Syntheses and molecular structures of some phosphine-gold(I) derivatives of 1,3-diynes

Article abstract of DOI:10.1016/j.jorganchem.2005.08.050

The syntheses of several diynylgold(I) phosphine complexes, including Au(C≡CC≡CH){P(tol)₃} (1), Au(C≡CC≡CSiMe ₃)(PR₃) (R = Ph 2-Ph, tol 2-tol), Au(C≡CC≡CFc) (PPh₃) (3), {(tol)₃P}Au(C≡C)_nAu{

Full text of DOI:10.1016/j.jorganchem.2005.08.050

Journal of Organometallic Chemistry 691 (2006) 361–370
www.elsevier.com/locate/jorganchem
Syntheses and molecular structures of some
phosphine–gold(I) derivatives of 1,3-diynes
a,
a
b
a
Michael I. Bruce *, Martin Jevric , Brian W. Skelton , Mark E. Smith ,
b
a
Allan H. White , Natasha N. Zaitseva
a
Department of Chemistry, University of Adelaide, Adelaide, SA 5005, Australia
Chemistry M313, University of Western Australia, Crawley, WA 6009, Australia
b
Received 3 June 2005; received in revised form 23 August 2005; accepted 23 August 2005
Available online 15 December 2005
Abstract
The syntheses of several diynylgold(I) phosphine complexes, including Au(C„CC„CH){P(tol)3} (1), Au(C„CC„CSiMe3)(PR3)
(R = Ph 2-Ph, tol 2-tol), Au(C„CC„CFc)(PPh3) (3), {(tol)3P}Au(C„C)nAu{P(tol)3} [n = 2 (4), 3 (6), 4 (7)], {(Ph3P)Au}C„
CC„C{Au[P(tol)3]} (5), [ppn][Au{C„CC„CAu[P(tol)3]}2] (8), [Au2(l-I)(l-dppm)2][Au(C„CC„CSiMe3)2] (9), Hg{C„CC„
CAu(PR3)}2 (R = Ph 10-Ph, tol 10-tol) and {(triphos)Cu}C„CC„C{Au[P(tol)3]} (11) are described. Of these, the X-ray molecular
structures of 1, 2-tol, 3, 4 and 9 have been determined.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Diynyl–gold(I) complexes; Phosphine–gold(I) complexes; X-ray diffraction; Crystal structures
1. Introduction
eral derivatives of 1,3-diynes, which extend the earlier stud-
ies and are summarised in Scheme 2.
Contemporary interest in gold(I) chemistry derives in
part from its tendency to adopt linear two-coordination
[1] and the formation of weak gold–gold intramolecular
interactions (aurophilicity) [2]. In conjunction with alkynyl
or poly-ynyl groups, this can result in the formation of
rigid-rod materials [3], which may have unusual non-linear
optical [4] or photo-emission properties [5]. The conscious
employment of the aurophilic character has resulted in
design and construction of unusual geometries [6 ]. Our
own interest has previously encompassed some of these fea-
tures (Scheme 1) [7], while more recently, we have used
elimination of phosphine–gold(I) halides as a component
of reactions designed to give long carbon chains end-
capped by redox-active metal centres, which are modifica-
tions of the well-known Sonogashira reaction [8]. In the
course of this work, we have made and characterised sev-
2. Results and discussion
Following established procedures, the reaction between
AuCl{P(tol)3} and buta-1,3-diyne was carried out in a
thf/diethylamine solvent mixture in the presence of CuI
to give pale yellow Au(C„CC„CH){P(tol)3} (1) in 63%
yield. The IR spectrum of this compound contains
m(„CH) and m(C„C) absorptions at 3300 and
2157 cmÀ1, respectively, while its H NMR spectrum con-
1
tains singlet resonances at d 1.66 and 2.38, assigned to
the „CH and Me protons, respectively, and a multiplet
between d 7.20 and 7.43 for the C6H4 protons. In the 13C
NMR spectrum, resonances at d 22.17 and between 125.7
and 142.0 arise from the tolyl groups; only three of the four
diynyl carbons were found, at d 60.14 (Cd), 69.55 (Cc) and
85.49 (Cb). The 31P NMR spectrum contains a singlet at d
40.3 from the P(tol)3 ligand.
*
Corresponding author. Tel.: +61 8 8303 5939; fax: + 61 8 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.08.050

362
M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
AuCl(PPh3)
HC
C
C
CH
HC
HC
C
C
C
C
C
C
Au(PPh3)
Au PPh2
(AuCl)2(µ-dppm)
HC
C
C
C
Au PPh2
AuCl(PPh3)
Cp(OC)3W
C
C
C
CH
Cp(OC)3W
Cp(OC)3W
C
C
C
C
Au(PPh3)
(AuCl)2(µ-dppm)
C
C
C C Au PPh2
Cp(OC)3W
C
C
C
C
Au PPh2
C
C
C
C
CH
Ph2P Au
C
C
C
C
C
C
C
Au PPh2
Au PPh2
Ph2P Au
{Au(OTf)}2(µ-dppm)
Ph2P Au C
C
CH
Ph2P Au C
HC
C
C
C
CH
[ppn][Au(C
C
C
C
CH)2]
W(CO)3Cp
C C CH
[ppn][Au{C
[ppn][Au{C
C
C
C
C
[W(CO)3Cp]}2]
Au(PPh3)}2]
[ppn][Au(acac)]2
HC
C C C Au(PPh3)
C
HC
C
C C
[ppn] Au
C
C
C
C
2
Scheme 1.
The related complexes Au(C„CC„CSiMe3)(PR3)
signals at d 69.19 and 72.85 assigned at the C5H4 carbons, a
multiplet between d 128.2 and 134.9 to the Ph carbons,
were accompanied by resonances at d 66.61 (Cd), 70.36
(Cipso of Fc), 70.65 (Fe–Cp), 74.82 (Cc) and 88.27 (Cb).
The 31P resonance for the PPh3 ligand is at d 41.4. In this
case, M+ in the ES-MS occurs at m/z 692.
(R = Ph 2-Ph, tol 2-tol) were obtained in 77% and 67%
yields from similar reactions of AuCl(PR3) employing
HC„CC„CSiMe3. Their spectroscopic properties include
three m(C„C) absorptions between 2184 and 2036 cmÀ1
(probably arising from Fermi coupling) and resonances
at d 0.14/0.13 (Ph/tol, SiMe3), 2.37 (tol Me) and multiplets
at d 7.19–7.51 (aromatic). The 13C NMR spectrum con-
tains the expected resonances at d À0.12/À0.14 (Ph/tol,
SiMe3), 21.41 (tol Me) and between d 128.8 and 142.0 (aro-
matic). Again, only three of the diynyl carbons were found,
at d 78.71/78.89 (Cd), 86.67/87.02 (Cc) and 89.52/89.62
(Cb).
