple macrocycle with no peak corresponding to
the [2]catenane. Thus, the spectroscopic evidence is
consistent with the complex having the simple 21-
membered macrocyclic structure 3a, as shown in
Scheme 1. The other complexes were characterized
similarly. The ring sizes of the macrocycles range from
21 in 3a to 35 in 6e.
It is clear from the competition between Liþ and Naþ
that complexes 3a, 3c and 3e do not discriminate greatly
between these cations, but that the larger ring complexes
Table 1
Cation binding for selected gold(I) macrocycles
Massa
Complex
Ring size
Li/Nab
Na/Kb
K/Csb
P + Li, Na, K, Cs
3a
3c
3e
6a
6c
6e
21
23
25
31
33
35
1009, 1025, 1041, 1135
1037, 1053, 1069, 1163
1065, 1081, 1097, 1191
1193, 1209, 1225, 1319
1221, 1237, 1253, 1347
1249, 1265, 1281, 1375
0.73
1.74
1.02
0.03
0.19
0.04
0.87
0.59
0.87
0.87
1.00
0.75
128
96
11.9
18.9
6.17
1.85
a Masses of [P + cation]þ ion peaks; P ¼ parent mass for macrocycle.
b Ratio of intensities [P + M1]þ/[P + M2]þ for pairs of alkali metal cations.

F. Mohr, R.J. Puddephatt / Journal of Organometallic Chemistry 689 (2004) 374–379
377
diluted with MeCN and treated with 10 ll of a solution
of CsI in MeCN/H2O to aid ionization. High-resolution
mass spectra were measured using a Finnigan MAT
8200 spectrometer. [AuCl(SMe2)] [32], a,x-bis(O-prop-
argyl)triethylene glycol [29] and 4,40-{ethylenebis(oxy-
ethyleneoxy)}diphenol [33] were prepared by literature
procedures. All reactions involving gold complexes were
carried out in reaction vessels shielded from light.
3.1. Gold(I) oligomer, 2
A solution of a,x-bis(O-propargyl)triethylene glycol
1 (0.138 g, 0.610 mmol) and Et3N (0.3 ml) in THF was
added to a solution of [AuCl(SMe2)] (0.359 g, 1.22
mmol) in THF (40 ml) and MeOH (30 ml). After stirring
for 0.5 h, the solid was isolated by filtration and was
washed with THF, MeOH, Et2O and pentane to give
0.297 g (79%) yellow solid. The compound was stored
cold and protected from light. IR (KBr disk, cmꢀ1) 1993
[w, m(CC)]; Anal. Calc. for C12H16Au2O4: C, 23.31; H,
2.61. Found: C, 23.47; H, 2.48%.
Fig. 1. The macrocyclic structures of complex 6c (above) and its
complex with Naþ (below), as predicted by molecular mechanics.
Hydrogen atoms and phenyl substituents of the diphosphine are
omitted for clarity.
3.2. Macrocycle, 3a
6a, 6c and 6e bind sodium cations more strongly. None
of the complexes discriminate greatly between Naþ and
Kþ, and all bind Kþ in preference to Csþ. For each
series 3a, 3c, 3e and 6a, 6c, 6e the selectivity for potas-
sium over cesium decreases as the ring size increases,
and the smaller ring complexes 3 discriminate more than
the larger ring complexes 6 (Table 1). Fig. 1 shows a
structure for the macrocycle 6c and for its complex with
a sodium ion, as predicted by molecular mechanics
calculations. It is clear from such structures that the
diphosphine digold(I) unit serves to make the macro-
cycle wider, with longer spacer groups in the diphos-
phine, or narrower, with shorter spacer groups, but that
the effect at the polyether unit is attenuated by the
flexibility of the connecting propargyl groups. Overall
these results show that the gold(I) macrocycles 3 and 6
show selectivity for binding of alkali metal cations based
on size, and that the selectivity can be tuned by changing
the length of the spacer group of the diphosphine li-
gands used.
