Macrocyclic gold(I) complexes with bridging diacetylide and diphosphine ligands

Article abstract of DOI:10.1515/znb-2004-11-1219

The new dialkynyldigold(I) complexes [Ar(OCH₂C≡CAu) ₂]_n {Ar = 1,4-C₆H₄(CMe ₂-4-C₆H₄)₂, 4,4′-C ₆H₄C₆H₄ and 1,5-C<

Full text of DOI:10.1515/znb-2004-11-1219

Macrocyclic Gold(I) Complexes with Bridging Diacetylide and
Diphosphine Ligands
William J. Hunks, Michael C. Jennings, and Richard J. Puddephatt
Department of Chemistry, University of Western Ontario, London, Canada N6A 5B7
Reprint requests to Prof. Dr. R. J. Puddephatt. E-mail: pudd@uwo.ca
Z. Naturforsch. 59b, 1488 – 1496 (2004); received August 26, 2004
Dedicated to Professor Hubert Schmidbaur, the undisputed champion of gold chemistry,
on the occasion of his 70th birthday
The new dialkynyldigold(I) complexes [Ar(OCH2C≡CAu)2]n {Ar = 1,4-C H4(CMe2-4-C H4)2,
4,4’-C6H4C6H4 and 1,5-C10H } react with diphosphines LL = Ph P(CH 6)nPPh (n = 16 to 6)
6
2
2
2
and trans-Ph2PCH=CHPPh2 to give luminescent macrocyclic digold(I) or tetragold(I) complexes
with bridging diphosphine and diacetylide ligands. The digold(I) complex [1,4-C6H4(CMe2-4-
C6H4OCH2C≡CAu)2(µ-LL)], with LL = trans-Ph2PCH=CHPPh2, forms a 28-membered ring, and
the rings associate through aurophilic bonding in the solid state. In contrast, the tetragold(I) complex
[4,4’-C6H4C6H4(OCH2C≡CAu)2(µ-LL)], with LL = Ph2PCH2PPh2, forms a more rigid 42-memb-
ered ring.
Key words: Gold, Macrocycle, Diacetylide, Diphosphine, Luminescence
Introduction
bonding [9, 10] may influence the structure by orient-
ing the diphosphine digold units, as for example in for-
mation of the tetragold(I) complex [R’(C≡CAu)2(µ-
LL)]2, with R’ = 1,4-C6H4 and LL = Ph2PCH2PPh2
[7, 8].
The construction of macrocyclic complexes with
a sufficiently large cavity to accommodate guest
molecules or to form interlocked structures such
as catenanes and rotaxanes is of great interest in
supramolecular chemistry [1]. Alkynylgold(I) com-
plexes are useful in this field because they are
easy to prepare, they have high thermal stability,
and they exhibit useful emission or non-linear opti-
cal properties [2 – 7]. The simplest compounds have
the formula [Au(C≡CR)L], often with L = ter-
tiary phosphine ligand, but many diphosphine deriva-
tives [(AuC≡CR)2(µ-LL)] or diacetylide derivatives
[R’(C≡CAuL)2], with R’ = a bridging spacer group,
are also known [2 – 7]. Phosphinoacetylide ligands
can bridge between gold centers to give binuclear or
polynuclear complexes [6, 7].
Gold complexes of diacetylide ligands containing
flexible angular propargyloxy units, R’(OCH2C≡
CAu)2, in combination with diphosphine ligands
can exist either as large macrocycles, such as A – C,
Chart 1, or as zigzag polymers [11, 12]. The macro-
cyclic complexes [X(C6H4-4-OCH2C≡CAu)2(µ-
LL)], C, can exist in equilibrium with the interlocked
[2]catenanes, E, or when X = cyclohexylidene
and LL = Ph2P(CH2)4PPh2, as a doubly braided
[2] catenane [{C6H10(C6H4-4-OCH2C≡CAu)2(µ-
LL)}2]2 [12]. The natural lability at the linear gold(I)
center allows easy equilibration between these isomers
[9, 12]. The tetragold derivatives, such as E (Chart 1),
are so far known only for more rigid diacetylide
ligands [7, 8].
Gold(I) complexes with diacetylide and diphos-
phine ligands can yield polymers [R’(C≡CAu)2(µ-
LL)]n [7], or digold or tetragold macrocycles,
Since the factors that determine the nature of the
[R’(C≡CAu)2(µ-LL)] or [R’(C≡CAu)2(µ-LL)]2 re- self-assembly processes in reactions of digold(I) di-
spectively [7 – 12]. The degree of aggregation is de- acetylides with diphosphines are still not fully under-
termined by the rigidity versus flexibility of the di- stood, it was of interest to investigate further examples
acetylide ligand and by the bite distance and preferred of gold(I) complexes with diacetylide and diphosphine
conformation of the neutral bridging ligand LL [7, 8]. bridging ligands, in order to determine the degree of
In addition, the presence of aurophilic (Au...Au) aggregation. This article reports complexes based on
c
0932–0776 / 04 / 1100–1488 $ 06.00 ꢀ 2004 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
1489
O
O
O
O
O
O
Au
Au
P
P
X
H
H
Au
Au
Au
P
Au
O
P
X
B, X = (CH2)3 or (CH2)4
A, X = CH2 or (CH2)4
O
n
O
O
O
4
1
Au
P
Au
Au
P
P
P
O
O
O
O
O
X
X
Y
Au
Y
X
Y
H
H
P
Au
Au
Au
P
O
O
O
C, Y = CMe2, X = (CH2)2
D, Y = CMe2, X = (CH2)3 or (CH2)4
Au
P
P
Au
Au
Au
Au
P
P
n
X
X
2
5
O
O
E, X = CH2
H
Au
Au
Chart 1. P = PPh2.
H
O
three new diacetylide ligands, with varying flexibil-
ity and bite distance, in combination with the diphos-
phine ligands Ph2P(CH2)nPPh2 (n = 1−6) and trans-
Ph2PCH=CHPPh2, and the structures of a digold and a
tetragold macrocycle.
n
3
6
Chart 2.
as (PhC≡CAu)n and (t-BuC≡CAu)6 [14]. The struc-
tures 4 – 6 in Chart 2 show only the σ-bonds to the
alkynyl groups since the nature of the oligomerization
through π-bonding is uncertain.
Results and Discussion
Synthesis and structures of gold(I) acetylide macro-
cycles
Reactions of the digold(I) diacetylides, 4 – 6, with
diphosphine ligands gave the corresponding com-
plexes [{R’(OCH2C≡CAu)2(µ-LL)}x], 7 – 9 respec-
tively, which were isolated as air-stable, white solids.