The molecular structures of 1, 2-tol and 3 were deter-
mined by single-crystal X-ray diffractometry and plots of
single molecules are shown in Fig. 1. Selected bond param-
eters are collected in Table 1. Generally, there are no unu-
sual intermolecular interactions. The phosphine–gold(I)
moiety is r-bonded to the diynyl ligand [Au–C(1)
˚
2.272(3), 2.2779(9), 2.276(2) A, respectively], while the
Treatment of a mixture of AuCl(PPh3) and HC„CC„
CFc in MeOH with KOH afforded orange Au(C„CC„
CFc)(PPh3) (3) in 85% yield. This compound has weak
m(C„C) bands at 2191 and 2053 cmÀ1, while the 1H
NMR spectrum contains multiplets for C5H4 (d 3.83,
4.34) and Ph protons (d 6.88–6.98, 7.10–7.16) accompanied
by the Fe–Cp singlet at d 4.01. In the 13C NMR spectrum,
short–long–short C–C separations along the chain are con-
sistent with the diynyl formulation, with there being no evi-
dence for p-electron delocalisation. In 1, the H atom
attached to C(4) was located in difference maps; in 2-tol,
˚
C(4)–Si(4) is 1.808(5) A, while in 3, the C(4)–C(41) distance
2
˚
is 1.417(9) A, a normal value for a C(sp)–C(sp ) separation.
The six-atom P–Au–C(1–4) chains are essentially linear,

M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
363
CuI
AuCl(PR3)
AuCl(PR3)
+
+
HC
C
C
CR'
(R3P)Au
C
C
C
CR'
thf/NHEt2
R = tol, R' = H; 1, SiMe3; 2-tol
R = Ph, R' = SiMe3; 2-Ph
KOH
(Ph3P)Au
[(tol)3P]Au
C
C
C
CFc
HC
C
C
CFc
MeOH
3
1. NaOH/MeOH
2. AuCl[P(tol)3]
Me3Si
C
C
SiMe3
C
C
Au[P(tol)3]
n
n
n = 2; (4), 3; (6), 4; (7)
[(tol)3P]Au
C
C
C
CH
CuI
[(tol)3P]Au
C
C
C
C
Au(PPh3)
+
thf/NHEt2
5
AuCl(PPh3)
CuCl / tmeda / O2 / acetone
OR
[(tol)3P]Au
C
C
Au[P(tol)3]
[(tol)3P]Au
C
C
C
CH
4
Cu(OAc)2 / pyridine / ∆
7
[ppn][Au(acac)2]
CH2Cl2 / NHEt2
Au
[(tol)3P]Au
C
C
C
CH
ppn
C
C
C
C
Au[P(tol)3]
2
8
(AuCl)2(µ-dppm)
CuI
Au2(µ-I)(µ-dppm)2 Au C
C
C
CSiMe3
2
+
thf/NHEt2
9
HC
C
C
CSiMe3
Hg(OAc)2
thf
Hg
C
C
C
C
Au[PR3]
(R3P)Au
C
C
C
CR'
2
R = Ph; 10-Ph, tol; 10-tol
1. nBuLi / thf
[(tol)3P]Au
C
C
C
C
Cu(triphos)
[(tol)3P]Au
C
C
C
CH
2. CuCl(triphos)
11
Scheme 2.
with maximum deviations being 9ꢁ [at C(1) in 1], 5.1ꢁ [at
Au in 2-tol] and 3.5ꢁ [at C(3) in 3]. Total bending amounts
to 20.5ꢁ (1), 19.55ꢁ (2-tol) and 11.4ꢁ (9).
compound in 85% yield, while coupling of Au(C„
CC„CH){P(tol)3} (1) with another equivalent of
AuCl{P(tol)3} in thf/NHEt2 in the presence of CuI gave
1
Of note are the larger displacement ellipsoids for C(3)
and C(4) in 1, suggesting relatively larger vibrational
amplitudes for these atoms, consistent with present ideas
concerning the low bending force constant in chains of
C(sp) atoms [9]. Molecules of 2-tol co-crystallise with
AuI{P(tol)3} in the proportion 80/20. The individual com-
ponents were independently isolable and refinable and data
are quoted to the relevant statistics.
a 78% yield. The H NMR spectrum contains signals at d
2.29 (Me) and between d 7.12 and 7.32 (C6H4), while the
13C NMR resonances at d 21.39 (Me) and between d
126.6 and 141.7 similarly arise from the P(tol)3 ligand,
which also gives a 31P resonance at d 40.6. The two diyndiyl
carbons are found at d 88.11 (Cb) and 119.89 (Ca); the lat-
ter shows a doublet J(CP) coupling of 140 Hz. Related
complexes containing PPh3 [8] or PCy3 [10] are known.
The molecular structure of 4 is shown in Fig. 2, with
selected bond parameters in Table 1. The molecule is not
centrosymmetric, but the dimensions of both halves are
essentially identical. The Au–P distances are 2.275,
The symmetrical digold complex {(tol)3P}AuC„
CC„CAu{P(tol)3} (4) was prepared by two routes. Treat-
ment of
a mixture of Me3SiC„CC„CSiMe3 and
AuCl{P(tol)3} in MeOH with NaOH gave the pale yellow

364
M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
The mixed ligand complex {(Ph3P)Au}C„CC„
C{Au[P(tol)3]} (5) was obtained in 51% yield from
Au(C„CC„CH)(PPh3) and AuCl{P(tol)3} in thf/NHEt2
in the presence of CuI. In addition to the resonances from
the PR3 ligands, the 13C NMR spectrum contained reso-
nances assigned to the diyndiyl chain at d 85.78 (Cb),
88.23 (Cc), 125.80 (Ca, broad) and 126.96 (Cd, broad);
the 31P NMR spectrum has two singlets at d 40.2
[P(tol)3] and 42.6 (PPh3). Assignments are based on com-
parisons with the homo-disubstituted compounds.
