Some molecular rods: Gold(I) complexes of 1,3-diynes. Crystal structures of Au(C≡CC≡CH)(PPh3) and {Cu3(μ-dppm)3}(μ3-I)-(μ 3-C≡CC≡CAuC≡CC≡CH)

Article abstract of DOI:10.1039/b107446f

Reaction of buta-1,3-diyne with AuCl(PPh3) and (AuCl)₂(μ-dppm) in the presence of base gave the diynyl complexes Au(C≡CC≡CH)(PPh₃) 1 and {Au(C≡CC≡CH)}₂(μ-dppm) 2, respectively. Similar reaction of W(C≡CC≡CH)(CO)₃Cp with the two gold(I) complexes gave the heteronuclear diyndiyls W{C≡CC≡C[Au(PPh₃]}(CO)₃Cp (known) and {Au(C≡CC≡C[W(CO)₃Cp])}₂(μ-dppm) 3. Reaction of [ppn][Au(acac)₂] with the appropriate diynes afforded [ppn][Au(C≡CC≡CH)₂] 4, [ppn][Au{C≡CC≡C[W(CO)₃Cp]}₂] 5, [ppn][Au{C≡CC≡C[Au(PPh₃)]}₂] 6 and [ppn][Au-(C≡CC₆H₄C≡CPh)₂] 7; the latter anion was also obtained as the very unstable NMe₄ salt. The reaction between 2 and {Au(OTf)}₂(μ-dppm) likely afforded cyclo-{Au₂(μ-C≡CC≡C)(μ-dppm)}₂ 8, although this compound was not structurally characterised. On one occasion, the molecular rod {Cu₃(μ-dppm)₃}(μ₃-I)(μ ₃-¹-C≡CC≡CAuC≡CC≡CH)9 was isolated and crystallographically characterised; a rational approach to 8 from [ppn][Au(C≡CC≡CH)₂] and [{Cu₃-(μ-dppm)₃}(μ₃-I)₂]I gave instead the molecular dumbbell [{Cu₃(μ3-I)(μ-dppm)₃}₂(μ ₃:μ₃-C≡CC≡CAuC≡CC≡C)]I 10.

Full text of DOI:10.1039/b107446f

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Some molecular rods: gold(I) complexes of 1,3-diynes. Crystal
᎐
᎐
᎐
᎐
structures of Au(C᎐CC᎐CH)(PPh ) and {Cu (ꢀ-dppm) }(ꢀ -I)-
᎐
᎐
3
3
3
3
᎐
᎐
᎐
(ꢀ -C᎐CC᎐CAuC᎐CC᎐CH)
᎐
᎐
᎐
3
Michael I. Bruce,*a Ben C. Hall,a Brian W. Skelton,b Mark E. Smitha and Allan H. Whiteb
a Department of Chemistry, Adelaide University, Adelaide, South Australia 5005, Australia.
E-mail: michael.bruce@adelaide.edu.au
b Department of Chemistry, University of Western Australia, Crawley, Western Australia 6009,
Australia
Received 16th August 2001, Accepted 12th December 2001
First published as an Advance Article on the web 11th February 2002
Reaction of buta-1,3-diyne with AuCl(PPh3) and (AuCl)2(µ-dppm) in the presence of base gave the diynyl complexes
᎐
᎐
᎐
᎐
᎐
᎐
Au(C᎐CC᎐CH)(PPh ) 1 and {Au(C᎐CC᎐CH)} (µ-dppm) 2, respectively. Similar reaction of W(C᎐CC᎐CH)(CO) Cp
᎐
᎐
᎐
᎐
᎐
᎐
3
2
3
᎐
᎐
with the two gold() complexes gave the heteronuclear diyndiyls W{C᎐CC᎐C[Au(PPh ]}(CO) Cp (known) and
᎐
᎐
3
3
᎐
᎐
{Au(C᎐CC᎐C[W(CO) Cp])} (µ-dppm) 3. Reaction of [ppn][Au(acac) ] with the appropriate diynes afforded
᎐
᎐
3
2
2
᎐
᎐
᎐
᎐
᎐
᎐
[ppn][Au(C᎐CC᎐CH) ] 4, [ppn][Au{C᎐CC᎐C[W(CO) Cp]} ] 5, [ppn][Au{C᎐CC᎐C[Au(PPh )]} ] 6 and [ppn][Au-
(C᎐CC H C᎐CPh) ] 7; the latter anion was also obtained as the very unstable NMe salt. The reaction between 2
and {Au(OTf )} (µ-dppm) likely afforded cyclo-{Au (µ-C᎐CC᎐C)(µ-dppm)} 8, although this compound was not
structurally characterised. On one occasion, the molecular rod {Cu (µ-dppm) }(µ -I)(µ -η -C᎐CC᎐CAuC᎐CC᎐CH) 9
was isolated and crystallographically characterised; a rational approach to 8 from [ppn][Au(C᎐CC᎐CH) ] and [{Cu -
(µ-dppm) }(µ -I) ]I gave instead the molecular dumbbell [{Cu (µ -I)(µ-dppm) } (µ :µ -C᎐CC᎐CAuC᎐CC᎐C)]I 10.
᎐
᎐
᎐
᎐
᎐
᎐
2
3
2
3
2
᎐
᎐
᎐
᎐
6
4
2
4
᎐
᎐
᎐
᎐
2
2
2
1
᎐
᎐
᎐
᎐
᎐
᎐
᎐
᎐
3
3
3
3
᎐
᎐
᎐
᎐
2
3
᎐
᎐
᎐
᎐
᎐
᎐
᎐
᎐
3
3
2
3
3
3
2
3
3
of molecular rectangles based on the Au2(µ-dppm) subunit is
Introduction
᎐
᎐
also possible, complexes such as {Au(C᎐CC H C᎐C)} (µ-PPh -
᎐
᎐
6
4
2
2
Gold() chemistry continues to excite researchers. This stems, in
part, from its linear two-coordination1 and from the property
of aurophilicity,2 or the weak intra-molecular attractions
between gold atoms, displayed in many of its compounds. The
former results in formation of rigid-rod polymeric materials,3
currently of interest for their unusual photo-emission4 and
non-linear optical properties,5 while aurophilic effects have
resulted in the construction of systems having a variety of
unusual geometries.6
C6H4PPh2) having been described previously.5 The lability of
the acac ligands in [Au(acac)2]Ϫ in reactions of compounds con-
taining acidic CH, NH, PH or SH groups enables an extensive
range of neutral and anionic gold() complexes to be pre-
pared.19 This paper describes some of our results obtained
when examining the synthesis and behaviour of gold() deriv-
atives of buta-1,3-diyne.
There is much current interest in preparing molecules con-
taining linear conjugated systems end-capped by two metal–
ligand fragments (molecular wires or rods). One reason for this
is that suitable substructures may allow electronic communi-
cation between the two units which cap each end of the rod.7
Recent examples include the poly-yndiyl complexes of transi-
tion metals, among which complexes containing MnI(dppe)2,8
Re(NO)(PPh3)Cp*,9 Fe(dppe)Cp*,10 Ru(PPh3)2Cp11 or PtR-
{P(tol)3}2 (R = tol, C6F5)12 fragments as end-caps to Cn chains
(n = 2, 4, 6, 8, 12, 16, 20) have been studied recently. Others
have used the linear two-coordinate geometry of gold(), in
particular, to link alkynyl ligands, thereby generating molecular
rods, squares, rectangles and sundry other geometries,13
together with catenanes, all of which form readily by self-
assembly.14 Extension to cyclic and polymeric materials con-
taining dialkynylaryl,15 isocyanide16 and alkynylisocyanide
ligands3 as the carbon linkers has also been achieved.