The complexes were soluble in dichloromethane, in
contrast to the known insoluble polymeric complexes,
suggesting that they have macrocyclic structures, but
the size of the macrocycle (x = 1 or 2) and possi-
bility of catenation is to be determined. Molecular
modeling indicated moderate ring strain for the sim-
ple macrocycles (x = 1) for the complexes with LL =
Ph2P(CH2)nPPh2 only when n = 1, and very little ring
strain in any case when x = 2; entropy effects favor
the smaller ring with x = 1 [12]. The complexes failed
to give parent ions in the mass spectra, so they were
characterized by their IR and NMR spectra and, when
crystals could be grown, by X-ray structure determina-
tion.
The diacetylene ligands 1,4-C6H4(CMe2-4-C6H4-
OCH2C≡CH)2, 1, 4,4’-C6H4C6H4(OCH2C≡CH)2, 2,
and 1,5-C10H6(OCH2C≡CH)2, 3, (Chart 2) were pre-
pared by standard methods [13]. They have decreas-
ing sizes of the spacer groups, while ligand 1 is
much more flexible than 2 and 3. In each case, re-
action with two equivalents of [AuCl(SMe2)] in the
presence of base gave the corresponding digold(I)
diacetylide 1,4-C6H4(CMe2-4-C6H4OCH2C≡CAu)2,
4, 4,4’-C6H4C6H4(OCH2C≡CAu)2, 5, and 1,5-C10H6
(OCH2C≡CAu)2, 6, which were isolated as yellow,
insoluble solids. The infrared spectra of compounds
4, 5 and 6 contained bands at 1999, 2009, and
2000 cm−1, respectively, assigned to ν(C≡C). These
vibrations are shifted to lower frequency by approxi-
mately 100 cm−1 from the free ligands, and suggests
the presence of linearly coordinated gold(I) centers
Reaction of [1,4-C6H4(CMe2-4-C6H4-OCH2C≡
with both η1 and η2 coordination of the alkynyl groups CAu)2], 4, with diphosphine ligands, LL, gave
to gold(I), as in simple alkynylgold(I) compounds such the complexes [{1,4-C6H4(CMe2-4-C6H4-OCH2C≡C
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

1490
W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
◦
displays a weak band at 2134 cm−1 corresponding
to the v(C≡C) stretch. In the 1H NMR spectrum,
there were single resonances for the CMe2, OCH2
and CH=CH protons and, in the 31P NMR spectrum,
a singlet resonance at 33.5, indicating a symmetrical
structure. The molecular structure of, 7f, is shown in
Fig. 1, with relevant bond parameters listed in Table 1.
The complex forms a digold(I) macrocycle with a 28
atom circumference. The transannular Au...Au dis-
˚
Table 1. Selected bond lengths (A) and angles ( ) for com-
plex 7f a.
Au(1)-C(2)
Au(1)-P(1)
Au(1)-Au(2)
2.00(1)
2.275(2)
2.9644(5)
Au(2)-C(10)
Au(2)-P(2)
P(2)-C(71)
2.02(1)
2.270(2)
1.76(2)
C(2)-Au(1)-P(1)
C(2)-Au(1)-Au(2)
172.0(2)
92.7(2)
C(10)-Au(2)-P(2)
C(10)-Au(2)-Au(1)
P(2)-Au(2)-Au(1)
173.8(2)
88.0(2)
P(1)-Au(1)-Au(2)
a
95.00(5)
97.92(5)
Symmetry transformations used to generate equivalent atoms:
−x+1, −y+1, −z+1.
˚
tance is 6.46 A and the longest transannular distances
˚
are C(5)...P(1A) = 12.56 A and O(1)...C(103A) =
˚
12.68 A. Clearly, the macrocycle cavity is large
enough to allow catenation, but pairs of macrocycles
associate instead one above the other (such that there
is a center of symmetry located between them) as
shown in Fig. 1. The conformation of the diphos-
phine ligand is neither syn nor anti, with dihedral
angle Au(1)-P(1)...P(2A)-Au(2A) = 80◦. The angles
P-Au-C = 172.0(2) and 173.8(2)◦ are distorted from
linearity, with each gold atom displaced towards the
neighboring molecule so as to form an inter-ring au-
˚
rophilic bond [Au(1)...Au(2) = 2.964(1) A]. The large
cavity of each macrocycle is occupied by pairwise
interpenetration of a phenyl group of the neighboring
molecule, as shown in Fig. 1. In this conformation of
the macrocycle pairs, there are two aurophilic bonds
and multiple attractive aryl...aryl interactions between
pairs of phenylphosphorus groups and between phenyl
groups and aryloxy groups. The dihedral angle C(2)-
Au(1)...Au(2)-C(10) = 90.7◦ is ideal for forming a
strong aurophilic bond [9].
These pairs of macrocycles of complex 7f pre-
sumably dissociate in solution to give the individual
macrocycles. The structures of the other macrocycles
in the solid state have not been determined because
suitable single crystals could not be grown, but it is
likely that they also exist as the simple macrocycles
in solution. For the complexes [1,4-C6H4(CMe2-4-
C6H4-OCH2C≡CAu)2(µ-Ph2P(CH2)nPPh2)], 7a – 7e,
the ring size ranges from 28 (7a, n = 2) to 32 (7e,
n = 6) atoms. The structure of the second isomer of
7a, when n = 2, is unknown.
Fig. 1. Molecular structure of [1,4-C6H4(CMe2-4-C6H4
OCH2C≡CAu)2(µ-trans-Ph2PCH=CHPPh2)], 7f: (a) Top
view of a pair of macrocycles, with phenyl groups omitted
for clarity. (b) Side view, showing interpenetration of each
macrocycle by a phenyl group of its neighbor.
Au)2(µ-LL)}x], 7a – 7e for LL = Ph2P(CH2)nPPh2
with n = 2 − 6 respectively, and 7f when LL =
trans-Ph2PCH=CHPPh2. The reaction of 4 with
Ph2PCH2PPh2 gave a soluble product, but it could not
be isolated in analytically pure form and its 31P NMR
spectrum contained many resonances, indicating that
it exists in solution as a complex mixture. Complex 7a
(n = 2) was isolated in analytically pure form but the
31P NMR spectrum contained two singlet resonances
with approximately equal intensities, indicating that it
exists in solution as a mixture of two isomers. In all
other cases, the 31P NMR spectra contained only one
singlet resonance, as expected for a single isomer.