11
32
4
31
3
2
1
Au
12
P
21
22
Use of NaOH as base was also applicable to complexes
containing longer carbon chains, reactions between
AuCl{P(tol)3} and Me3Si(C„C)nSiMe3 (n = 3, 4) giving
the corresponding {(tol)3P}Au(C„C)nAu{P(tol)3} [n = 3
(6), 4 (7)] in 76 and 20% yields, respectively. Compound
7 was also obtained by oxidative coupling of 1 using either
Cu(OAc)2 in pyridine (57%) or dioxygen in the presence of
a
42
1
CuCl/tmeda (33%). These two compounds contained H,
13C and 31P resonances for the P(tol)3 ligands in the
expected positions. In the IR spectrum, medium intensity
m(C„C) bands are found at 2139 and 2115 (6) and at
2167 and 2134 cmÀ1 (7), while we assign singlets at d
81.63 (Cc), 88.13 (Cb) and 127.94 (Ca, broad) (6) and at d
60.91 (Cd), 67.23 (Cc), 86.94 (Cb, broad) and 131.29 (Ca,
broad) (7) to the various carbons of the poly-ynyl chains.
4
Si(4)
41
3
2
32
12
1
31
Au
26
P
43
I
11
Che and co-workers have described analogues with PCy3
3
for n = 2–4 [10] and have studied their (pp ) emissivities.
*
In turn, theoretical studies have characterised the geome-
tries of the singlet and triplet states [11].
b
The use of [ppn][Au(acac)2] for the preparation of anio-
nic gold(I) derivatives of alkynes has been described on sev-
eral occasions [12]. During the present work, we have
found that the direct reaction between [ppn][Au(acac)2]
and 1 in a dichloromethane/diethylamine solvent mixture
afforded [ppn][Au{C„CC„CAu[P(tol)3]}2] (8) in 39%
yield as a creamy white solid. In the NMR spectra, signals
for the P(tol)3 ligand were found at dH 2.29 and dC 21.36
(Me), between dH 7.15 and 7.62 and dC 125.5 and 141.8
(C6H4) and at dP 39.62; the ppn resonance is at dP 22.21.
The weak IR m(C„C) band is at 2145 cmÀ1. Overall, this
compound is very similar to the PPh3 analogue [7].
45’
44’
22
41’
45
41
44
43
32
Fe
43’
42
Au
1
3
2
4
21
P
42’
11
12
A
similar anionic complex, [Au2(l-I)(l-dppm)2]-
c
[Au(C„CC„CSiMe3)2] (9), was obtained from the reac-
tion between (AuCl)2(l-dppm) and HC„CC„CSiMe3 in
a thf/NHEt2 mixture in the presence of CuI. This light yel-
Fig. 1. Plots of single molecules of: (a) Au(C„CC„CH){P(tol)3} (1), (b)
Au(C„CC„CSiMe3){P(tol)3} (2-tol), also showing co-crystallised
AuI{P(tol)3}, and (c) Au(C„CC„CFc)(PPh3) (3).
low compound shows m(C„C) at 2176 and 2122 cmÀ1
,
1
while the H NMR spectrum contains a singlet at d 0.16
for the SiMe3 protons, as well as multiplets at d 4.57 and
between d 7.24 and 7.76 from the dppm protons. The 31P
resonance is at d 27.7. Both components of the salt were
found in the positive or negative ion mode ES-MS, the
[Au2I(dppm)2]+ cation at m/z 1289 and the [Au(C4-
SiMe3)2]À anion at m/z 439, respectively.
The cation in 9 (Fig. 3(a)) has been structurally charac-
terised on two previous occasions, with iodide [13, no atom
coordinates available] and [Au(CN)2]À counter-ions [14],
these being obtained serendipitously from reactions of
˚
˚
2.273(1) A and the Au–C separations are both 1.996(5) A.
Along the chain, the short–long–short separations support
the diyndiyl formulation with no delocalisation of p-elec-
tron density. The P–Au–C4–Au–P chain is essentially lin-
ear, with a maximum deviation at C(4) (10.8ꢁ) and total
bending of 22.2ꢁ, all in the same sense; the separation
˚
˚
P(1)Á Á ÁP(2) is 12.235(2) A, some 0.20 A shorter than the
˚
sum of interatomic distances (12.43 A). In the cell
(Fig. 2(b)), it can be seen that packing of individual mole-
cules is influenced by PhÁ Á ÁPh interactions.

M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
365
Table 1
Selected bond distances (A) and angles (ꢁ)
˚
Complex
1
2a
3
4
9b
˚
Bond distances (A)
Au–P
Au–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–X
2.272(3)
1.99(1)
1.19(2)
1.38(2)
1.19(3)
2.2779(9)
1.993(6)
1.163(9)
1.418(8)
1.229(7)
2.276(2)
2.010(7)
1.18(1)
1.39(1)
1.20(1)
2.275(1), 2.273(1)
1.996(5)
1.196(6)
1.390(6)
1.215(6)
2.009, 1.984(8)
1.15, 1.21(1)
1.42, 1.39(1)
1.21, 1.21(1)
1.808(5) [Si(4)]
1.417(9) [C(41)]
1.996(5) [Au(2)]
1.83, 1.84(1) [Si]
Bond angles (ꢁ)
P–Au–C(1)
Au–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–X
a
172.5(3)
171(1)
177(1)
179(1)
174.9(2)
176.3(6)
176.6(6)
177.1(6)
178.6(2)
177.3(6)
177.6(9)
176.5(7)
178.6(8)
178.7(2), 176.2(2)
176.3(6)
178.6(6)
178.8(5)
169.2(6) [Au(2)]
174.0(7), 175(1)
174, 175(1)
177, 180(1)
177.7(4) [Si(4)]
170(1), 170.5(9) [Si]
˚
For 2, AuI{P(tol)3} component (19%): Au–I 2.598(3) A, P–Au–I 177.85(6)ꢁ.
For 5, [Au2(l-I)(l-dppm)2]+ cation: Au(1)–Au(2) 2.9576(4). Au(1,2)–I 3.1014, 3.1071(6), Au–P 2.310–2.320(3) A; Au(1)–I–Au(2) 56.90(1), P–Au–P
b
˚
164.70, 166.34(7), P–C(0)–P 115.9(4), 115.0(4)ꢁ. For anion, C(11)–Au(3)–C(21) 178.1(3)ꢁ.
{Au[l-(PPh2)2CH]}2 (containing deprotonated dppm
ligands) with MeI, or from [Au2(l-dppm)2][BH3(CN)]2
with NaI; the latter was converted to the dicyanoaurate(I)
salt on attempted recrystallisation. In all three examples,
the two gold atoms are bridged by the iodine, with a
strongly acute Au–I–Au angle [56.90(1)ꢁ in 9, 54.2(1)ꢁ in
212
211
132
131
222
P(1)
Au(2)
Au(1)
1
2
4
3
P(2)
232
231
122
111
112
a
a
c
b
Fig. 2. Plots of: (a) a single molecule and (b) the packing in the unit cell, of {(tol)3P}AuC„CC„CAu{P(tol)3} (4).