Results and discussion
Copper-catalysed coupling of AuCl(PPh3) and buta-1,3-diyne
under Cadiot–Chodkiewicz conditions resulted in the for-
᎐
᎐
mation of Au(C᎐CC᎐CH)(PPh ) 1 (Scheme 1) in 75% yield.
᎐
᎐
3
This compound was identified from IR, 1H and 13C NMR,
and electrospray (ES) mass spectrometry, elemental analysis
and, ultimately, X-ray crystallography albeit with some co-
crystallised material modelled as the iodide. The IR spectrum
᎐
᎐
contained ν(᎐CH) (3283) and ν(C᎐C) bands (2148 and 2081
᎐
᎐
cmϪ1). The 1H NMR spectrum had a singlet for the diynyl
hydrogen at δ 1.76, while the 13C NMR spectrum showed
resonances at δ 60.39, 69.43, 128.79 and 129.55 for Cδ, Cγ, Cβ
and Cα, respectively, assigned by comparison with other
buta-1,3-diynyl compounds described previously.21,22 The ES
mass spectrum contained a molecular ion at m/z 508, with an
ion at m/z 459 corresponding to [Au(PPh3)]ϩ.
Several gold() complexes have been used as precursors for
alkynylgold() derivatives. These include AuCl(L) (L = PPh3,
SC4H8),17 (AuCl)2(µ-dppm)18 and [ppn][Au(acac)2].19 The dppm
complex is notable for the presence of an aurophilic interaction
between the two gold atoms, resulting in the two Cl atoms being
on the same side of the molecule.18 A similar structure has been
Although seemingly pure by other criteria, the only usefully
crystalline sample of 1 obtained for structural work has a co-
crystallised contaminant most sensibly modelled as AuI(PPh3).
Two independent molecules comprise the asymmetric unit
of the structure, each site having some ‘iodide’ residue in
association with the C4H ligand. Occupancies of the ‘iodide’
component were 0.043 and 0.097(2) (for molecules 1 and 2,
respectively); C4H occupancies were modelled as the comple-
ments. Despite this perturbation and these differences, associ-
t
20
᎐
found for {Au(C᎐CBu )} (µ-dppm). We hoped to use this
᎐
2
feature to generate novel systems in which the two diynyl units
also occupied sites on the same side of the molecule. Formation
DOI: 10.1039/b107446f
J. Chem. Soc., Dalton Trans., 2002, 995–1001
This journal is © The Royal Society of Chemistry 2002
995

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ated geometries as presented in Table 1 are plausible. A plot of
molecule 1 is given in Fig. 1. The PAuC4H fragment is essen-
tially linear, with angles at the Au and C atoms of between
170.6(4) and 178.0(6)Њ (molecule 1), and 172.6(6) and 172.7(2)Њ
(molecule 2). The Au–P and Au–C(1) distances are 2.276(1) and
2.001(5) Å (molecule 1), and 2.273(1) and 1.970(5) Å (molecule
2), respectively, while the carbon chains show alternating short/
long/short arrangements of the C–C separations [1.204(7),
1.379(7), 1.190(8) Å (molecule 1); 1.226(7), 1.374(8), 1.188(9) Å
(molecule 2)] corresponding to the conjugated 1,3-diyne
Similarly, addition of (AuCl)2(µ-dppm) to buta-1,3-diyne
᎐
᎐
resulted in the formation of cream {Au(C᎐CC᎐CH)} (µ-dppm)
᎐
᎐
2
᎐
2 in 74% yield. The IR spectrum showed a ν(᎐CH) band at 3131
᎐
cmϪ1 and two ν(C᎐C) bands at 2140 and 2080 cm . The H
Ϫ1
1
᎐
᎐
NMR spectrum contained a singlet resonance at δ 2.52 for the
᎐
᎐CH protons, together with multiplets at δ 3.57 and 7.06–7.76
᎐
arising from the dppm ligand. The 13C NMR had resonances
at δ 65.36, 71.37, 84.07 and 89.72 assigned to Cδ, Cγ, Cβ and
Cα, respectively, as well as those for the dppm ligand. The
ES mass spectrum contained Mϩ at m/z 874, which loses C4H
to give [Au2(dppm)(C4H)]ϩ at m/z 826. Crystals suitable for an
X-ray study have not yet been obtained, but it is likely that the
᎐
᎐
(–C᎐C–C᎐C–) formulation. These values may be compared
᎐
᎐
with those found in the electron diffraction study of buta-1,3-
diyne itself [1.217(1), 1.383(1) Å; strictly linear],23 replacement
of one H atom by the isolobal Au(PPh3) group having no
significant effect on the geometry.
t
20
᎐
structure is closely related to that of {Au(C᎐CBu )} (µ-dppm),
᎐
2
which has a U-shaped geometry, with an intramolecular
Au ؒ ؒ ؒ Au contact of 3.331(1) Å, each Au() centre being
Scheme 1
996
J. Chem. Soc., Dalton Trans., 2002, 995–1001

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᎐
᎐
Table 1 Selected structural data for Au(C᎐CC᎐CH)(PPh3) (1)
᎐
᎐
Bond distances/Å (molecules 1, 2)
Bond angles/Њ (molecules 1, 2)
Au–P
2.276, 2.273(1)
2.001, 1.970(5)
1.204, 1.226(7)
1.379(7), 1.374(8)
1.190(8), 1.188(9)
1.813, 1.819(4)
1.820(5), 1.805(4)
1.815, 1.808(5)
2.59(1), 2.659(4)
P–Au–C(1)
173.2(1), 172.7(2)
170.6(4), 172.2(6)
177.7(5), 176.9(7)
178.0(6), 176.5(7)
Au–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
P–C(11)
P–C(12)
P–C(13)
Au–‘I’
Au–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
Au–P–C(11)
Au–P–C(12)
Au–P–C(13)
‘I’–Au–P
115.1, 115.6(1)
111.8(1), 112.7(2)
110.9, 110.0(2)
175.5(3), 176.24(9)
1
2029 cmϪ1. The H and 13C NMR spectra contained singlet
resonances for the Cp groups at δH 5.20 and δC 91.60, while the
ppn cation gave multiplets between δH 7.40 and 7.67 and
between δC 126.22 and 133.91. Only one carbon of the C4 chain
was detected, at δ 63.57 (probably C–Au). The negative ion
ES mass spectrum showed [Au{C4[W(CO)3Cp]}2]Ϫ as the base
peak at m/z 959, with two other ions at m/z 931 and 903 formed
by loss of CO groups.
Addition of 1 to [ppn][Au(acac)2] resulted in the formation
᎐
᎐
of white [ppn][Au{C᎐CC᎐C[Au(PPh )]} ] 6 in 73% yield. The
᎐
᎐
3
2
Ϫ1
᎐
IR spectrum had ν(C᎐C) bands at 2140 and 2080 cm . The
᎐
1H NMR spectrum contained only a Ph multiplet between
δ 7.46–7.73 ppm. The 13C NMR spectrum showed two peaks of
low intensity at δ 88.34 and 118.78, which are assigned to two
carbons of the butadiynyl chain, with a multiplet between
δ 126.18–134.38 due to the phenyl carbons. The negative ion
ES mass spectrum displayed a single ion at m/z 1211 assigned to
[Au{C4[Au(PPh3)]}2]Ϫ.