The reaction of [4,4’-C6H4C6H4(OCH2C≡CAu)2]n
with diphosphines gave the complexes [{4,4’-
C6H4C6H4(OCH2C≡CAu)2(µ-LL)}x], 8a – 8f for
LL = Ph2P(CH2)nPPh2 with n = 1 − 6 respectively,
and 8g with LL = trans-Ph2PCH=CHPPh2. In all
cases, the 31P NMR spectra contained only a single
The IR spectrum of the complex [1,4-C6H4(CMe2- resonance, indicating that each compound exists in
4-C6H4-OCH2C≡CAu)2(µ-Ph2PCH=CHPPh2)], 7f, solution as a single isomer. The molecular structure
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
1491
◦
˚
Table 2. Selected bond lengths (A) and angles ( ) for com-
O
O
plex 8a a.
7a, X = (CH2)2
7b, X = (CH2)3
7c, X = (CH2)4
7d, X = (CH2)5
7e, X = (CH2)6
7f, X = trans-CH=CH
Au
Au
Au(1)-C(1)
Au(1)-Au(2)
Au(2)-P(2)
2.00(1)
Au(1)-P(1)
3.2129(5) Au(2)-C(20)
2.266(2)
2.03(1)
1.17(1)
P
P
X
2.272(2)
C(1)-C(2)
C(1)-Au(1)-P(1)
P(1)-Au(1)-Au(2)
P(2)-Au(2)-Au(1)
C(20)-C(19)-C(18)
a
175.7(3)
84.20(6)
89.99(6)
179(1)
C(20)-Au(2)-P(2)
C(1)-Au(1)-Au(2)
C(20)-Au(2)-Au(1)
C(19)-C(20)-Au(2)
175.6(3)
100.0(3)
94.1(3)
173(1)
P
P
Au
Au
X
Symmetry transformations used to generate equivalent atoms:
O
O
O
#1
−x, −y−1, −z+1.
Au
Au
O
P
P
X
8a, X = CH2
O
O
O
8b, X = (CH2)2
8c, X = (CH2)3
8d, X = (CH2)4
8e, X = (CH2)5
8f, X = (CH2)6
Au
Au
P
X
P
8g, X = trans-CH=CH
Fig. 2. Molecular structure of [{4,4’-C6H4C6H4(OCH2
C≡CAu)2(µ-Ph2PCH2PPh2)}2], 8a.
9a, X = (CH2)2
9b, X = (CH2)3
9c, X = (CH2)4
9d, X = (CH2)5
9e, X = (CH2)6
9f, X = trans-CH=CH
of 8a, LL = Ph2PCH2PPh2, was determined and is
shown in Fig. 2, with selected bond lengths and angles
listed in Table 2. The complex exists as the tetragold(I)
macrocycle (x = 2), and is present as a remarkable
42-membered ring, which adopts an extended chair
conformation with a center of symmetry at the mid-
point of the macrocycle. The bridging diphosphine
ligand has the syn conformation, with dihedral angle
Au(1)P(1)...P(2)Au(2) = 18◦, as in other gold(I) com-
plexes with bridging Ph2PCH2PPh2 ligands [9, 10].
The angles at gold are roughly linear with CAuP =
175.6(3) and 175.7(3)◦, and there is a transannular
O
Au
P
P
X
Au
Chart 3. P = PPh2.
transannular aurophilic bonding will be absent, or at
least much weaker, for the complexes 8b – 8g with
other diphosphine ligands. None of these complexes
yielded single crystals suitable for X-ray structure de-
termination, but we tentatively propose that they have
the simpler macrocyclic structures with x = 1.
The reaction of [1,5-C10H6(OCH2C≡CAu)2]n, 6,
with diphosphine ligands gave the complexes [{1,5-
C10H6(OCH2C≡CAu)2(µ-LL)}x], 9a– 9e for LL =
Ph2P(CH2)nPPh2 with n = 2 − 6 respectively, and 9f
with LL = trans-Ph2PCH=CHPPh2. In all these cases,
the 31P NMR spectra contained only a single reso-
nance, indicating that each compound exists in solu-
tion as a single isomer. The similar reaction of complex
6 with LL = Ph2PCH2PPh2 gave a mixture of com-
plexes that could not be purified. This behavior is sim-
ilar to that observed in formation of complexes 7 from
the precursor 4 and, by analogy, it is likely that all of
the isolated complexes have the macrocyclic structures
with x = 1. The ring sizes (taking the shortest route
˚
aurophilic bond with Au(1)...Au(2) = 3.213(1) A.
The gold acetylide units are directed slightly apart,
with increasing transannular distances C(1)...C(20) =
˚
˚
˚
3.77 A, C(2)...C(19) = 4.11 A, C(3)...C(18) = 4.69 A,
˚
and O(4)...O(17) = 4.99 A, and this appears to occur
in order to optimize the offset side-by-side, transan-
nular aryl...aryl interactions between the biphenyl
groups [shortest CC distances are C(7)...C(14) =
˚
3.50 and C(9)...C(12) = 3.65 A]. The closest analogy
to the structure of 8a is the found in the rigid rod
diacetylide derivative E (Chart 1) [7, 15], but the
additional -OCH2- spacer units in 8a give much
greater flexibility in forming the chair conformation
rather than the planar conformation in E.
The double ring (x = 2) for the complexes 8, [{4,4’- through the naphthyl groups) then vary from 18 in 9a
C6H4C6H4(OCH2C≡CAu)2(µ-LL)}x], is likely to be to 22 in 9e. A summary of the proposed structures is
unique for 8a, with LL = Ph2PCH2PPh2, since the shown in Chart 3.
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

1492
W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
Table 3. Luminescence data for phosphine gold(I) acetylide
macrocyclesa.
Red-shifts, on going from solution to solid state, of 47
to 83 nm were observed when n = 1 − 4, but smaller
shifts of 19 and 7 nm were observed when n = 5 and 6
respectively.
Diphosphine
Spacer X
(CH2)2
Emission
max, nm
425, 664
415
454, 603
415
452, 563
426
458, 574
416
448, 554
413
467, 555
447
501
446
503
427
514
431
503
456
470
467
Complex
Medium
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
7a
Experimental Section
7b
7c
7d
7e
7f
(CH2)3
(CH2)4
(CH2)5
(CH2)6
CH=CH
CH2
The complex [AuCl(SMe2)] [16] and ligands 2 and 3
[13] were prepared by literature methods. NMR spectra were
recorded by using a Varian Mercury 400 MHz spectrometer.