366
M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
I
2212
1212
2211
1122
Au(2)
20
P(22)
P(21)
10
P(12)
2111
Au(1)
2112
2221
P(11)
1111
1221
2222
2121
1222
2122
1112
a
142
241
243
21
Au(3)
22
11
23
12
24
13
14
143
Si(24)
Si(14)
b 141
242
Fig. 3. Plots of: (a) the cation and (b) the anion in [Au2(l-I)(l-dppm)2][Au(C„CC„CSiMe3)2] (9).
the [Au(CN)2]À salt]. For 9, the two Au–I distances are
21.43 (Me), dH 7.18–7.39 and dC 126.8–141.7 (C6H4) and
dP 40.6. Resonances at dC 72.52, 88.15 [J(CP) 29 Hz] and
102.52 are tentatively assigned to Cc, Ca and Cd, respec-
tively, on the basis of the observed C–P coupling for Ca
and the anticipated shift of Cd upon coordination to the
mercury centre. Only aromatic resonances were found for
10-Ph.
The first complex containing two different Group 11
metal centres linked by a diyndiyl ligand was obtained by
treating 1 with LiBu, followed by addition of CuCl(triphos)
[triphos = MeC(CH2PPh2)3], when creamy white {(tri-
phos)Cu}C„CC„C{Au[P(tol)3]} (11) was isolated in
62% yield. The IR spectrum contains two m(C„C) bands
at 2158 and 2127 cmÀ1, while only phosphorus ligand res-
onances are found in the 1H [d 1.44 (C–Me), 2.28 (P–CH2),
2.36 (tol-Me), 6.82–7.46 (aromatic)], 13C [21.43 (tol-Me),
36.47 and 37.53 (C–Me), 39.93 (P–CH2) and 125.3–142.3
(aromatic)] and 31P [À25.1 (triphos), 45.2 {P(tol)3}]
NMR spectra.
˚
3.1014, 3.1071(6) A, their near equality being similar to
˚
those in the iodide (3.127, 3.196(2) A) but contrasting with
those in the [Au(CN)2]À salt (3.161, 3.342(3) A). The
˚
AuÁ Á ÁAu separations are 2.9576(4) (9), 2.948(2) (iodide)
˚
and 2.967(1) A (dicyanoaurate), while the closest
approaches to the I atom are from the phenyls of adjacent
˚
cations [IÁ Á ÁC(2213) (x, 1 À y, 1 À z) 3.890(8) A].
In the anion (Fig. 3(b)), the two Au–C(sp) distances are
˚
2.009, 1.984(8) A, with alternating short–long–short C–C
separations along the chain [C(n1)–C(n2) 1.15, 1.21(1),
˚
C(n2)–C(n3) 1.42, 1.39(1), C(n3)–C(n4) 1.21, 1.21(1) A
(n = 1,2)]. The anion contains an 11-atom Si–C4–Au–C4–
Si chain which is essentially linear, with angles at Au
178.1(3)ꢁ and ranging from 170 to 180 ꢁ at C. Bending is
all in the same sense, the total summing to 36.9ꢁ and result-
˚
ing in the two Si atoms being 15.053(4) A apart, some
˚
0.20 A shorter than the sum of interatomic distances
˚
(15.25 A).
Bridging of two diynyl-gold chains through mercury was
achieved by direct reaction of Hg(OAc)2 with 1 in thf, when
white Hg{C„CC„CAu[P(tol)3]}2 (10-tol) was isolated in
54% yield. The PPh3-analogue, Hg{C„CC„CAu(PPh3)}2
3. Conclusions
This paper has described the syntheses of several
examples of phosphine–gold(I) complexes containing var-
ious diynyl fragments, the molecular structures of four of
these being determined by single-crystal X-ray diffraction
studies. Some of these compounds have found use as
(10-Ph) was obtained from
a similar reaction of
Au(C„CC„CH)(PPh3). Weak m(C„C) bands are found
at 2166 and 2052 (tol) or 2100 and 2014 (Ph) cmÀ1, while
for 10-tol, P(tol)3 resonances occur at dH 2.35 and dC

M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
367
intermediates, particularly in the synthesis of longer car-
bon chains by elimination of phosphine–gold(I) halides,
as described elsewhere [8].
7.43 (m, 12H, tol). 13C NMR: d 22.17 (s, Me), 60.14 (s,
Cd), 69.55 (s, Cc), 85.49 (br, Cb), 125.75–141.97 (m, tol).
31P NMR: d 40.30.
4. Experimental
4.3.2. Au(C„CC„CSiMe3)(PPh3) (2-Ph)
To a suspension of AuCl(PPh3) (500 mg, 1.01 mmol) in
thf/NHEt2 (30 mL, 1/2) containing CuI (20 mg,
0.105 mmol) was added HC„CC„CSiMe3 (185 mg,
1.52 mmol) and the mixture was stirred at r.t. for 1h. The
solvent was removed and the residue extracted with
CH2C12 and loaded onto a SiO2 column. The product
was eluted with hexane. Reduction of solvent volume
resulted in precipitation of pale yellow Au(C„CC„CSi-
Me3)(PPh3) (2-Ph) (450 mg, 77%). Anal. Found: C, 49.78;
H, 3.38. C25H24AuPSi.0.5CH2Cl2 requires: C, 49.16; H,
4.05; M, 580. IR (nujol): m(C„C) 2184m, 2129m, 2038m
4.1. General
All reactions were carried out under dry nitrogen,
although normally no special precautions to exclude air
were taken during subsequent work-up. Common solvents
were dried, distilled under nitrogen and degassed before
use. Separations were carried out by preparative thin-layer
chromatography on glass plates (20 · 20 cm2) coated with
silica gel (Merck, 0.5 mm thick).
4.2. Instruments
cmÀ1 1H NMR: d 0.14 (s, 9H, SiMe3), 7.51–7.42 (m,
.
15H, Ph). 13C NMR d À0.12 (s, SiMe3), 78.71 (s, Cd),
86.67 (s, Cc), 89.52 (br, Cb), 134.31–129.08 (m, Ph). 31P
NMR: d 42.41.
IR spectra were obtained on a Bruker IFS28 FT-IR
spectrometer. Spectra in CH2Cl2 were obtained using a
0.5 mm path-length solution cell with NaCl windows.
Nujol mull spectra were obtained from samples mounted
between NaCl discs. NMR spectra were recorded on a Var-
ian 2000 instrument (1H at 300.13 MHz, 13C at 75.47 MHz,
31P at 121.503 MHz). Unless otherwise stated, samples
were dissolved in CDCl3 contained in 5 mm sample tubes.