A
mixture of 2 (0.050 g, 0.081 mmol) and
Ph2P(CH2)PPh2 (0.026 g, 0.068 mmol) in CH2Cl2 (10
ml) was stirred at room temperature for 3 h. The mix-
ture was filtered through Celite and concentrated in
vacuum. Addition of pentane gave a colourless solid,
which was isolated by filtration, washed with Et2O and
pentane and dried. Yield: 0.057 g, 69% cream coloured
solid. 31P NMR (CD2Cl2) d 32.89; 1H NMR (CD2Cl2) d
2
3.63 (t, JPH ¼ 11 Hz, 2H, PCH2P) 3.64–3.75 (m, 12H,
OCH2CH2O), 4.36 (s, 4H, OCH2CO), 7.32–7.47 (m,
12H, PPh2), 7.58–7.65 (m, 8H, PPh2); ES-MS (m=z):
1135 [M + Cs]þ; Anal. Calc. for C37H38Au2O4P2: C,
44.33; H, 3.82. Found: C, 44.35; H, 3.72%.
Similarly were prepared from 2 and the appropriate
diphosphine ligand: 3b: Yield: 57% beige solid. 31P
NMR (CD2Cl2) d 40.08; H NMR (CD2Cl2) d 2.64 (s
1
br, 4H, CH2P), 3.59–3.79 (m, 12H, OCH2CH2O), 4.25
(s, 4H, OCH2CO), 7.44–7.66 (m, 20H, PPh2); ES-MS
(m=z) 1149 [M + Cs]þ; Anal. Calc. For C38H40Au2O4P2:
C, 44.90; H, 3.97. Found: C, 44.63, H, 3.87%. 3c: Yield:
75% beige solid. 31P NMR (CD2Cl2) d 34.76; H NMR
1
(CD2Cl2) d 1.87 (s br, 2H, CH2CH2P), 2.66 (s br, 4H,
CH2P), 3.59–3.77 (m, 12H, OCH2CH2O), 4.28 (s, 4H,
OCH2C), 7.42–7.55 (m, 12H, PPh2), 7.64–7.75 (m, 8H,
PPh2); ES-MS (m=z) 1163 [M + Cs]þ; Anal. Calc. for
C39H42Au2O4P2: C, 45.45; H, 4.11. Found: C, 45.74; H,
4.22%. 3d: Yield: 69% beige solid. 31P NMR (CD2Cl2) d
3. Experimental
NMR spectra were measured using a Varian Mercury
400 MHz spectrometer. 1H and 13C NMR chemical
shifts are reported relative to TMS, while 31P chemical
shifts are reported relative to 85% H3PO4 as an external
standard. IR spectra were recorded using a Perkin–El-
mer 2000 FT-IR instrument. Electrospray mass spectra
were recorded using a Micromass LCT instrument in
positive ion mode. Samples were dissolved in CH2Cl2,
1
38.59; H NMR (CD2Cl2) d 1.79 (s br, 4H, CH2CH2P),
2.42 (s br, 4H, CH2P), 3.59–3.76 (m, 12H, OCH2CH2O),
4.26 (s, 4H, OCH2CO), 7.43–7.54 (m, 12H, PPh2), 7.61–
7.70 (m, 8H, PPh2); ES-MS (m=z) 1177 [M + Cs]þ; Anal.
Calc. for C40H44Au2O4P2: C, 45.99; H, 4.25. Found: C,

378
F. Mohr, R.J. Puddephatt / Journal of Organometallic Chemistry 689 (2004) 374–379
45.70; H, 4.25%. 3e: Yield: 81% beige solid. 31P NMR
(CD2Cl2) d 37.87; H NMR (CD2Cl2) d 1.62 (s br, 6H,
J ¼ 5 Hz, 4H, OCH2CH2O), 4.04 (t, J ¼ 5 Hz, 4H,
OCH2CH2O), 4.77 (s, 4H, OCH2 CO), 6.86 (d, J ¼ 9
Hz, 4H, C6H4), 7.01 (d, J ¼ 9 Hz, 4H, C6H4), 7.38–7.65
(m, 20H, PPh2); ES-MS (m=z) 1333 [M + Cs]þ; Anal.