᎐
᎐
Fig. 1 Plot of a molecule of Au(C᎐CC᎐CH)(PPh3) (1), showing the
᎐
᎐
atom numbering scheme.
A further example of a long molecular rod was obtained in
᎐
᎐
the course of studies of the reactions of 4-HC᎐CC H C᎐CPh.
᎐
᎐
6
4
᎐
᎐
White [ppn][Au(C᎐CC H C᎐CPh) ] 7 was obtained in 68%
᎐
᎐
6
4
2
approximately linearly coordinated by the phosphorus atom
and the alkynyl group.
Yellow {Au(C᎐CC᎐C[W(CO) Cp])} (µ-dppm)
yield from the diyne and [ppn][Au(acac)2]. The resonances
of the four alkynyl carbons were observed in the 13C NMR
spectrum as sharp singlets between δ 89.56 and 119.10, while an
ES mass spectrum contained a strong negative ion at m/z 598,
assigned to the molecular anion. While the ppn salt is stable to
air and light over prolonged periods, the analogous [NMe4]ϩ
salt decomposes rapidly so that, despite being more soluble
than the ppn salt, no 13C NMR spectrum could be obtained.
᎐
᎐
3
was
᎐
᎐
3
2
obtained in 77% yield from the CuI-catalysed reaction between
᎐
᎐
᎐
two equivalents of W(C᎐CC᎐CH)(CO) Cp and (AuCl) -
᎐
3
2
᎐
(µ-dppm) in diethylamine. The IR spectrum had a ν(C᎐C) band
᎐
at 2144 cmϪ1 and the ν(CO) bands of the W(CO)3Cp group
occurred at 2039 and 1954 cmϪ1. The 1H NMR spectrum
contained a singlet Cp resonance at δ 5.60, together with the
expected signals from the phosphine ligand at δ 3.94 (CH2) and
between δ 7.29 and 7.64 (Ph). The carbons of the butadiynyl
chain were not detected in the 13C NMR spectrum, probably
due to their long relaxation times. However, the Cp and dppm
methylene carbons were seen at δ 91.91 and 44.05, respectively.
The ES mass spectrum, from solutions containing NaOMe,
showed ions at m/z 1563 for [M ϩ Na]ϩ, with additional ions
A molecular rectangle
We sought to prepare rectangular complexes that contained
butadiyndiyl ligands (C4) as two of the edges. Addition of a
solution of {Au(OTf )}2(µ-dppm), from (AuCl)2(µ-dppm) and
AgOTf, to a solution of 2 containing diethylamine via syringe
pump under high dilution conditions afforded, after concen-
tration and precipitation with hexane, a cream compound
᎐
᎐
at m/z 1159 and 778 formed by successive loss of C᎐CC᎐C-
᎐
᎐
᎐
᎐
[W(CO)3Cp] fragments. The increased steric bulk of the
W(CO)3Cp moieties is likely to result in breaking of the intra-
molecular Au ؒ ؒ ؒ Au contact, with twisting of the Au–
phosphine backbone; presently we have been unable to obtain
crystals suitable for X-ray analysis to confirm the exact con-
formation of 3.
formulated as cyclo-{Au (µ-C᎐CC᎐C)(µ-dppm)} 8 (87%). The
᎐
᎐
2
2
Ϫ1
᎐
IR spectrum contained a single ν(C᎐C) band at 2141 cm . The
᎐
NMR spectra showed signals at δH 2.49 and δC 24.26 (CH2),
and δH 7.28–8.05 and δC 128.74–133.36 for the phenyl groups.
An unresolved multiplet at δ 89.39 is assigned to the carbons
of the buta-1,3-diynyl chain. The 31P NMR spectrum had a
single peak at δ 34.50 (dppm). The ES mass spectrum of a
solution containing NaOMe displayed three ions at m/z 1725,
1675 and 1653 corresponding to [M ϩ NH2Et2]ϩ, [M ϩ Na]ϩ
and [M ϩ H]ϩ, respectively. The former peak originates from
the interaction with [NH2Et2][OTf], formed as a by-product;
similar adducts were found in the spectra of the square mole-
Addition of buta-1,3-diyne to [ppn][Au(acac)2] under basic
conditions (NHEt ) gave white [ppn][Au(C᎐CC᎐CH) ] 4 in
᎐
᎐
᎐
᎐
2
2
96% yield. The IR spectrum showed two bands at 3302 and
2141 cmϪ1 assigned to ν(᎐CH) and ν(C᎐C), respectively. The
᎐
᎐
᎐
᎐
1
᎐
H NMR spectrum contained a singlet at δ 2.50 for the ᎐CH
᎐
protons and a Ph multiplet between δ 7.39 and 7.66. The 13C
NMR spectrum displayed butadiynyl carbon resonances at
δ 83.56 (Cα), 71.84 (Cβ) and 56.73 (Cδ), Cγ not being detected.
The negative ion ES mass spectrum showed a single intense
ion at m/z 295 corresponding to [Au(C4H)2]Ϫ.
cules cyclo-{Pt(µ-C᎐CC᎐C)(PR ) } (PR3 = PEt3, ½dppe)24
᎐
᎐
᎐
᎐
3
2 4
and between organic macrocycles and secondary amines.25
᎐
Alternative formulations, for example as a salt of [Au(C᎐C-
C᎐CH) ] with an Au–dppm cation, can be ruled out on the
᎐
Ϫ
᎐
᎐
2
᎐
᎐
The related complex [ppn][Au{C᎐CC᎐C[W(CO) Cp]} ] 5
was prepared as a yellow solid in 85% yield from W(C᎐C-
basis of the mass spectra (which contain neither this anion nor
᎐
᎐
3
2
᎐
any sensible cationic peaks) and the IR spectrum, which does
᎐
᎐
᎐
C᎐CH)(CO) Cp using the same method. The IR spectrum had
not contain a ν(᎐CH) absorption (cf. 4). Unfortunately, crystals
᎐
᎐
3
ν(CO) bands at 1959 and 1924 cmϪ1 and a single ν(C᎐C) band at
suitable for an X-ray study have not yet been obtained. The
᎐
᎐
J. Chem. Soc., Dalton Trans., 2002, 995–1001
997

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᎐
᎐
᎐
᎐
Table 2 Selected structural data for {Cu3(µ-dppm)3}(µ3-I)(µ3-C᎐CC᎐CAuC᎐CC᎐CH) (9)
᎐
᎐
᎐
᎐
Bond distances/Å (molecules 1, 2)
Bond angles/Њ (molecules 1, 2)
Cu(1)–Cu(2)
Cu(1)–Cu(3)
Cu(2)–Cu(3)
Cu(1)–I
Cu(2)–I
Cu(3)–I
Cu(1)–P(1)
Cu(1)–P(6)
Cu(2)–P(2)
Cu(2)–P(3)
Cu(3)–P(4)
Cu(3)–P(5)
Cu(1)–C(11)
Cu(2)–C(11)
Cu(3)–C(11)
Au–C(14)
2.7236, 2.7761(9)
2.7722, 2.7354(8)
2.6846(8), 2.6894(9)
2.9055(8), 2.8259(9)
2.7804, 2.8092(7)
2.8001(7), 2.8514(8)
2.285, 2.276(1)
2.290, 2.282(1)
2.264, 2.266(1)
2.275, 2.277(1)
2.267, 2.271(1)
2.250, 2.256(1)
2.096(4), 2.094(5)
2.082, 2.112(6)
2.156(5), 2.110(5)
1.964, 1.975(6)
1.972, 1.970(6)
1.196, 1.184(8)
1.380, 1.404(8)
1.238, 1.226(9)
Cu(1)–I–Cu(2)
Cu(1)–I–Cu(3)
Cu(2)–I–Cu(3)
57.19, 59.03(2)
58.10, 57.61(2)
57.51, 56.73(2)
Cu(1)–C(11)–Cu(2)
Cu(1)–C(11)–Cu(3)
Cu(2)–C(11)–Cu(3)
81.4, 82.6(2)
81.4, 81.2(2)
78.6, 79.1(2)
P(1)–C(1)–P(2)
P(3)–C(3)–P(4)
P(5)–C(5)–P(6)
109.8, 111.6(3)
110.9, 109.6(3)
109.9(2), 112.0(3)
C(11)–C(12)–C(13)
C(12)–C(13)–C(14)
C(13)–C(14)–Au
C(14)–Au–C(21)
Au–C(21)–C(22)
C(21)–C(22)–C(23)
C(22)–C(23)–C(24)
176.1, 174.8(5)
176.2, 173.0(6)
177.8, 172.6(5)
178.3, 176.7(2)
176.8, 175.0(5)
177.7(6), 178.8(7)
178.1(6), 178.8(7)
Au–C(21)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
C(21)–C(22)
C(22)–C(23)
C(23)–C(24)
1.224(8), 1.225(9)
1.345(8), 1.379(9)
1.210(9), 1.18(1)
high selectivity for ring formation relies on the U-shaped
conformations of 2 and {Au(OTf )}2(µ-dppm) being maintained
in solution, a process favoured by the short intramolecular
Au ؒ ؒ ؒ Au contacts, together with the reactions being carried
out under high dilution conditions to minimise polymer
formation.