Chemical shifts are given in ppm relative to internal tetra-
4.3.3. Au(C„CC„CSiMe3){P(tol)3} (2-tol)
To a solution of AuCl{P(tol)3} (250 mg, 0.47 mmol) in
thf/NHEt2 (15 mL, 1/3) was added CuI (ca 5 mg) followed
by HC„CC„CSiMe3 (114 mg, 0.94 mmol). The yellow
solution was stirred for 1h in the dark and the solvent
removed. Extraction with CH2Cl2 and passage through a
SiO2 column eluting with hexane yielded a pale yellow
band which gave pale yellow solid Au(C„CC„CSi-
Me3){P(tol)3} (2-tol) (195 mg, 67%). Anal. Found: C,
53.98; H, 4.83%. Calc. for C28H30AuPSi: C, 54.02; H,
4.86; M, 623. IR (CH2Cl2): m(C„C) 2183m, 2131m,
methylsilane for H and 13C NMR spectra and external
1
H3PO for 31P NMR spectra. Electrospray mass spectra
(ES-MS) were obtained from samples dissolved in MeOH
unless otherwise indicated. Solutions were injected into a
Varian Platform II spectrometer via a 10 mL injection
loop. Nitrogen was used as the drying and nebulising gas.
Chemical aids to ionisation were used [15]. Elemental anal-
yses were by CMAS, Belmont, Vic., Australia.
2036m cmÀ1 1H NMR: d 0.13 (s, 9H, SiMe3), 2.37 (s,
.
9H, Me), 7.19–7.42 (m, 12H, tol). 13C NMR: d À0.14 (s,
SiMe3), 21.41 (s, Me), 78.89 (s, Cd), 87.02 (s, Cc), 89.62
(br, Cb), 125.82–142.00 (m, tol). 31P NMR: d 40.25.
4.3. Reagents
4.3.4. Au(C„CC„CFc)(PPh3) (3)
AuCl(PR3) (R = Ph [16], tol [17]), [ppn][Au(acac)2] [18],
(AuCl)2(l-dppm) [19], Au(C„CC„CH)(PPh3) [7], CuCl-
(triphos) [20], HC„CC„CR (R = H [21], Fc [22]) and
Me3Si(C„C)nSiMe3 (n = 2 [23], 3 [24], 4 [25]) were
obtained as previously described.
KOH (100 mg, 1.8 mmol) was added to a suspension of
AuCl(PPh3) (105 mg, 0.212 mmol) and HC„CC„CFc
(55 mg, 0.235 mmol) in dry MeOH (15 mL) and the mix-
ture was stirred for 1 h. After cooling on ice, the precipitate
was collected on a sinter and washed with cold MeOH to
give Au(C„CC„CFc)(PPh3) (3) (120 mg, 85%) as an
orange powder. Anal. Found: C, 55.53; H, 3.40%. Calc.
for C32H24AuFeP: C, 55.52; H, 3.49; M, 000. IR (nujol):
4.3.1. Au(C„CC„CH){P(tol)3} (1)
To a solution of AuCl{P(tol)3} (2.0 g, 3.73 mmol) in thf/
NHEt2 (60 mL, 1/3) was added CuI (71 mg, 0.37 mmol)
followed by HC„CC„CH (6.9 mL of a 2.7 M solution
in thf, 18.6 mmol) and the mixture was stirred at r.t. for
30 min. The solvent was removed and the residue extracted
with CH2C12 and loaded onto a SiO2 column. The product
was eluted with CH2Cl2, addition of hexane and reduction
of solvent volume resulting in precipitation of pale yellow
Au(C„CC„CH){P(tol)3} (1) (1.3 g, 63%). Anal. Found:
C, 54.51; H, 4.01. C25H22AuP requires: C, 54.56; H, 4.03;
1
m(C„C) 2191w, 2053w cmÀ1. H NMR (C6D6): d 3.83,
4.34 (2 · m, 2 · 2H, C5H4), 4.01 (s, 5H, Fe–Cp), 6.88–
6.98, 7.10–7.16 (2 · m, 8 + 7H, Ph). 13C NMR (C6D6): d
66.61 (Cx), 69.19, 72.85 (2 · s, C5H4), 70.65 (Fe–Cp),
74.82, 88.27, 128.19–134.92 (m, Ph). 31P (C6D6): d 41.36.
ES-MS (MeOH, m/z): 692, M+.
4.3.5. {[(tol)3P]Au}C„CC„C{Au[P(tol)3]} (4)
(a) From Me3SiC„CC„CSiMe3. Me3SiC„CC„
CSiMe3 (50 mg, 0.26 mmol) and NaOH (206 mg, 5.20 mmol)
were dissolved in MeOH (25 mL) and stirred for 30 min.
M, 550. IR (CH2Cl2): m(„CH) 3300; m(C„C) 2157 cmÀ1
1H NMR: d 1.66 (s, 1H, C„CH), 2.38 (s, 9H, Me), 7.20–
.

368
M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
AuCl{P(tol)3} (276 mg, 0.52 mmol) was added and the
mixture was stirred a further 1.5 h. The pale yellow precip-
itate which formed was collected and washed with MeOH,
Et2O and pentane and air-dried to give {[(tol)3-
P]Au}C„CC„C{Au[P(tol)3]} (4) (230 mg, 85%). Anal.
Found: C, 52.43; H, 3.96%. Calc. for C46H42Au2P2: C,
52.58; H, 4.03; M, 1051. IR (CH2Cl2): m(C„C)
precipitate had formed and was collected and washed with
MeOH, Et2O and pentane and air-dried to give {[(tol)3-
P]Au}(C„C)4{Au[P(tol)3]} (7) (60 mg, 20%). Anal.
Found: C, 54.59; H, 3.77%. Calc. for C50H42Au2P2: C,
54.66; H, 3.85; M, 1099. IR (nujol): m(C„C) 2167w,
1
2134m cmÀ1. H NMR: d 2.36 (s, 9H, Me), 7.20–7.38 (m,
12H, tol). 13C NMR: d 21.42 (s, Me), 60.91 (s, Cd), 67.23
(s, Cc), 86.94 (br, Cb), 131.29 (br, Ca), 126.15–142.02 (m,
tol). 31P NMR: d 40.26 (s).
1
2157 cmÀ1. H NMR: d 2.29 (s, 9H, Me), 7.12–7.32 (m,
12H, tol). 13C NMR: d 21.39 (s, Me), 88.11 (br, Cb),
2
119.89 (d, JCP = 140 Hz, Ca), 126.67–141.69 (m, tol). 31P
(b) From Au(C„CC„CH){P(tol)3} + CuCl/tmeda.