Chemical shifts are reported relative to TMS (1H, 13C) or
85% H3PO4 (31P). IR spectra were recorded as Nujol mulls
by using a Perkin-Elmer 2000 FTIR. Emission spectra were
recorded at room temperature using a Fluorolog-3 spectroflu-
orometer. For recording the emission and excitation spectra,
solutions were placed in quartz cuvettes, while solids were
ground finely with FTIR grade KBr. A 1 nm slit width was
used for the solid samples and a 3 nm slit width for the solu-
tions. CAUTION: gold acetylides are potentially shock sen-
sitive and should be handled in small quantities using protec-
tive equipment.
8a
8b
8c
8d
8e
8f
(CH2)2
(CH2)3
(CH2)4
(CH2)5
(CH2)6
CH=CH
[1,4-C6H4(CMe2-4-C6H4OCH2C≡CH)2], 1. A mixture
of 1,4-C6H4(CMe2-4-C6H4OH)2 (10.0 g, 28.9 mmol), 3-
bromopropyne (6.43 ml, 80% solution, 57.8 mmol) and
potassium carbonate (11.97 g, 86.6 mmol) in acetone
(100 ml) was heated under reflux for 24 h. The reaction mix-
ture was filtered to remove KBr, the solvent was removed
under vacuum, and the yellow oily residue extracted with
ether. The ether solution was washed with aqueous sodium
bicarbonate, then dried with magnesium sulphate, filtered,
and the solvent removed under vacuum. The product was
recrystallized from MeOH (50 ml) to give a colorless solid
496
480
487
CH2Cl2
solid
8g
CH2Cl2
461
a
Excitation was at 350 nm in each case.
Luminescence of the gold(I) complexes
The photophysical properties of the gold acetylide
macrocycles are summarized in Table 3. Upon
excitation at 350 nm, the gold(I) complexes [1,4- which was collected by filtration and washed with ether.
Yield: 5.8 g, 48%. NMR (CDCl3): δ(1H) = 7.15 [d, 4H,
C6H4(CMe2-4-C6H4OCH2C≡CAu)2(µ-Ph2P(CH2)n-
3J(HH) = 9 Hz, OArH2,6], 7.08 [s, 4H, CArC], 6.86 [d, 4H,
PPh2)], 7a– 7e, in solution in dichloromethane,
3J(HH) = 9 Hz, OArH3,5], 4.64 [d, 4J(HH) = 2 Hz, OCH2],
displayed single emission bands with maxima between
413 (7e) to 426 (7c) nm but, in the solid state, two
emission bands were observed in each case. A higher
energy emission band in the range 425 (7a) to 458
3.00 [t, 2H, 4J(HH)=2 Hz, CCH], 1.62 [s, 12H, CCH3];
δ(13C) = 155.40, 147.72, 143.85 [ipso-C’s], 127.78 [ArC3,5],
126.20 [C-Ar-C], 114.14 [ArC2,6], 78.82 [CCH], 75.31
[CCH], 55.92 [OCH2], 41.92 [CCH3], 30.88 [CH3]; IR (Nu-
(7d) nm is assigned to an excited state having mostly
jol): v(C≡C) = 2127 cm−1, v(C≡CH) = 3271, 3284 cm−1
;
intraligand π-π∗ (acetylide) character, while a lower
energy band in the range 554 (7e) to 664 (7a) nm is
assigned to a metal centered emissive state, based on
literature precedents [2, 9]. Both bands are red shifted
compared to the solution state, as a result of either
enhanced Au... Au bonding or π-stacking in the solid
state. The complexes [{4,4’-C6H4C6H4(OCH2C≡C-
Au)2(µ-Ph2P(CH2)nPPh2)}x], 8, gave only single
emission peaks either in solution in dichloromethane
or in the solid state. The emission maxima ranged
between 427 (8b) and 480 (8f) nm in solution, and
EI-MS: m/z = 422.224, calcd. m/z = 422.227.
[1,4-C6H4(CMe2-4-C6H4OCH2C≡CAu)2]n, 4. To a so-
lution of [AuCl(SMe2)] (0.500 g, 1.70 mmol) in THF
(20 ml)/MeOH (10 ml) was added a solution of [1,4-
C6H4(CMe2-4-C6H4OCH2C≡CH)2] (0.36 g, 0.85 mmol)
and sodium acetate (0.31 g, 2.55 mmol) in THF
(10 ml)/MeOH (10 ml). The reaction mixture was stirred
for 3 h, forming a yellow precipitate which was collected by
filtration, washed with THF, MeOH, ether, and pentane and
dried. Yield: 0.643 g, 93%. IR(Nujol): 1999 (w) cm−1
.
[4,4’-C6H4C6H4(OCH2C≡C-Au)2]n, 5. This was pre-
between 470 (8e) and 514 (8c) nm in the solid state. pared similarly from [AuCl(SMe2)] (0.50 g, 1.70 mmol) and
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
1493
4,4’-C6H4C6H4(OCH2C≡CH)2 (0.22 g, 0.85 mmol). Yield:
[1,4-C6H4(CMe2-4-C6H4OCH2C≡C-Au)2(µ-Ph2P-
0.512 g, 92%. IR(Nujol): 2009 (w) cm−1
.
(CH2)6 PPh2)], 7e, from 4 (0.210 g, 0.26 mmol) and
Ph2P(CH2)6PPh2 (0.117 g, 0.26 mmol). Yield: 0.168 g,
51%. NMR (CD2Cl2): δ(1H)= 7.57 − 7.36 [m, 20H, Ph],
7.13 [d, 4H, 3J = 8.8 Hz, OArH2,6], 7.15 [s, 4H, CArC], 6.88
[d, 4H, 3J = 8.7 Hz, OArH3,5], 4.73 [s, 4H, OCH2], 2.32
[m, 4H, CH2P], 1.39 [m, 8H, CH2], 1.63 [s, 12H, CCH3];
[1,5-C10H6(OCH2C≡C-Au)2]n, 6. This was prepared
similarly from [AuCl(SMe2)] (1.00 g, 3.40 mmol) and 1,5-
C10H6(OCH2C≡CH)2 (0.40 g, 1.70 mmol). Yield: 0.953 g,
89%. IR(Nujol): 2000 (w) cm−1
.
[1,4-C6H4(CMe2-4-C6H4OCH2C≡C-Au)2(µ-Ph2P-
(CH2)2PPh2)], 3a. A solution of Ph2P(CH2)2PPh2 (0.098 g,
0.25 mmol) in CH2Cl2 (10 ml) was added to a suspension
of complex 4 (0.200 g, 0.25 mmol) in CH2Cl2 (10 ml).