61.67(2)Њ. The C4AuC4H chains are slightly bent, with angles at
the carbon atoms of between 172.6 and 178.8(7)Њ, those at the
central Au atoms being 178.3(2), 176.7(2)Њ. The Cu–I distances
range between 2.7804(7) and 2.9055(8) Å [average 2.83(4) Å],
with Cu–C separations of 2.082–2.156(5) Å [average 2.11(3) Å].
The Au–C(14, 21) separations average 1.970(5) Å. The C–C
On one occasion, attempted crystallisation of the product
from a copper()-catalysed reaction between 2 and (AuCl)2(µ-
dppm) gave material suitable for a single crystal X-ray structure
determination. Unexpectedly, however, this product was found
distances show the expected short and long alternation, the
᎐
formal C᎐C triple bonds being between 1.18(1) and 1.238(9) Å
᎐
and the C–C single bond lengths being between 1.345 and
᎐
1.404(8) Å. There are significant differences among the C᎐C
᎐
to be the triangulo-tricopper complex {Cu3(µ-dppm)3}(µ3-I)-
triple bond lengths, those attached to the Cu3 cluster or to
H [1.18(1)–1.210(9) Å] being shorter than those appended to
Au [1.224(8)–1.238(9) Å]. Previously described examples of
this type of complex have widely varying Cu–Cu separations
(between 2.557 and 2.758 Å when spanned by two alkynyl
groups, or between 2.754 and 2.927 Å when a µ-halide ligand is
present).
1
᎐
᎐
᎐
᎐
(µ -η -C᎐CC᎐CAuC᎐CC᎐CH) 9; again two molecules comprise
᎐
᎐
᎐
᎐
3
the asymmetric unit of the structure, as for 1. Fig. 2 shows a
The triangulo-Cu3 core is presumably formed by transfer
of dppm from gold to CuI and subsequent aggregation
and rearrangement of the butadiyndiyl groups around the gold
Ϫ
᎐
᎐
centre. The [Au(C᎐CC᎐CH) ] fragment so-formed in situ
᎐
᎐
2
reacts further with the copper cluster.
The reaction between equimolar amounts of [{Cu3(µ-
dppm)3}(µ3-I)2]ϩ and 4 was examined as a potential direct
route to 9. This reaction gave instead the salt [{Cu3(µ3-I)-
᎐
᎐
᎐
᎐
(µ-dppm) } (µ -C᎐CC᎐CAuC᎐CC᎐C)]I 10 in 50% yield,
᎐
᎐
᎐
᎐
3
2
3
increasing to 100% if a 2 : 1 ratio of reagents was used. Under
these reaction conditions, the addition of the second Cu3(µ3-I)-
(µ-dppm)3 fragment appears to be the favoured process. The
compound was identified by microanalysis, IR, NMR and mass
᎐
spectrometry. The IR spectra contained two ν(C᎐C) bands at
᎐
2137 and 2084 cmϪ1. The NMR spectra displayed multiplets
between δH 3.12–3.81 and at δC 28.42 (CH2), and between
δH 6.82–7.62 and at δC 127.93–133.93 (Ph). The resonances
of the carbon atoms of the C4 chains were not observed. The
ES mass spectrum showed a peak corresponding to [M ϩ H]ϩ
(m/z 3232), which loses three dppm ligands to give fragment
ions at m/z 2847, 2463 and 2079.
1
᎐
᎐
Fig. 2 Plot of a molecule of {Cu3(µ-dppm)3}(µ3-I)(µ3-η -C᎐CC᎐
᎐
᎐
᎐
᎐
CAuC᎐CC᎐CH) (9).
᎐
᎐
plot of molecule 1 of 9, while selected bond distances and
angles are listed in Table 2. Many complexes containing this
triangulo-tricopper cluster attached to an η1-alkynyl group have
been described previously26 and the structure of 9 is closely
related to them.
Compounds 4–7 further demonstrate the ability of gold()
compounds to form linear complexes. The complex [ppn]-
[Au(acac)2] was considered as a possible source of linked
systems, either to extend the length of molecular wires or to
prepare larger molecular species. Thus, addition of [ppn][Au-
᎐
᎐
In 9, the Cu3 cores are equilateral triangles, with internal
angles at the three Cu atoms ranging between 58.41(2) and
(acac) ] to Pt(C᎐CC᎐CH) (dppe) via syringe pump over 1 h
᎐
2 2
᎐
᎐
᎐
resulted in the formation of [ppn] [cyclo-{Pt(µ-C᎐CC᎐CAu-
᎐
᎐
4
998
J. Chem. Soc., Dalton Trans., 2002, 995–1001

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᎐
᎐
᎐
C᎐CC᎐C)(dppe)} ] 11 in a yield of 91%. Correct microanalyses
Au2(µ-dppm), allowed synthesis of the bis-diynylgold complex
᎐
4
and spectroscopic data are consistent with the proposed formu-
2. By analogy with a previously described t-butylalkynyl
᎐
lation. The IR spectrum contained two ν(C᎐C) bands at 2142
complex, the structure of 2 is probably as depicted in Scheme 1.
᎐
and 2073 cmϪ1. The NMR spectra showed only peaks arising
from the dppe ligands, with multiplets at δH 2.46 and δC 26.99
(CH2) and between δH 7.15–7.94 and δC 126.10–133.74 (Ph).
Resonances due to the butadiynyl carbons were found at δ 60.31
(Cδ), 76.08 (Cγ), 97.26 (Cβ) and 99.56 (Cα). The ES mass
spectrum contained an ion centred at m/z 2310.5 assigned to
[M Ϫ 2ppn]2Ϫ.