The Hay catalyst was prepared from CuCl (100 mg,
1.01 mmol) in acetone (5 mL) and tmeda (0.15 mL,
0.3 mmol) which was added dropwise. The resulting blue
solution was stirred a further 30 min. Dioxygen was bub-
bled through a solution of 1 (300 mg, 0.55 mmol) in ace-
tone (25 mL). The Hay catalyst was added in 1 mL
portions over 1 h after which the reaction was adjudged
complete (t.l.c). The solvent was removed and the residue
chromatographed on a SiO2 column (hexane–CH2Cl2,
1/1). Removal of the solvent from the bright yellow
fraction yielded 7 (100 mg, 33%).
NMR: d 40.57 (s).
(b) From 1 and AuCl{P(tol)3}. A Schlenk flask was
charged with
1 (100 mg, 0.18 mmol), AuCl{P(tol)3}
(97 mg, 0.18 mmol), CuI (ca. 5 mg) and thf/NHEt2
(20 mL, 1/2). The suspension cleared to give a yellow solu-
tion that was stirred for 1 h at r.t. The solution was filtered,
solvent removed and a CH2Cl2 extract of the residue was
passed through a SiO2 column (CH2Cl2–hexane, 1/1) to
give gave pale yellow 4 (148 mg, 78%).
4.3.6. {(Ph3 P)Au}C„CC„C{Au[P(tol)3]} (5)
To a solution of Au(C„CC„CH)(PPh3) (250 mg,
0.49 mmol) and AuCl{P(tol)3} (264 mg, 0.49 mmol) in
thf/NHEt2 (30 mL, 1/3) was added CuI (ca. 5 mg) and
the resulting yellow solution was stirred for 1 h. The yel-
low-brown precipitate was collected and washed with
H2O, EtOH, MeOH and Et2O and air-dried to give
{(Ph3P)Au}C„CC„C{Au[P(tol)3]} (5) (250 mg, 51%).
Anal. Found: C, 51.09; H, 3.45%. Calc. for C43H36Au2P2:
C, 51.20; H, 3.60; M, 1009. IR (CH2Cl2): m(C„C)
(c) From Au(C„CC„CH){P(tol)3} and Cu(OAc)2/
pyridine. To a solution of 1 (100 mg, 0.18 mmol) in pyridine
(3 mL) was added Cu(OAc)2 Æ H2O (55 mg, 0.27 mmol) and
the mixture was stirred at 80 ꢁC for 2 h. The solvent was
removed and the dark brown residue passed down a SiO2
column eluting with CH2Cl2. A bright yellow fraction
was collected and hexane (10 mL) added. Removal of the
solvent gave yellow 7 (56 mg, 57%).
1
2153 cmÀ1. H NMR: d 2.35 (s, 9H, Me), 7.17–7.54 (m,
4.3.9. [ppn][Au{C„CC„CAu[P(tol)3]}2] (8)
27H, tol). 13C NMR: d 21.44 (s, Me), 85.78 (br, Cb),
88.23 (br, Cc), 125.80 (br, Ca), 126.96 (br, Cd), 129.00–
142.38 (m, tol). 31P NMR: d 40.24 [s, P(tol3)], 42.60 (s,
PPh3).
A solution of 1 (110 mg, 0.2 mmol) and [ppn][Au(acac)2]
(92 mg, 0.1 mmol) in CH2Cl2/NHEt2 (10 mL, 10/1) was
stirred at r.t for 2 h. The solvent was then removed and
the residue extracted with CH2Cl2 and filtered into cold
hexane. The cream-white precipitate was collected and
washed with Et2O (2 · 10 mL) and n-pentane (20 mL)
and air-dried to give [ppn][Au{C„CC„CAu[P(tol)3]}2]
(8) (72 mg, 39%). Anal. Found: C, 56.49; H, 4.06%. Calc.
for C86H72Au3NP4: C, 56.31; H, 3.96; M, 1296. IR (nujol):
m(C„C) 2145w cmÀ1. 1H NMR: d 2.29 (s, 18H, Me), 7.15–
7.62 (m, 54H, Ph, tol). 13C NMR: d 21.36 (s, Me), 125.54–
141.81 (m, Ph, tol). 31P NMR: d 22.21 (s, ppn), 39.62 [s,
P(tol)3].
4.3.7. {[(tol)3P]Au}(C„C)3{Au[P(tol)3]} (6)
A solution of Me3Si(C„C)3SiMe3 (50 mg, 0.23 mmol)
and NaOH (184 mg, 4.60 mmol) in MeOH (25 mL) was
stirred for 30 min. AuCl{P(tol)3} (246 mg, 0.46 mmol)
was added and the mixture was stirred a further 1.5 h.
The pale yellow precipitate was collected and washed with
MeOH, Et2O and pentane and air-dried to give {[(tol)3-
P]Au}(C„C)3{Au[P(tol)3]} (6) (188 mg, 76%). Anal.
Found: C, 53.66; H, 3.87%. Calc. for C48H42Au2P2: C,
53.64; H, 3.94; M, 1075. IR (CH2Cl2): m(C„C) 2139sh,
4.3.10. [Au2 (l-I)(l-dppm)2][Au(C„CC„CSiMe3)2]
(9)
1
2115m cmÀ1. H NMR: d 2.38 (s, 9H, Me), 7.20–7.40 (m,
12H, tol). 13C NMR: d 21.42 (s, Me), 81.63 (s, Cc), 88.13
(br, Cb), 127.94 (br, Ca), 129.77–142.06 (m, tol). 31P
NMR: d 40.26 (s).
HC„CC„CSiMe3 (88 mg, 0.72 mmol) and CuI
(20 mg, 0.07 mmol) were added to a suspension of
(AuCl)2(l-dppm) (200 mg, 0.24 mmol) in thf/NHEt2
(45 mL, 8/1). The resulting clear solution was stirred at
r.t. for 2 h, a small amount of precipitate was filtered off,
and the filtrate was evaporated. A benzene extract of the
residue was added dropwise to stirred hexane to give a light
yellow precipitate, which was filtered off and reprecipitated
twice. Crystallisation (CH2Cl2/hexane) gave pure [Au2(l-
I)(l-dppm)2][Au(C„CC„CSiMe3)2] (9) (50 mg, 42%) as
4.3.8. {[(tol)3P]Au}(C„C)4{Au[P(tol)3]} (7)
(a) From AuCl{P(tol)3} and Me3Si(C„C)4SiMe3. A
solution of Me3Si(C„C)4SiMe3 (75 mg, 0.31 mmol) and
NaOH (248 mg, 6.20 mmol) in MeOH (25 mL) was stirred
for 30 min. AuCl{P(tol)3} (302 mg, 0.56 mmol) was added
and the mixture stirred for a further 1.5 h. A pale yellow

M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
369
pale lime-yellow crystals. Anal. Found: C, 44.27; H, 3.70%.