The mixture was stirred for 3 h, then decolorizing charcoal
δ(31P) = 38.03 (s). IR(Nujol): v(C≡C) = 2134 cm−1
.
Analysis for C60H60O2P2Au2: calcd. C 56.79, H 4.77;
found C 57.17, H 5.04.
[1,4-C6H4CMe2-4-C6H4OCH2C≡C-Au)2(µ-trans-Ph2-
(100 mg) was added and the mixture stirred for 15 min. PCH=CHPPh2)], 7f, from 4 (0.400 g, 0.49 mmol) and
The mixture was filtered and pentane (100 ml) was added trans-Ph2PCH=CHPPh2 (0.195 g, 0.49 mmol). Yield:
to the filtrate to precipitate the product as a colorless solid, 0.318 g, 54%. NMR (CD2Cl2): δ(1H)= 7.49 − 7.36
which was collected by filtration, washed with ether and [m, 20H, Ph], 7.10 [d, 4H, 3J = 9 Hz, OArH2,6], 7.04
pentane, and dried under vacuum. Yield: 0.16 g, 54%. NMR [s, 4H, CArC], 7.03 [t, 2H, 2J(PH)= 19 Hz, CH=],
(CD2Cl2): δ(1H)= 7.40 − 7.65 [m, 20H, Ph], 7.12 [d, 4H, 6.81 [d, 4H, 3J = 9 Hz, OArH3,5], 4.71 [s, 4H, OCH2],
3J(HH) = 8.5 Hz, ArH2,6], 7.10 [s, 4H, CArC], 6.96 [4H, 1.60 [s, 12H, CCH3]; δ(31P) = 33.47 (s). IR(Nujol):
OArH3,5], 4.76 [s, 4H, OCH2], 2.63, 2.51 [m, 4H, CH2P]; v(C≡C) = 2134 cm−1. Analysis for C56H50O2P2Au2: calcd.
δ(31P) = 39.59, 40.13. IR(Nujol): v(C≡C)=2130 cm−1
.
C 55.55, H 4.16; found C 55.76, H 4.25.
Analysis for C56H52O2P2Au2: calcd. C 55.45, H 4.32; found
C 56.11, H 4.80.
[{4,4’-C6H4C6H4(OCH2C≡C-Au)2(µ-Ph2PCH2-
PPh2)}2], 8a. A solution of Ph2PCH2PPh2 (0.176 g,
0.46 mmol) in CH2Cl2 (10 ml) was added to a suspension
of complex 5 (0.300 g, 0.46 mmol) in CH2Cl2 (10 ml).
The mixture was stirred for 3 h, then decolorizing charcoal
(100 mg) was added and the mixture stirred for a further
15 min. The solution was filtered and pentane (100 ml) was
added to precipitate the product as a colorless solid, which
was collected by filtration, washed with ether and pentane,
and dried under vacuum. Yield: 0.164 g, 34%. NMR
(CD2Cl2): δ(1H)= 7.27 −−7.61 [m, 24H, Ph, Ar], 6.90 [d,
4H, 3J = 8.8 Hz, ArH), 4.80 [s, 4H, OCH2], 3.62 [t, 2H,
3J(PH) = 11.2 Hz, CH2P]; δ(31P) = 32.99 (s). IR(Nujol):
v(C≡C) = 2124 cm−1. Analysis for C43H34O2P2Au2: calcd.
Similarly prepared were:
[1,4-C6H4(CMe2-4-C6H4OCH2C≡C-Au)2(µ-Ph2P-
(CH2)3PPh2)], 7b, from 4 (0.200 g, 0.25 mmol) and
Ph2P(CH2)3PPh2 (0.101 g, 0.25 mmol). Yield: 0.167 g,
55%. NMR (CD2Cl2): δ(1H)= 7.66 − 7.61, 7.44 − 7.40
[m, 20H, Ph], 7.10 [d, 4H, 3J(HH) = 9 Hz, OArH2,6],
7.09 [s, 4H, CArC], 6.90 [d, 4H, 3J = 8.6 Hz, OArH3,5],
4.75 [s, 4H, OCH2], 2.78 [m, 4H, CH2P], 1.82 [m, 2H,
CH2P], 1.60 [s, 12H, CCH3]; δ(31P)=34.85 (s). IR(Nujol):
v(C≡C) = 2125 cm−1. Analysis for C57H54O2P2Au2: calcd.
C 55.80, H 4.44; found C 56.43, H 4.54.
[1,4-C6H4(CMe2-4-C6H4OCH2C≡C-Au)2(µ-Ph2P-
(CH2)4PPh2)], 7c, from 4 (0.200 g, 0.25 mmol) and C 49.73, H 3.30; found C 49.27, H 2.95.
Ph2P(CH2)4PPh2 (0.105 g, 0.246 mmol). Yield: 0.143 g,
Similarly were prepared:
47%. NMR (CD2Cl2): δ(1H)= 7.44 − 7.65, [m, 20H, Ph],
7.43 [d, 4H, 3J = 7.2 Hz, OArH2,6], 7.40 [s, 4H, CArC], 6.88
[d, 4H, 3J = 8.8 Hz, OArH3,5], 4.73 [s, 4H, OCH2], 2.51
[m, 4H, CH2P], 1.69 [m, 4H, CH2], 1.62 [s, 12H, CCH3];
δ(31P) = 35.98 (s). IR(Nujol): v(C≡C)=2134 cm−1. Anal-
ysis for C58H56O2P2Au2: calcd. C 56.14, H 4.55; found
C 55.89, H 4.59.
[1,4-C6H4(CMe2-4-C6H4OCH2C≡C-Au)2(µ-Ph2P-
(CH2)5PPh2)], 7d, from 4 (0.200 g, 0.25 mmol) and
Ph2P(CH2)5PPh2 (0.112 g, 0.25 mmol). Yield: 0.155 g,
[4,4’-C6H4C6H4(OCH2C≡C-Au)2(µ-Ph2P(CH2)2P-
Ph2)], 8b, from (0.200 g, 0.31 mmol) and
5
Ph2P(CH2)2PPh2 (0.122 g, 0.31 mmol). Yield: 0.204 g,
63%. NMR (CD2Cl2): δ(1H)= 7.37 − 7.59 [m, 24H, Ph,
3
Ar], 7.05 [d, 4H, J(HH) = 8 Hz, Ar], 4.81 [s, 4H, OCH2],
2.62 [sbr, 4H, CH2P]; δ(31P) = 39.86 (s). IR(Nujol):
v(C≡C)=2133 cm−1. Analysis for C44H36O2P2Au2: calcd.