Further replacement of the remaining ᎐CH protons, using
᎐
᎐
triflate as the leaving group, allowed construction of the
molecular rectangle 8.
In one case, X-ray crystallographic characterisation of an
HC4AuC4 rod capped by a Cu3(µ-dppm)3 triangle in 9 was
achieved; directed syntheses gave instead the bicapped C4AuC4
dumb-bell 10.
Combination of two linear diynyl ligands on the otherwise
ligand-free Au() centre gives the anionic molecular rod [Au-
Ϫ
᎐
᎐
(C᎐CC᎐CH) ] , in which a linear eleven-atom sequence is
᎐
᎐
2
probably (no X-ray structure being available) present. Exten-
᎐
᎐
sion of the above reactions to a metalladiyne, W(C᎐CC᎐CH)-
᎐
᎐
(CO)3Cp, gives heterometallic systems containing C4 ligands;
Ϫ
᎐
᎐
the anion [Au{C᎐CC᎐C[W(CO) Cp]} ] also contains a linear
᎐
᎐
3
2
eleven-atom fragment. Finally, evidence has been obtained for
the formation of a tetra-anionic 40-atom square 11, in which
the corners are Pt(dppe) groups and the edges are C4AuC4
fragments.
Experimental
General reaction conditions
Reactions were carried out under an atmosphere of nitrogen,
but no special precautions were taken to exclude oxygen during
work-up. Common solvents were dried and distilled under
nitrogen before use. Elemental analyses were performed by the
Canadian Microanalytical Service, Delta, B.C., Canada.
Conclusions
Instrumentation
The work described above shows that alkynylgold() chemistry
is readily extended to derivatives of 1,3-diynes, including the
parent buta-1,3-diyne. It is possible to attach several common
IR: Perkin Elmer 1720X FT IR. NMR: Bruker CXP300
or ACP300 (1H at 300.13 MHz, 13C at 75.47 MHz, 13P at
121.50 MHz) or Varian Gemini 200 (1H at 199.8 MHz, 13C at
50.29 MHz). Unless otherwise stated, spectra were recorded
using solutions in CDCl3 in 5 mm sample tubes. ES mass
spectra: Finnegan LCQ. Solutions were directly infused into
the instrument, chemical aids to ionisation being used as
required.27
gold() fragments, including Au(PPh3) and Au2(µ-dppm), to the
᎐
diyne, replacing the ᎐CH proton. In addition, reaction of the
᎐
[Au(acac)2]Ϫ anion readily proceeds with loss of the labile β-
diketonate ligands. Extension to systems in which an aurophilic
interaction holds two gold atoms in a defined manner, such as
J. Chem. Soc., Dalton Trans., 2002, 995–1001
999

View Article Online
᎐
᎐
᎐
Starting materials
yellow [ppn][Au{C᎐CC᎐C[W(CO) Cp]} ] 5 (157 mg, 85%).
᎐
3 2
Anal. found: C, 48.05; H, 2.74, N, 0.98; C60H40AuNO6P2W2
AuCl(PPh3),28 (AuCl)2(µ-dppm),20 {Au(OTF)}2(µ-dppm),20
(M = 1497) requires: C, 48.12; H, 2.69; N, 0.94%. IR (Nujol):
22
[ppn][Au(acac)2],29 W(C᎐CC᎐CH)(CO) Cp and [Cu3(µ3-I)2-
᎐
᎐
᎐
᎐
Ϫ1 1
3
᎐
ν(C᎐C) 2029; ν(CO) 1959, 1924 cm . H NMR: δ 5.20 (s, 10H,
᎐
(µ-dppm)3]I30 were prepared by literature methods.
Cp), 7.40–7.67 (m, 30H, Ph). 13C NMR (d6-dmso): δ 63.57 (s,
C᎐C), 91.60 (s, Cp), 126.22–133.91 (m, Ph). ES mass spectrum
᎐
᎐
Syntheses
(CH2Cl2–MeOH, with added NaOMe, m/z): 959, [Au{C4-
Ϫ
Ϫ
Ϫ
᎐
[W(CO) Cp]} ] (᎐ M); 931, [M Ϫ CO] ; 903, [M Ϫ 2CO] .
᎐
3
2
᎐
᎐
᎐
Au(C᎐CC᎐CH)(PPh ) 1. To a suspension of AuCl(PPh )
᎐
3
3
(1.17 g, 2.37 mmol) in NHEt2–thf (30 ml/15 ml) containing CuI
᎐
᎐
᎐
[ppn][Au{C᎐CC᎐C[Au(PPh )]} ] 6. Similarly, [ppn][Au-
᎐
᎐
᎐
3
2
(46 mg, 0.24 mmol) was added HC᎐CC᎐CH (23 ml of a 1.34 M
᎐
᎐
(acac)2] (92 mg, 0.1 mmol) and 1 (100 mg, 0.2 mmol) in NHEt2–
CH2Cl2 (1 ml/10 ml) gave white [ppn][Au{C᎐CC᎐C[Au-
(PPh3)]}2] 6 (125 mg, 73%). Anal. found: C, 54.91; H, 3.61, N,
1.21; C80H60Au3NP4 (M = 1750) requires: C, 54.89; H, 3.43;
solution in thf, 3.1 mmol) and the mixture was stirred at r.t.
for 15 min. The solvent was removed and the residue extracted
with CH2Cl2 and loaded onto a squat column. The product
was eluted with CH2Cl2, addition of hexane and reduction of
solvent volume resulting in precipitation of pale yellow
᎐
᎐
᎐
᎐
Ϫ1
1
᎐
N, 0.80%. IR (Nujol): ν(C᎐C) 2140, 2080 cm . H NMR:
᎐
δ 7.46–7.73 (m, 60H, Ph). 13C NMR: δ 88.34, 118.78 (2 × s, ᎐C),
᎐
᎐
᎐
᎐
Au(C᎐CC᎐CH)(PPh ) 1 (908 mg, 75%). Anal. found: C, 49.75;
᎐
᎐
3
126.18–134.38 (m, Ph). ES mass spectrum (CH2Cl2–MeOH
H, 3.26; C22H16AuPؒ0.5CH2Cl2 (M = 508) requires: C, 49.09;
with added NaOMe, m/z): 1211, [Au{C4Au(PPh3)}2]Ϫ.
Ϫ1
1
᎐
᎐
H, 3.12. IR (Nujol): ν(᎐CH) 3283; ν(C᎐C) 2081 cm . H NMR:
᎐
᎐
δ 1.76 (s, 1H, C᎐CH), 7.30–7.63 (m, 15H, Ph). 13C NMR:
᎐
᎐
᎐
᎐
᎐
δ 60.45 (s, Cδ), 69.45 (s, Cβ), 85.79 (s, Cα), 128.79–133.80 (m,
Ph). ES mass spectrum (CH2Cl2–MeOH, m/z): 508, Mϩ; 459,
[M Ϫ C4H]ϩ.
[X][Au(C᎐CC H C᎐CPh) ] (X ؍ ppn, NMe ) 7. (a) X = ppn.