Calc. for C50H48Au2O6P2: C, 50.01; H, 4.03. Found: C,
50.02; H, 3.94%. 6c: Yield: 0.052 g, 81%. 31P NMR
1
CH2CH2P), 2.40 (s br, 4H, CH2P), 3.59–3.73 (m, 12H,
OCH2CH2O), 4.25 (s, 4H, OCH2CO), 7.43–7.54 (m,
12H, PPh2), 7.63–7.72 (m, 8H, PPh2); ES-MS (m=z)
1191 [M + Cs]þ; Anal. Calc. for C41H46Au2O4P2: C,
46.51; H, 4.38. Found: C, 46.33; H, 4.46%. 3f: Yield:
70%. 31P NMR (CD2Cl2) d 21.51; 1H NMR (CD2Cl2) d
3.60–3.75 (m, 12H, OCH2CH2O), 4.26 (s, 4H,
OCH2CO), 7.47–7.61 (m, 12H, PPh2), 7.72–7.81 (m, 8H,
PPh2); ES-MS (m=z) 1145 [M + Cs]þ; Anal. Calc. for
C38H36Au2O4P2: C, 44.44; H, 3.56. Found: C, 44.36; H,
3.47%.
1
(CD2Cl2) d 34.88; H NMR (CD2Cl2) d 1.85 (s br, 2H,
CH2CH2P), 2.75 (s br, 4H, CH2P), 3.67 (s, 4H,
OCH2CH2O), 3.77 (t, J ¼ 5 Hz, 4H, OCH2CH2O), 4.01
(t, J ¼ 5 Hz, 4H, OCH2CH2O), 4.76 (s, 4H, OCH2CO),
6.83 (d, J ¼ 9 Hz, 4H, C6H4), 6.96 (d, J ¼ 9 Hz, 4H,
C6H4), 7.39–7.53 (m, 12H, PPh2), 7.61–7.71 (m, 8H,
PPh2); ES-MS (m=z) 1347 [M + Cs]þ; Anal. Calc. for
C51H50Au2O6P2: C, 50.42; H, 4.15. Found: C, 50.16; H,
1
3.3. Bis(alkyne), 4
4.15%. 6d: Yield: 80%. 31P NMR (CD2Cl2) d 37.74; H
NMR (CD2Cl2) d 1.71 (s br, 4H, CH2CH2P), 2.37 (s br,
4H, CH2P), 3.69 (s, 4H, OCH2CH2O), 3.79 (t, J ¼ 5 Hz,
4H, OCH2CH2O), 4.05 (t, J ¼ 5 Hz, 4H, OCH2CH2O),
4.75 (s, 4H, OCH2CO), 6.85 (d, J ¼ 9 Hz, 4H, C6H4),
6.94 (d, J ¼ 9 Hz, 4H, C6H4), 7.41–7.53 (m, 12H, PPh2),
7.57–7.66 (m, 8H, PPh2); ES-MS (m=z) 1361 [M+Cs]þ;
Anal. Calc. for C52H52Au2O6P2: C, 50.82; H, 4.27.
Found: C, 50.52; H, 4.25%. 6e: Yield: 89%. 31P NMR
A mixture of 4,40-{ethylenebis(oxyethyleneoxy)}di-
phenol (1.0 g, 2.99 mmol), K2CO3 (1.2 g, 8.69 mmol)
and propargyl bromide (0.8 ml, 7.48 mmol) in acetone
(60 ml) was heated to reflux for ca. 18 h. The suspension
was filtered and the filtrate was evaporated to dryness to
1
give 0.66 g, 54% pale yellow solid. H NMR (CDCl3) d
2.50 (t, J ¼ 2 Hz, 2H, OCH), 3.74 (t, J ¼ 5 Hz, 4H,
OCH2CH2O), 3.83 (s, 4H, OCH2CH2O), 4.07 (t, J ¼ 5
Hz, 4H, OCH2CH2O), 4.62 (d, J ¼ 2 Hz, 4H, OCH2-
CO), 6.85 (d, J ¼ 9 Hz, 4H, C6H4), 6.89
(d, J ¼ 9 Hz, 4H, C6H4); 13C NMR (CDCl3) d 56.8
(OCH2CO), 68.2, 70.1, 71.1 (OCH2CH2O), 75.6
(COCH), 79.1 (COCH), 115.8, 116.3, 152.0, 153.9
(C6H4); IR (KBr disk, cmꢀ1) 3251 (s, OCH), 2115 [w,
m(CC)]; HR-MS found m=z 410.1725, calculated for
C24H26O6 m=z 410.1729.