C 50.21, H 3.45; found C 50.52, H 3.41.
[4,4’-C6H4C6H4(OCH2C≡C-Au)2(µ-Ph2P(CH2)3P-
50%. NMR (CD2Cl2): δ(1H)= 7.65 − 7.39 [m, 20H, Ph], Ph2)], 8c, from 5 (0.500 g, 0.76 mmol) and Ph2P(CH2)3PPh2
7.12 [d, 4H, 3J = 8 Hz, OArH2,6], 7.14 [s, 4H, CArC], 6.88 (0.315 g, 0.76 mmol). Yield: 0.457, 56%. NMR (CD2Cl2):
[d, 4H, 3J = 8 Hz, OArH3,5], 4.72 [s, 4H, OCH2], 2.44 δ(1H)= 7.3 − 7.6 [m, 24H, Ph, Ar], 7.03 [d, 4H,
[m, 4H, CH2P], 1.59 [m, 6H, CH2], 1.63 [s, 12H, CCH3]; 3J(HH) = 9 Hz, Ar], 4.73 [s, 4H, OCH2], 2.76 [m, 4H,
δ(31P) = 36.93 (s). IR(Nujol): v(C≡C)=2133 cm−1. Anal- CH2P], 1.83 [m, 2H, CH2P]; δ(31P) = 34.62 (s). IR(Nujol):
ysis for C59H58O2P2Au2: calcd. C 56.47, H 4.66; found v(C≡C)=2120 cm−1. Analysis for C45H38O2P2Au2: calcd.
C 56.26, H 4.86.
C 50.67, H 3.59; found C 50.98; H 3.85.
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

1494
W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
v(C≡C)=2133 cm−1. Analysis for C44H34O2P2Au2: calcd.
Table 4. Crystal data and experimental details for 7f and 8a.
C 50.30, H 3.26; found C 49.99, H 3.03.
Complex
7f.2CH2Cl2
8a
Empirical formula
Formula weight
Temperature [K]
Wavelength [A]
Crystal system
Space group
C58H54Au2Cl4O2P2 C86H68Au4O4P4
[1,5-C10H6(OCH2C≡C-Au)2(µ-Ph2P(CH2)2PPh2)], 9a.
A solution of Ph2P(CH2)2PPh2 (0.400 g, 0.64 mmol) in
CH2Cl2 (10 ml) was added to a suspension of 6 (0.253 g,
0.64 mmol) in CH2Cl2 (10 ml). The product was isolated
as above as a colorless solid. Yield: 0.379 g, 58%. NMR
(CD2Cl2): δ(1H)=7.82 [d, 2H, 3J(HH) = 8 Hz, ArH4,8],
7.38 − 7.60 [m, 22H, Ph and ArH3,7], 7.06 [d, 2H, 3J =
8 Hz, ArH2,6], 4.99 [s, 4H, CH2O], 2.62 [sbr, 4H, CH2P];
δ(31P) = 39.95 (s). IR(Nujol): v(C≡C) = 2133 cm−1. Anal-
ysis for C42H34O2P2Au2: calcd. C 49.14, H 3.34; found
C 49.21, H 3.39.
1380.69
2077.15
200(2)
150(2)
˚
0.71073
0.71073
monoclinic
P21/n
monoclinic
C2/c
Unit cell dimensions
a = 16.4885(4)
b = 14.7849(5)
c = 23.1772(6)
β = 108.757(2)
5350.1(3)
4
a = 29.0161(14)
b = 13.2611(4)
c = 23.9963(11)
β = 108.2611(4)
8752.1(6)
4
◦
˚
[A, ]
3
˚
Volume [A ]
Z
Density
1.714
1.576
(calculated) [g/cm3]
Absorption
Similarly were prepared:
5.779
6.801
coefficient [mm−1
]
[1,5-C10H6(OCH2C≡C-Au)2(µ-Ph2P(CH2)3PPh2)], 9b,
F(000)
Crystal size [mm3]
Absorption correction
Data / restraints / params 12294 / 34 / 667
Final R indices
[I > 2σ(I)]
2696
3968
from
6 (0.200 g, 0.32 mmol) and Ph2P(CH2)3PPh2
0.10×0.10×0.05
0.25×0.15×0.13
(0.131 g, 0.32 mmol). Yield: 0.135 g, 41%. NMR (CD2Cl2):
integration
integration
3
δ(1H) = 7.80 [d, 2H, J(HH) = 8 Hz, ArH4,8], 7.20 − 7.60
9634 / 0 / 394
R1 = 0.0558,
wR2 = 0.1484
3
[m, 22H, Ph and ArH3,7], 7.08 [d, 2H, J = 8 Hz, ArH2,6],
R1 = 0.0524,
wR2 = 0.1108
5.00 [s, 4H, CH2O], 2.70 [sbr, 4H, CH2P], 1.79 [sbr, 2H,
CH2P]; δ(31P) = 35.10 (s). IR(Nujol): v(C≡C) = 2134 cm−1
.
Analysis for C43H36O2P2Au2: calcd. C 49.63, H 3.49; found
C 50.10, H 3.50.
[4,4’-C6H4C6H4(OCH2C≡C-Au)2(µ-Ph2P(CH2)4P-
Ph2)], 8d, from (0.500 g, 0.76 mmol) and
5
[1,5-C10H6(OCH2C≡C-Au)2(µ-Ph2P(CH2)4PPh2)], 9c,
Ph2P(CH2)4PPh2 (0.326 g, 0.76 mmol). Yield: 0.464,
56%. NMR (CD2Cl2): δ(1H)= 7.3−7.6 [m, 24H, Ph], 7.05
[s, 4H, 3J(HH) = 9 Hz, Ar], 4.82 [s, 4H, OCH2], 2.39 [m, 4H,
CH2P], 1.68 [m, 4H, CH2]; δ(31P) = 36.82 (s). IR(Nujol):
v(C≡C) = 2133 cm−1. Analysis for C46H40O2P2Au2: calcd.