A solution containing [ppn][Au(acac)2] (120 mg, 0.13 mmol)
and HC᎐CC H C᎐CPh (51 mg, 0.42 mmol) in NHEt –CH Cl
᎐
6
4
2
4
᎐
᎐
᎐
᎐
6
4
2
2
2
(10 ml/4 ml) was stirred at r.t. for 1 h. The solvent was removed
and the residue was extracted with CH2Cl2. The filtered solu-
tion was added dropwise to cold Et2O (50 ml) to precipitate
᎐
᎐
᎐
᎐
᎐
{Au(C᎐CC᎐CH)} (ꢀ-dppm) 2. HC᎐CC᎐CH (1.5 ml of 2.4 M
᎐
᎐
᎐
2
solution in thf, 3.4 mmol) was rapidly added to (AuCl)2-
(µ-dppm) (300 mg, 0.34 mmol) dissolved in NHEt2–thf (10 ml/
5 ml) containing CuI (5 mg) and stirred at r.t. for 30 min. The
resulting white precipitate was filtered, washed with EtOH,
MeOH and Et O and then air dried, to give {Au(C᎐C-
᎐
᎐
white [ppn][Au(C᎐CC H C᎐CPh) ] 7 (100 mg, 68%). Anal.
᎐
᎐
6
4
2
found: C, 69.89; H, 3.95; N, 1.53; C68H48AuNP2ؒ0.5CH2Cl2
(M = 1136) requires: C, 69.70; H, 4.18; N, 1.19%. IR (Nujol):
Ϫ1
1
ν(C᎐C) 2101 cm . H NMR: δ 7.38–7.67 (m, Ph ϩ C H ). 13C
᎐
᎐
6
4
᎐
᎐
2
᎐
NMR: δ 89.56, 90.05, 102.65, 119.10 (4 × s, 4 × ᎐C), 126.09–
᎐
᎐
C᎐CH)} (µ-dppm) 2 (220 mg, 74%). Anal. found: C, 45.57; H,
᎐
2
133.81 (m, Ph ϩ C6H4). ES mass spectrum (MeCN, m/z): 598,
2.77; C33H24Au2P2 (M = 876) requires: C, 45.23; H, 2.76%. IR
[M Ϫ 2ppn]Ϫ.
(Nujol): ν(᎐CH) 3131; ν(C᎐C) 2140, 2080 cm . 1H NMR:
Ϫ1
᎐
᎐
᎐
᎐
(b) X = NMe4. Similarly, addition of [NMe4][Au(acac)2]
᎐
δ 2.52 (s, 2H, ᎐CH), 3.57 (m, 2H, CH ), 7.06–7.76 (m, 20H, Ph).
᎐
2
᎐
᎐
(235 mg, 0.5 mmol) to a solution of HC᎐CC H C᎐CPh
13C NMR (d6-dmso): δ 25.57 (s, CH2), 65.36 (s, Cδ), 71.37 (s, Cγ),
84.07 (s, Cβ), 89.72 (s, Cα), 129.03–133.60 (m, Ph). ES mass
spectrum (dmso–MeOH with added NaOMe, m/z): 874, Mϩ;
826, [M Ϫ C4H]ϩ.
᎐
᎐
6
4
(202 mg, 1.0 mmol) in NHEt2–CH2Cl2 (10 ml/4 ml) afforded
᎐
᎐
cream [NMe ][Au(C᎐CC H C᎐CPh) ] (220 mg, 60%). IR
᎐
᎐
4
6
Ϫ1
4
1
2
᎐
(Nujol): ν(C᎐C) 2101 cm . H NMR: δ 3.50 (s, 12H, NMe ),
᎐
4
7.34–7.54 (m, 18H, Ph ϩ C6H4). ES mass spectrum (C2H4Cl2,
m/z): 615, [M ϩ O]Ϫ; 599, MϪ. This compound is extremely
sensitive to light and air, decomposing to a brown solid; repro-
ducible analyses were not obtained.
᎐
᎐
᎐
{Au(C᎐CC᎐C[W(CO) Cp])} (ꢀ-dppm) 3. Cul (5 mg) and
᎐
3
2
᎐
᎐
W(C᎐CC᎐CH)(CO) Cp (90 mg, 0.22 mmol) were added to a
᎐
᎐
3
solution of (AuCl)2(µ-dppm) (100 mg, 0.11 mmol) in NHEt2
(10 ml) and stirred at r.t. for 10 min. The resulting bright yellow
precipitate was filtered, washed with EtOH, MeOH and Et2O
᎐
᎐
᎐
cyclo-{Au (ꢀ-C᎐CC᎐C)(ꢀ-dppm)} 8. {Au(OTf )}2(µ-dppm)
᎐
2
2
(209 mg, 0.20 mmol) in CH2Cl2 (10 ml) was added over 1 h via
syringe pump to a solution of 2 (170.4 mg, 0.20 mmol)
in NHEt2–CH2Cl2 (1 ml/20 ml). After stirring for an additional
30 min, the solvent was removed and a CH2Cl2 extract of the
residue was added to cold hexane, precipitating cream cyclo-
᎐
᎐
and air dried, to give {Au(C᎐CC᎐C[W(CO) Cp])} (µ-dppm) 3
᎐
᎐
᎐
3
2
᎐
(130 mg, 77%). IR (Nujol): ν(C᎐C) 2144; ν(CO) 2039, 1954
cmϪ1. H NMR: δ 3.94 (s, 2H, CH2), 5.60 (s, 10H, Cp), 7.29–
1
7.64 (m, 20H, Ph). 13C NMR (d6-dmso): δ 44.05 (s, CH2),
91.91 (s, Cp), 129.28–133.80 (m, Ph). ES mass spectrum
(MeOH with added NaOMe, m/z): 1563, [M ϩ Na]ϩ; 1159,
[M Ϫ C4W(CO)3Cp]ϩ; 778, [M Ϫ 2C4W(CO)3Cp]ϩ.
᎐
᎐
{Au (µ-C᎐CC᎐C)(µ-dppm)} 8 (280 mg, 87%). IR (Nujol):
᎐
᎐
2
2
Ϫ1
1
᎐
ν(C᎐C) 2141 cm . H NMR (d -dmso): δ 2.49 (m, 4H, CH ),
᎐
6
2
7.28–8.05 (m, 40H, Ph). 13C NMR (d6-dmso): δ 24.26 (m, CH2),
89.39 (m, C᎐C), 128.74–133.36 (m, Ph) . 31P NMR (d6-dmso):
᎐
᎐
᎐
᎐
᎐
᎐
᎐
δ 34.50 (s, dppm). ES mass spectrum (MeOH containing
[ppn][Au(C᎐CC᎐CH) ] 4. HC᎐CC᎐CH (0.5 ml of 2.4 M
᎐
᎐
᎐
2
NaOMe, m/z): 1725, [M ϩ NH2Et2]ϩ; 1675, [M ϩ Na]ϩ; 1653,
[M ϩ H]ϩ.
solution in thf, 1.1 mmol) was added to a solution of
[ppn][Au(acac)2] (100 mg, 0.11 mmol) in NHEt2–CH2Cl2
(10 ml/2 ml) and stirred at r.t. for 1 h. The colour changed to
yellow. The solvent was removed and a filtered CH2Cl2 extract
of the residue was added dropwise to cold Et2O to give cream
᎐
᎐
᎐
᎐
᎐
[{Cu (ꢀ -I)(ꢀ-dppm) } (ꢀ :ꢀ -C᎐CC᎐CAuC᎐CC᎐C)]I
[Cu3(µ3-I)2(µ-dppm)3]I (41.4 mg, 0.02 mmol) and [ppn][Au-
(C᎐CC᎐CH) ] (20 mg, 0.02 mmol) were dissolved in thf (5 ml)
and stirred for 4 h. Evaporation, extraction of the residue
(CH2Cl2) and addition to hexane precipitated white [{Cu3(µ3-I)-
10.