Calc. for C64H62Au3IP4Si2: C, 44.45; H, 3.61; M (cation),
1289; M (anion), 439. IR (CH2Cl2): m(C„C) 2176w,
1H NMR: d 2.35 (s, 18H, Me), 7.18–7.39 (m, 24H, tol).
3
13C NMR: d 21.43 (s, Me), 72.52, 88.15 (d, JPC = 29 Hz),
102.52, 126.80–141.70 (m, tol). 31P NMR: d 40.62 [s,
P(tol)3].
1
2122m cmÀ1. H NMR (CDCl3): d 0.16 (s, 18H, SiMe3),
4.57 (m, 4H, CH2), 7.24–7.76 (m, 40H, Ph). 31P NMR
(CDCl3): d 27.7 (s, dppm). ES-MS (positive ion, C2H4Cl2,
m/z): 1289, [Au2I(dppm)2]+; (negative ion, C2H4Cl2, m/z):
439, [Au(C4SiMe3)2]À.
4.3.13. {[(tol)3P]Au}C„CC„C{Cu(triphos)} (11)
To a solution of 1 (100 mg, 0.18 mmol) in thf (30 mL) at
À100 ꢁC was added nBuLi (73 lL, 0.18 mmol of a 2.5 M
solution in hexane). Stirring was continued for 15 min.
CuCl(triphos) (123 mg, 0.17 mmol) was added and the yel-
low solution turned into a cream-coloured suspension
which on allowing to warm to r.t slowly cleared to give a
yellow solution. After stirring for 3.5 h at r.t the solvent
was removed. The residue was extracted with CH2Cl2
(min) and then filtered into cold hexane. A cream-white
precipitate was collected and washed with Et2O
(2 · 5 mL) and n-pentane (2 · 5 mL) and air-dried to give
4.3.11. Hg{C„CC„CAu(PPh3)}2 (10-Ph)
A
solution of Au(C„CC„CH)(PPh3) (200 mg,
0.39 mmol) and Hg(OAc)2 (62 mg, 0.19 mmol) in thf
(15 mL) was refluxed for 1h. After allowing to cool to
r.t., a grey/white precipitate had formed which was col-
lected and washed with H2O, EtOH, MeOH and Et2O
and air-dried to give Hg{C„CC„CAu(PPh3)}2 (10-Ph)
(114 mg, 49%). Anal. Found: C, 43.61; H, 2.27%. Calc.
for C44H30Au2Hg2P2: C, 43.49; H, 2.49; M, 967. IR (nujol):
{[(tol)3P]Au}C„CC„C{Cu(triphos)}
(11)
(130 mg,
1
m(C„C) 2100w, 2014w cmÀ1. H NMR: d 7.34–7.52 (m,
62%). Anal. Found: C, 63.62; H, 5.07%. Calc. for
Ph). 13C NMR d 128.99–134.46 (m, Ph). 31P NMR: d
C66H60AuP4Cu: C, 64.05; H, 4.89; M, 1238. IR (nujol):
1
42.68 (s).
m(C„C) 2158m, 2127w cmÀ1. H NMR: d 1.44 (s, 3H,
CH3), 2.28 (s, 6H, CH2), 2.36 (s, 9H, Me), 6.82–7.46 (m,
42H, Ph, tol). 13C NMR: d 21.43 (s, Me), 36.47 (m, C-
CH3), 37.53 (s, C–CH3), 39.93 (m, P–CH2), 125.27–
142.31 (m, Ph, tol). 31P NMR: d À25.08 (triphos), 45.20
[s, P(tol)3].
4.3.12. Hg{C„CC„CAu[P(tol)3]}2 (10-tol)
A solution of 1 (200 mg, 0.36 mmol) and Hg(OAc)2
(57 mg, 0.18 mmol) in thf (15 mL) was warmed to 45 ꢁC
and stirred for 2 h. Filtration and addition of hexane
(150 mL) to the filtrate produced a milky-white precipitate
which was collected and washed with Et2O (2 · 10 mL) and
n-pentane (20 mL) and air-dried to give Hg{C„CC„
CAu[P(tol)3]}2 (10-tol) (126 mg, 54%). Anal. Found: C,
46.35; H, 3.35%. Calc. for C50H42Au2HgP2: C, 46.22; H,
4.4. Structure determinations
Full spheres of diffraction data were measured at ca.
153 K using a Bruker AXS CCD area-detector instrument.
Ntot reflections were merged to N unique (Rint cited) after
3.26; M, 1299. IR (nujol): m(C„C) 2166w, 2052w cmÀ1
.
Table 2
Crystal data and refinement detail
Complex
1
2a
3
4
9
Formula
MW
C
550.4
25H22AuP
C26.67H28.28AuI0.19PSi0.81
623.6
C32H24AuFeP
692.3
C46H42Au2P2
1050.7
C64H62Au3IP4Si2
1729.1
Crystal system
Space group
a (A)
Hexagonal
P61
18.454(1)
Monoclinic
P21/c
12.454(2)
11.623(2)
18.781(3)
Triclinic
Monoclinic
P21/c
19.691(2)
11.507(1)
19.286(2)
Triclinic
ꢀ
ꢀ
P1
P1
˚
9.715(2)
10.442(3)
12.742(3)
99.732(3)
102.120(3)
91.681(3)
1243
14.320(1)
15.198(1)
17.330(1)
77.276(2)
67.048(2)
64.328(2)
3124
˚
b (A)
˚
c (A)
12.4035(7)
a (ꢁ)
b (ꢁ)
c (ꢁ)
103.404(4)
115.219(3)
3
˚
V (A )
3658
2645
3953
qcalc
1.499
1.566
1.850
1.765
1.838
Z
6
4
2
4
2
2hmax (ꢁ)
l(Mo Ka) (mmÀ1
Tmin/max
75
6.1
0.70
75
5.9
0.60
55
6.6
0.65
60
7.5
0.69
65
7.7
0.66
)
Crystal dimensions (mm3)
0.35 · 0.08 · 0.07
76293
6486 (0.068)
3353
0.48 · 0.07 · 0.05
54606
13925 (0.063)
7978
0.18 · 0.14 · 0.12
10698
5589 (0.038)
4819
0.07 · 0.05 · 0.03
55061
11506 (0.065)
7933
0.60 · 0.07 · 0.05
64271
22906 (0.069)
14069
Ntot
N (Rint
No
)
R
0.043
0.037
0.046
0.032
0.050
Rw (nw)
0.047(8)
0.033(2)
0.058(9)
0.031(2)
0.053(6)
a
The material modelled as diynyl co-crystallised with iodide, both components resolvable and refinable with occupancies 0.813(2) and complement.