C 51.12, H 3.73; found C 51.41, H 4.04.
from
6 (0.400 g, 0.64 mmol) and Ph2P(CH2)4PPh2
(0.271 g, 0.64 mmol). Yield: 0.369 g, 55%. NMR (CD2Cl2):
3
δ(1H) = 7.81 [d, 2H, J(HH) = 8 Hz, ArH4,8], 7.35 − 7.57
[m, 22H, Ph and ArH3,7], 7.05 [d, 2H, 3J(HH) = 8 Hz,
ArH2,6], 4.98 [s, 4H, CH2O], 2.38 [m, 4H, CH2P],
1.63 [m, 4H, CH2]; δ(31P) = 36.90 (s). IR(Nujol):
v(C≡C) = 2133 cm−1. Analysis for C44H38O2P2Au2: calcd.
C 50.11, H 3.63; found C 50.16, H 3.52.
[4,4’-C6H4C6H4(OCH2C≡C-Au)2(µ-Ph2P(CH2)5P-
Ph2)], 8e, from 5 (0.250 g, 0.38 mmol) and Ph2P(CH2)5PPh2
(0.174 g, 0.38 mmol). Yield: 0.262 g, 62%. NMR
(CD2Cl2): δ(1H)= 7.4 − 7.6 [m, 24H, Ph, Ar], 7.05 [s, 4H,
3J(HH) = 8 Hz, Ar), 4.81 [s, 4H, OCH2], 2.35 [m, 4H,
CH2P], 1.53 [m, 6H, CH2]; δ(31P) = 35.21 (s). IR(Nujol):
v(C≡C)=2132 cm−1. Analysis for C48H42O2P2Au2: calcd.
C 51.57, H 3.87; found C 51.98, H 3.84.
[1,5-C10H6(OCH2C≡C-Au)2(µ-Ph2P(CH2)5PPh2)], 9d,
from
6 (0.200 g, 0.32 mmol) and Ph2P(CH2)5PPh2
(0.144 g, 0.32 mmol). Yield: 0.148 g, 44% NMR (CD2Cl2):
3
δ(1H) = 7.85 [d, 2H, J(HH) = 8 Hz, ArH4,8], 7.36 − 7.63
3
[m, 22H, Ph and ArH3,7], 7.06 [d, 2H, J = 8 Hz, ArH2,6],
5.08 [s, 4H, CH2O], 2.14 [sbr, 4H, CH2P], 1.42 [sbr, 6H,
CH2P]; δ(31P) = 37.80 (s). IR(Nujol): v(C≡C) = 2133 cm−1
.
[4,4’-C6H4C6H4(OCH2C≡C-Au)2(µ-Ph2P(CH2)6P-
Ph2)], 8f, from 5 (0.300 g, 0.46 mmol) and Ph2P(CH2)6PPh2
(0.208 g, 0.46 mmol). Yield: 0.370 g, 73%. NMR (CD2Cl2):
δ(1H)= 7.4−7.6 [m, 24H, Ph], 7.06 [d, 4H, 3J(HH) = 8 Hz,
Ar], 4.82 [s, 4H, OCH2], 2.35 [m, 4H, CH2P], 1.50 [m, 4H,
CH2], 1.37 [m, 4H, CH2]; δ(31P) = 33.15 (s). IR(Nujol):
v(C≡C) = 2134 cm−1. Analysis for C50H44O2P2Au2: calcd.
C 52.00, H 4.00; found C 51.89, H 3.76.
Analysis for C45H40O2P2Au2: calcd. C 50.58, H 3.77; found
C 50.10, H 3.52.
[1,5-C10H6(OCH2C≡C-Au)2(µ-Ph2P(CH2)6PPh2)],
9e, from 6 (0.200 g, 0.32 mmol) and Ph2P(CH2)6PPh2
(0.144 g, 0.32 mmol). Yield: 0.199 g, 58%. NMR (CD2Cl2):
δ(1H) = 7.83 [d, 2H, 3J = 8 Hz, ArH4,8], 7.40 − 7.65 [m,
22H, Ph and ArH3,7], 7.05 [d, 2H, 3J = 8 Hz, ArH2,6],
5.02 [s, 4H, CH2O], 2.31 [sbr, 4H, CH2P], 1.52 [sbr, 8H,
[4,4’-C6H4C6H4(OCH2C≡C-Au)2(µ-trans-Ph2PCH=
CHPPh2)], 8g, from 5 (0.500 g, 0.76 mmol) and trans-Ph2 CH2]; δ(31P) = 37.54 (s). IR(Nujol): v(C≡C)=2133 cm−1
.
PCH=CHPPh2 (0.303 g, 0.76 mmol). Yield: 0.459 g, 57%. Analysis for C46H42O2P2Au2: calcd. C 50.70, H 3.91; found
NMR (CD2Cl2): δ(1H)= 7.35−7.55 [m, 24H, Ph, Ar], 7.10 C 51.03, H 3.86.
3
3
[t, 2H, J(PH) = 19.0 Hz, CH=], 7.02 [d, 4H, J = 8.6 Hz,
[1,5-C10H6(OCH2C≡C-Au)2(µ-trans-Ph2PCH=CHP-
Ar], 4.72 [s, 4H, OCH2]; δ(31P) = 34.80 (s). IR(Nujol): Ph2)], 9f, from 6 (0.300 g, 0.48 mmol) and trans-Ph2PCH=
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
1495
CHPPh2 (0.189 g, 0.48 mmol). Yield: 0.318 g, 65%. NMR Crystals of [1,4-C6H4CMe2-4-C6H4OCH2C≡C-Au)2(µ-
(CD2Cl2): δ(1H) = 7.82 [m, 2H, ArH4,8], 7.58 − 7.38 [m, trans-Ph2PCH=CHPPh2)] were grown by slow diffusion
24H, Ph, ArH3,7, CH=], 7.04 [m, 2H, ArH2,6], 4.98 [s, 4H, of ether into a solution of 7f in CH2Cl2. The centre of the
CH2O]; δ(31P) = 21.27 (s). IR(Nujol): v(C≡C)=2133 cm−1
.
dimer was located on a crystallographic centre of symme-
Analysis for C42H32O2P2Au2: calcd. C 49.24, H 3.15; found try. The phenyl ring, C71-C76, was disordered and was
C 49.87, H 3.17.
modeled with 70/30 occupancy. Two molecules of CH2Cl2
were refined with anisotropic thermal motion, with fixed
C–Cl bond lengths of 1.76(2) A. 5a: Crystals of [Au2(µ-
X-ray structure determinations
˚
CCCH2OC6H4C6H4OCH2CC)2(µ-Ph2PCH2PPh2)2] were
grown by slow diffusion of ether into a solution of 8a in
CH2Cl2 at −4 ◦C. The molecule was located on a symmetry
element. There was disordered solvent present which could
Crystals were mounted on glass fibers. Data were
collected using a Nonius Kappa-CCD diffractometer with
COLLECT (Nonius B.V., 1998). The unit cell parameters
were calculated and refined from the full data set. Crystal
cell refinement and data reduction were carried out using
DENZO (Nonius B.V., 1998). The absorption correction
was carried out by integration using SCALEPACK (Nonius
B.V., 1998). The crystal data and refinement parameters
for 3f and 5a are listed in Table 4. The SHELXTL-NT
V5.1 (Sheldrick, G. M.) suite of programs was used to solve
the structures by direct methods. All of the non-hydrogen
atoms were refined with anisotropic thermal parameters.