᎐
᎐
᎐
3
3
3
2
3
3
᎐
᎐
[ppn][Au(C᎐CC᎐CH) ] 4 (85 mg, 96%). Anal. found: C, 63.16;
᎐
᎐
᎐
᎐
᎐
2
᎐
2
H, 3.86, N, 1.77; C44H32AuNP2 (M = 833) requires: C, 63.37;
Ϫ1
᎐
᎐
H, 3.87; N, 1.68%. IR (Nujol): ν(᎐CH) 3302; ν(C᎐C) 2141 cm .
᎐
᎐
H NMR: δ 2.50 (s, 2H, ᎐CH), 7.39–7.66 (m, 30H, Ph). 13C
NMR: δ 56.73 (s, ᎐CH), 71.84, 83.56 (2 × s, C᎐C), 125.83–
1
᎐
᎐
᎐
᎐
᎐
᎐
(µ-dppm) } (µ :µ -C᎐CC᎐CAuC᎐CC᎐C)]I 10 (41 mg, 50%).
᎐
᎐
᎐
᎐
3
2
3
3
᎐
᎐
᎐
᎐
Anal. found: C, 56.46; H, 4.08; C158H132AuCu6I3P12 (M = 3361)
133.89 (m, Ph). ES mass spectrum (CH2Cl2–MeOH, m/z): 295,
᎐
requires: C, 56.49; H, 3.96%. IR (Nujol): ν(C᎐C) 2137, 2084
᎐
[Au(C4H)2]Ϫ.
cmϪ1. H NMR: δ 3.12–3.81 (m, CH2), 6.82–7.62 (m, Ph). 13C
1
NMR (d6-dmso): δ 28.42 (m, CH2), 127.93–133.93 (m, Ph).
ES mass spectrum (CH2Cl2, m/z): 3232, [M ϩ H]ϩ; 2847,
[M Ϫ dppm]ϩ; 2463, [M Ϫ 2dppm]ϩ; 2079, [M Ϫ 3dppm]ϩ;
1346, [Cu3(dppm)3]ϩ.
᎐
᎐
᎐
[ppn][Au{C᎐CC᎐C[W(CO) Cp]} ] 5. Similarly, [ppn][Au-
᎐
3
2
᎐
᎐
(acac) ] (100 mg, 0.12 mmol) and W(C᎐CC᎐CH)(CO) Cp
(91.4 mg, 0.24 mmol) in NHEt2–CH2Cl2 (10 ml/2 ml) gave
᎐
᎐
2
3
1000 J. Chem. Soc., Dalton Trans., 2002, 995–1001

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᎐
᎐
᎐
᎐
᎐
Oxford, 1995, vol. 3, p. 1; (e) H. Schmidbaur, A. Grohmann and
[ppn] [cyclo-{Pt(ꢀ-C᎐CC᎐CAuC᎐CC᎐C)(dppe)} ] 11. [ppn]-
᎐
᎐
᎐
4
4
M. E. Olmos, in Gold: Progress in Chemistry, Biochemistry and
Technology, ed. H. Schmidbaur, Wiley, Chichester, 1999, p. 647.
2 H. Schmidbaur, Gold Bull., 1990, 23, 11; H. Schmidbaur, Pure Appl.
Chem., 1993, 65, 691.
3 (a) G. Jia, R. J. Puddephatt, J. J. Vittal and N. C. Payne,
Organometallics, 1993, 12, 263; (b) G. Jia, R. J. Puddephatt,
J. J. Vittal and N. C. Payne, Organometallics, 1993, 12, 4771.
4 M. J. Irwin, J. J. Vittal and R. J. Puddephatt, Organometallics, 1997,
16, 3541.
[Au(acac)2] (135 mg, 0.15 mmol) in CH2Cl2 (10 ml) was added
via syringe pump over a period of 1 h to Pt(C᎐CC᎐CH) (dppe)
(100 mg, 0.15 mmol) in the same solvent (20 ml). After evapor-
ation to dryness, a CH2Cl2 extract of the residue was added
dropwise to cold hexane, to give white [ppn]4[cyclo-{Pt(µ-
C᎐CC᎐CAuC᎐CC᎐C)(dppe)} ] 11 (191 mg, 91%). Anal. found:
C, 58.38; H, 4.08, N, 0.99; C280H216Au4N4P16Pt4 (M = 5697)
᎐
᎐
᎐
᎐
2
᎐
᎐
᎐
᎐
᎐
᎐
᎐
᎐
4
᎐
requires: C, 58.98; H, 3.82; N, 0.98%. IR (Nujol): ν(C᎐C) 2142,
᎐
5 G. C. Jia, R. J. Puddephatt, J. D. Scott and J. J. Vittal,
Organometallics, 1993, 12, 3565.
2073 cmϪ1. H NMR (d6-dmso): δ 2.46 (m, CH2), 7.15–7.94
1
(m, Ph). 13C NMR (d6-dmso): δ 26.99 (m, PCH2), 60.31, 76.08,
6 M.-A. MacDonald, R. J. Puddephatt and G. P. A. Yap,
Organometallics, 2000, 19, 2194 and references therein.
7 (a) F. Paul and C. Lapinte, Coord. Chem. Rev., 1998, 178–180, 427;
(b) F. Barigelletti and L. Flamigni, Chem. Soc. Rev., 2000, 29, 1.
8 S. Kheradmandan, K. Heinze, H. W. Schmalle and H. Berke,
Angew. Chem., 1999, 111, 2412; S. Kheradmandan, K. Heinze,
H. W. Schmalle and H. Berke, Angew. Chem., Int. Ed., 1999, 38,
2270.
᎐
᎐
97.26 (3 × m, 3 × ᎐C), 99.56 (s, ᎐CAu), 126.10–133.74 (m, Ph).
᎐
᎐
31P NMR (d6-dmso): δ 21.39 [s, J(PPt) 107 Hz, ppn], 43.03
[s, J(PPt) 2289 Hz, dppe] . ES mass spectrum (CH2Cl2, m/z):
2310.5 [11 Ϫ 2ppn]2Ϫ.
Structure determinations
9 (a) M. Brady, W. Weng, Y. Zhou, J. W. Seyler, A. L. Amoroso,
A. M. Arif, M. Böhme, G. Frenking and J. A. Gladysz, J. Am. Chem.
Soc., 1997, 119, 775; (b) R. Dembinski, T. Bartik, B. Bartik,
M. Jaeger and J. A. Gladysz, J. Am. Chem. Soc., 2000, 122, 810.
10 (a) N. Le Narvor, L. Toupet and C. Lapinte, J. Am. Chem. Soc.,
1995, 117, 7129; (b) F. Coat, M.-A. Guillevic, L. Toupet, F. Paul
and C. Lapinte, Organometallics, 1997, 16, 5988; (c) F. Coat,
M. Guillemot, F. Paul and C. Lapinte, J. Organomet. Chem., 1999,
578, 76.
11 (a) M. I. Bruce, P. J. Low, K. Costuas, L.-K. Halet, S. P. Best and
G. A. Heath, J. Am. Chem. Soc., 2000, 122, 1949; (b) M. I. Bruce,
B. D. Kelly, B. W. Skelton and A. H. White, J. Organomet. Chem.,
2000, 604, 150.