370
M.I. Bruce et al. / Journal of Organometallic Chemistry 691 (2006) 361–370
[2] (a) H. Schmidbaur, Gold Bull. 23 (1990) 11;
(b) H. Schmidbaur, Pure Appl. Chem. 65 (1993) 691.
[3] (a) R.J. Puddephatt, Coord. Chem. Rev. 216–217 (2001) 313;
(b) K.-L. Cheung, S.-K. Yip, V.W.-W. Yam, J. Organomet. Chem.
689 (2004) 4451;
‘‘empirical’’/multiscan absorption correction (proprietary
software), No with F > 4r(F) being used in the full-matrix
least-squares refinements. All data were measured using
˚
monochromatic Mo Ka radiation, k = 0.71073 A. Aniso-
tropic displacement parameter forms were refined for the
(c) G. Jia, R.J. Puddephatt, J.J. Vittal, N.C. Payne, Organometallics
12 (1993) 263;
(d) G. Jia, R.J. Puddephatt, J.J. Vittal, N.C. Payne, Organometallics
12 (1993) 4771.
non-hydrogen atoms, (x, y, z, Uiso H being refined. Con-
)
ventional residuals R, Rw on |F| are quoted [weights:
(r2(F) + 0.000nwF2)À1]. Neutral atom complex scattering
factors were used; computation used the XTAL-3.7 program
system [26]. Pertinent results are given in the figures (which
show non-hydrogen atoms with 50% probability amplitude
displacement ellipsoids and hydrogen atoms with arbitrary
[4] G. Jia, R.J. Puddephatt, J.D. Scott, J.J. Vittal, Organometallics 12
(1993) 3565.
[5] M.J. Irwin, J.J. Vittal, R.J. Puddephatt, Organometallics 16 (1997)
3541.
[6] M.-A. MacDonald, R.J. Puddephatt, G.P.A. Yap, Organometallics
19 (2000) 2194, and references cited therein.
[7] M.I. Bruce, B.C. Hall, B.W. Skelton, M.E. Smith, A.H. White,
Dalton Trans. (2002) 995.
˚
radii of 0.1 A) and in Table 2.
5. Supplementary material
[8] A.B. Antonova, M.I. Bruce, B.G. Ellis, M. Gaudio, P.A. Humphrey,
M. Jevric, G. Melino, B.K. Nicholson, G.J. Perkins, B.W. Skelton,
B. Stapleton, A.H. White, N.N. Zaitseva, Chem. Commun. (2004)
960.
[9] S. Szafert, J.A. Gladysz, Chem. Rev. 103 (2003) 4175.
[10] (a) W. Lu, H.-F. Xiang, N. Zhu, C.-M. Che, Organometallics 21
(2002) 2343;
Full details of the structure determinations (except
structure factors) have been deposited with the Cambridge
Crystallographic Data Centre as CCDC 272500–272504.
Copies of this information may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (fax: + 44 1223 336 033; e-mail: depos-
it@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
(b) C.-M. Che, H.Y. Chao, V.M. Miskowski, Y. Li, K.K. Cheung, J.
Am. Chem. Soc. 123 (2001) 4985.
[11] Z. Cao, Q. Zhang, Chem. Eur. J. 10 (2004) 1920.
[12] J. Vicente, M.T. Chicote, Coord. Chem. Rev. 193–195 (1999) 1143.
[13] J. Shain, J.P. Fackler Jr., FOJDOX, Inorg. Chim. Acta 131 (1987) 157.
[14] M.N.I. Khan, C. King, D.D. Heinrich, J.P. Fackler Jr., L.C. Porter,
SAVROW, Inorg. Chem. 28 (1989) 2150.
Acknowledgements
[15] W. Henderson, J.S. McIndoe, B.K. Nicholson, P.J. Dyson, J. Chem.
Soc., Dalton Trans. (1998) 519.
[16] M.I. Bruce, B.K. Nicholson, O. bin Shawkataly, Inorg. Synth. 26
(1989) 325.
We thank Professor Brian Nicholson (University of
Waikato, Hamilton, New Zealand) for providing the mass
spectra and the ARC for support of this work.
[17] R. Uson, A. Laguna, Inorg. Synth. 21 (1982) 71.
[18] J. Vicente, M.T. Chicote, Inorg. Synth. 32 (1998) 172.
[19] N.C. Payne, R. Ramachandran, R.J. Puddephatt, Can. J. Chem. 73
(1995) 6.
References
[1] (a) R.J. Puddephatt, The Chemistry of Gold, Elsevier, Amsterdam,
1978;
[20] L. Sacconi, S. Midollini, J. Chem. Soc., Dalton Trans. (1972) 1213.
[21] L. Brandsma, Preparative Acetylenic Chemistry, Elsevier, Amster-
dam, 1971, p. 122.
[22] Z. Yuan, G. Stringer, I.R. Jobe, D. Kreller, K. Scott, L. Koch, N.
Taylor, T.B. Marder, J. Organomet. Chem. 452 (1993) 115.
[23] G.E. Jones, D.A. Kendrick, A.B. Holmes, Org. Synth. Coll. vol. 8
(1993) 63.
[24] Y. Rubin, S.S. Lin, C.B. Knobler, J. Antony, A.M. Boldi, F.
Diederich, J. Am. Chem. Soc. 113 (1991) 6943.
[25] D.R.M. Walton, F. Waugh, J. Organomet. Chem. 37 (1972) 45.
[26] S.R. Hall, D.J.du Boulay, R. Olthof-Hazekamp (Eds.), The System,
University of Western Australia, 2000.
(b) R.J. Puddephatt, in: G. Wilkinson, F.G.A. Stone, E.W. Abel
(Eds.), Comprehensive Organometallic Chemistry, vol. 2, Pergamon
Press, Oxford, 1982, p. 756;
(c) G.K. Anderson, Adv. Organomet. Chem. 20 (1982) 39;
(d) A. Grohmann, H. Schmidbaur, in: E.W. Abel, F.G.A. Stone, G.
Wilkinson (Eds.), Comprehensive Organometallic Chemistry II, vol.
3, Pergamon Press, Oxford, 1995, p. 1;
(e) H. Schmidbaur, A. Grohmann, M.E. Olmos, in: H. Schmidbaur
(Ed.), Gold: Progress in Chemistry, Biochemistry and Technology,
Wiley, Chichester, 1999, p. 647.