The hydrogen atoms were calculated geometrically and
were riding on their respective carbon atoms. Complex 7f:
not be modeled successfully. The program SQUEEZE
3
˚
found two voids (each 1045 A in size) at (0,0,0) and
(1/2, 1/2, 1/4). For each void 93 electrons were removed
(CH2Cl2 = 42 e and ether = 42 e).
Acknowledgements
We thank the NSERC (Canada) for financial support and
for a scholarship to WH. RJP thanks the Government of
Canada for a Canada Research Chair.
[1] S. Leininger, B. Olenyuk, P. J. Stang, Chem. Rev. 100,
853 (2000).
Davies, M. Samoc, J. Chem. Soc., Dalton Trans. 4167
(1997).
[2] a) J. M. Forward, J. P. Fackler (Jr), Z. Assefa, in D. M.
Roundhill and J. P. Fackler (Jr) (eds): Optoelectronic
Properties of Inorganic Compounds, Plenum Press,
pp. 195 – 239, New York (1999); b) V. W. W. Yam,
K. K. W. Lo, Chem. Soc. Rev. 28, 323 (1999); c) C. M.
Che, H. Y. Chao, V. M. Miskowski, Y. Li, K. K. Che-
ung, J. Am. Chem. Soc. 123, 4985 (2001); d) V. W. W.
Yam, K. K. W. Lo, K. M. C. Wong, J. Organomet.
Chem. 578, 1999; e) M. J. Irwin, J. J. Vittal, R. J. Pud-
dephatt, Organometallics 16, 3541 (1997); f) V. W. W.
Yam, S. W. K. Choi, J. Chem. Soc., Dalton Trans. 4227
(1996).
[3] a) R. Y. Liau, A. Schier, H. Schmidbaur,
Organometallics 22, 3199 (2003); b) J. Vicente,
M. T. Chicote, M. D. Abrisqueta, Organometallics
16, 5628 (1997); c) T. E. Mu¨ller, D. M. P. Mingos,
D. J. Williams, J. Chem. Soc., Chem. Commun. 1787
(1994); d) R. J. Cross, M. F. Davidson, J. Chem. Soc.,
Dalton Trans. 411 (1986).
[4] a) N. C. Payne, R. Ramachandran, R. J. Pudde-
phatt, Can. J. Chem. 73, 6 (1995); b) N. C. Payne,
R. Ramachandran, I. Treurnicht, R. J. Puddephatt,
Organometallics 9, 880 (1990).
[5] a) C. E. Powell, M. G. Humphrey, Coord. Chem. Rev.
248, 725 (2004); b) R. H. Naulty, M. P. Cifuentes,
M. G. Humphrey, S. Houbrechts, C. Boutton, A. Per-
soons, G. A. Heath, D. C. R. Hockless, B. Luther-
[6] M. Bardaji, A. Laguna, P. G. Jones, Organometallics
20, 3906 (2001).
[7] a) R. J. Puddephatt, Coord. Chem. Rev. 216 – 217, 313
(2001); b) R. J. Puddephatt, J. Chem. Soc., Chem.
Commun. 1055 (1998); c) M. I. Bruce, B. C. Hall,
B. W. Skelton, M. E. Smith, A. H. White, J. Chem.
Soc. Dalton Trans. 995 (2002); d) M. J. Irwin, G. Jia,
N. C. Payne, R. J. Puddephatt, Organometallics 15, 51
(1996).
[8] a) M. J. Irwin, L. M. Rendina, J. J. Vittal, R. J. Pudde-
phatt, J. Chem. Soc., Chem. Commun. 1281 (1996);
b) M. A. MacDonald, R. J. Puddephatt, G. P. A. Yap,
Organometallics 19, 2194 (2000).
[9] H. Schmidbaur, Gold: Progress in Chemistry, Bio-
chemistry and Technology, Wiley, Chichester (1999).
[10] N. C. Payne, R. J. Puddephatt, R. Ravindranath,
I. Treurnicht, Can. J. Chem. 66, 3176 (1988).
[11] a) W. J. Hunks, M. A. MacDonald, M. C. Jennings, R. J.
Puddephatt, Organometallics 19, 5063 (2000); b) W. J.
Hunks, J. Lapierre, H. A. Jenkins, R. J. Puddephatt, J.
Chem. Soc., Dalton Trans. 2885 (2002).
[12] a) C. P. McArdle, M. C. Jennings, J. J. Vittal, R. J. Pud-
dephatt, Chem. Eur. J. 7, 3572 (2001); b) C. P. McAr-
dle, M. J. Irwin, M. C. Jennings, J. J. Vittal, R. J. Pud-
dephatt, Chem. Eur. J. 8, 723 (2002); c) F. Mohr, R. J.
Puddephatt, J. Organomet. Chem. 689, 374 (2004).
[13] a) D. Z. Simon, S. Brookman, J. Beliveau, R. L. Sal-
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM

1496
W. J. Hunks et al. · Macrocyclic Gold(I) Complexes
vador, J. Pharm. Sci. 66, 431 (1977); b) B. Venu-
gopalen, K. K. Balasubramanian, Heterocycles 23, 81
(1985).
[15] a) M. J. Irwin, J. J. Vittal, G. P. A. Yap, R. J. Pudde-
phatt, J. Am. Chem. Soc. 118, 13101 (1996); b) M. C.
Brandys, M. C. Jennings, R. J. Puddephatt, J. Chem.
Soc., Dalton Trans. 4601 (2000).
[16] A. Tamaki, J. K. Kochi, J. Organomet. Chem. 64, 411
(1974).
[14] a) G. E. Coates, C. Parkin, J. Chem. Soc. 3220 (1962);
b) D. M. P. Mingos, J. Yau, S. Menzer, D. J. Williams,
Angew. Chem. Int. Ed. Engl. 34, 1894 (1995).
Brought to you by | University Paris-Sud
Authenticated
Download Date | 4/9/19 1:41 PM