1
(CD2Cl2) d 37.96; H NMR (CD2Cl2) d 1.59 (s br, 6H,
CH2CH2CH2P), 2.36 (s br, 4H, CH2P), 3.69 (s, 4H,
OCH2CH2O), 3.79 (t, J ¼ 5 Hz, 4H, OCH2CH2O), 4.05
(t, J ¼ 5 Hz, 4H, OCH2CH2O), 4.72 (s, 4H, OCH2CO),
6.84 (d, J ¼ 9 Hz, 4H, C6H4), 6.89 (d, J ¼ 9 Hz, 4H,
C6H4), 7.42–7.52 (m, 12H, PPh2), 7.61–7.69 (m, 8H,
PPh2); ES-MS (m=z) 1375 [M + Cs]þ; Anal. Calc. for
C53H54Au2O6P2: C, 51.22; H, 4.38. Found: C, 51.19; H,
1
4.24%. 6f: Yield: 92%. 31P NMR (CD2Cl2) d 18.26; H
NMR (CD2Cl2) d 3.69 (s, 4H, OCH2CH2O), 3.79 (t,
J ¼ 5 Hz, 4H, OCH2CH2O), 4.05 (t, J ¼ 5 Hz, 4H,
OCH2CH2O), 4.76 (s, 4H, OCH2CO), 6.85 (d, J ¼ 9 Hz,
4H, C6H4), 6.96 (d, J ¼ 9 Hz, 4H, C6H4), 7.44–7.59 (m,
12H, PPh2), 7.69–7.78 (m, 8H, PPh2); ES-MS (m=z) 1329
[M+Cs]þ; Anal. Calc. for C50H44Au2O6P2: C, 50.18; H,
3.71. Found: C, 49.91; H, 3.77%.
3.4. Gold(I) oligomer, 5
This was prepared from (4) (0.25g, 0.61 mmol) and
[AuCl(SMe2)] (0.35 g, 1.19 mmol) as described for 2.
Yield: 0.37 g, 76% pale yellow solid. IR (KBr disk,
cmꢀ1) 2003 [w, m(CC)]; Anal. Calc. for C24H24Au2O6: C,
35.93; H, 3.01. Found: C, 36.15; H, 3.02%.
3.6. ES-MS cation binding studies
3.5. Gold(I) macrocycles, 6a–6f
Samples of the gold(I) macrocycles were dissolved in
CH2Cl2, diluted with MeCN and treated with 20 ll of a
solution of the cation pair under investigation (5 mM
Cs/K, K/Na and Na/Li as iodide salts in H2O/MeCN).
Relative proportions of the gold(I) complex/cation ad-
ducts were estimated from the intensities of the
[M + cat]þ peaks corrected, when necessary, for the
natural abundance of the isotope of the alkali metal.
The following gold(I) macrocycles were prepared
from 5 and the appropriate diphosphine as described
above for complex 3a:6a: Yield: 75%. 31P NMR
(CD2Cl2) d 32.85; 1H NMR (CD2Cl2) d 3.61 (t,
2JPH ¼ 10 Hz, 2H, PCH2P), 3.67 (s, 4H, OCH2CH2O),
3.76 (t, J ¼ 5 Hz, 4H, OCH2CH2O), 3.99 (t, J ¼ 5 Hz,
4H, OCH2CH2O), 4.69 (s, 4H, OCH2CO), 6.77 (d, J ¼ 9
Hz, 4H, C6H4), 6.83 (d, J ¼ 9 Hz, 4H, C6H4), 7.29–7.47
(m, 12H, PPh2), 7.55–7.64 (m, 12H, PPh2); ES-MS (m=z)
1319 [M + Cs]þ; Anal. Calc. for C49H46Au2O6P2: C,
49.59; H, 3.91. Found: C, 49.34; H, 3.91. 6b: Yield: 97%.
Acknowledgements
1
31P NMR (CD2Cl2) d 38.79; H NMR (CD2Cl2) d 2.60
We thank the NSERC (Canada) and EMK (Ontario)
for financial support.
(s br, 4H, CH2P), 3.69 (s, 4H, OCH2CH2O), 3.79 (t,

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