12 (a) T. B. Peters, J. C. Bohling, A. M. Arif and J. A. Gladysz,
Organometallics, 1999, 18, 3261; (b) W. Mohr, J. Stahl, F. H. Ampel
and J. A. Gladysz, Inorg. Chem., 2001, 40, 3263; (c) J. C. Bohling,
T. B. Peters, A. M. Arif, F. Hampel and J. A. Gladysz,
in Coordination Chemistry at the Turn of the Century, ed.
G. Ondrejovic and A. Sirota, Slovak Technical University Press,
Bratislava, Slovakia, 1999, p. 47.
Full spheres of data were measured at ca. 153 K using a Bruker
AXS CCD area-detector instrument and merged to unique sets
after “empirical”/multiscan absorption corrections (proprietary
software). Ntot data gave N unique (Rint quoted), No with F >
4σ(F) being used in the refinements. All data were measured
using monochromatic Mo-Kα radiation, λ 0.71073 Å. In the
refinements, anisotropic thermal parameter forms were used for
the non-hydrogen atoms, (x, y, z, Uiso)H being constrained at
estimated values.
In all cases, conventional residuals R, Rw on |F| (statistical
weights) are quoted. Neutral atom complex scattering factors
were used: computation was carried out using the XTAL 3.7 pro-
gram system.31 Pertinent results are given in the figures (which
show 50% thermal ellipsoids for the non-hydrogen atoms,
hydrogen atoms having arbitrary radii of 0.1 Å) and tables.
᎐
᎐
᎐
Crystal data for 1. 0.93Au(C᎐CC᎐CH)(PPh )ؒ0.07AuI-
᎐
3
13 R. J. Puddephatt, Chem. Commun., 1998, 1055.
᎐
(PPh )ؒ0.5PhMe ᎐ (C H AuP) ؒ(C18H15AuIP)0.07ؒC7H8, M =
᎐
3
22 16
0.93
14 C. P. McArdle, M. J. Irwin, M. C. Jennings and R. J. Puddephatt,
Angew. Chem., 1999, 111, 3571; C. P. McArdle, M. J. Irwin,
M. C. Jennings and R. J. Puddephatt, Angew. Chem., Int. Ed., 1999,
38, 3376.
15 M. J. Irwin, L. M. Rendina, J. J. Vittal and R. J. Puddephatt, Chem.
Commun., 1996, 1281.
16 M. J. Irwin, G. Jia, N. C. Payne and R. J. Puddephatt,
Organometallics, 1996, 15, 51.
17 (a) R. Usón, A. Laguna and J. Vicente, J. Organomet. Chem., 1977,
131, 471; (b) R. Usón, A. Laguna, M. Laguna and E. Fernández,
J. Chem. Soc., Dalton Trans., 1982, 1971.
559.8. Monoclinic, space group P21/n, a = 9.9695(5), b =
27.819(1), c = 15.4860(7) Å, β = 90.242(1)Њ, V = 4295 Å3 for
Z = 8, ρ = 1.731 g cmϪ3. Crystal: 0.35 × 0.13 × 0.13 mm, µ =
70 cmϪ1, ‘T ’min,max = 0.34, 0.70. 2θ = 68Њ, Ntot = 58585, N = 16831
(Rint = 0.033), No = 12380, R = 0.040, Rw = 0.048.
Variata. As described above, significant residues in the
vicinities of the gold atoms were modelled in terms of cocrystal-
lised iodide.
18 H. Schmidbaur, A. Wohlleben, F. Wagner, O. Orama and
G. Huttner, Chem. Ber., 1977, 110, 1748.
19 J. Vicente and M. T. Chicote, Coord. Chem. Rev., 1999, 193–195,
1143.
20 N. C. Payne, R. Ramachandran and R. J. Puddephatt, Can.
J. Chem., 1995, 73, 6.
21 M. Akita, M.-C. Chung, A. Sakurai, S. Sugimoto, M. Terada,
M. Tanaka and Y. Moro-oka, Organometallics, 1997, 16, 4882.
22 M. I. Bruce, M. Ke, P. J. Low, B. W. Skelton and A. H. White,
Organometallics, 1998, 17, 3539.
᎐
᎐
᎐
Crystal data for 9. {Cu (µ-dppm) }(µ -I)(µ -C᎐CC᎐CAu-
᎐
3
3
3
3
᎐
᎐
᎐
C᎐CC᎐CH) ᎐ C H AuCu IP , M = 1764.8. Monoclinic, space
᎐
᎐
᎐
83 67
3
6
group P21/c, a = 30.858(2), b = 26.304(1), c = 19.0257(9) Å, β =
105.150(1)Њ, V = 14906 Å3 for Z = 8, ρ = 1.573 g cmϪ3. Crystal:
0.25 × 0. 13 × 0.06 mm, µ = 33.9 cmϪ1, ‘T ’min,max = 0.55, 0.72.
2θ = 58Њ, Ntot = 166649, N = 38015 (Rint = 0.037), No = 22941,
R = 0.045, Rw = 0.043.
CCDC reference numbers 168997 and 168998.
See http://www.rsc.org/suppdata/dt/b1/b107446f/ for crystal-
lographic data in CIF or other electronic format.
23 M. Tanimoto, K. Kuchitsu and Y. Morino, Bull. Chem. Soc. Jpn.,
1971, 44, 386.
24 M. I. Bruce, K. Costuas, J.-F. Halet, B. C. Hall, P. J. Low,
B. K. Nicholson, B. W. Skelton and A. H. White, J. Chem. Soc.,
Dalton Trans., 2002, 383.
25 S. J. Cantrill, A. R. Pease and J. F. Stoddart, J. Chem. Soc., Dalton
Trans., 2000, 3715 and ref. 25 and 26 therein.
26 See, for example: (a) J. Diez, M. P. Gamasa, J. Gimeno, A. Aguirre
and S. García-Granda, Organometallics, 1991, 10, 380; (b) V. W.-W.
Yam, W. K.-M. Fung and K. K. Cheung, Organometallics, 1998, 17,
3293 and references cited therein.
Acknowledgements
We thank the Australian Research Council for support of
this work. B. C. H. and M. E. S. acknowledge receipt of Post-
graduate Research Awards.
27 W. Henderson, J. S. McIndoe, B. K. Nicholson and P. J. Dyson,
J. Chem. Soc., Dalton Trans., 1998, 519.
28 M. I. Bruce, B. K. Nicholson and O. bin Shawkataly, Inorg. Synth.,
1989, 26, 325.
29 J. Vicente and M. T. Chicote, Inorg. Synth., 1998, 32, 172.
30 N. Bresciani, G. Marsich, G. Nardin and L. Randaccio, Inorg. Chim.
Acta, 1974, 10, L5.
31 The XTAL 3.7 System, ed. S. R. Hall, D. J. du Boulay and R. Olthof-
Hazekamp, University of Western Australia, Perth, 2000.
References
1 (a) R. J. Puddephatt, The Chemistry of Gold, Elsevier, Amsterdam,
1978; (b) R. J. Puddephatt, in Comprehensive Organometallic
Chemistry, ed. G. Wilkinson, F. G. A. Stone and E. W. Abel,
Pergamon, Oxford, 1982, vol. 2, p. 756; (c) G. K. Anderson,
Adv. Organomet. Chem., 1982, 20, 39; (d ) A. Grohmann and
H. Schmidbaur, in Comprehensive Organometallic Chemistry II,
ed. E. W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon,
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1001