Selectivity in the self-assembly of organometallic gold(I) rings and [2]catenanes

Article abstract of DOI:10.1021/om050588o

The selectivity of formation of organometallic rings or [2]catenanes [{X(4-C₆H₄OCH₂-C≡CAu)₂(μ- Ph₂PZPPh₂)}_n], n =1 or 2, respectively, has been studied as a function of the hinge group X and the diphosphine ligand [X = O, S, SO₂, CH₂, CMe₂, CPh₂, C(CF₃)₂, C₆H₁₀; Z = (CH ₂)_m with m = 2-5]. When Z = (CH₂)₃, mixing of pairs of compounds with different C_2v-symmetrical hinge groups (X, X′ = SO₂, CH₂, CMe₂, CPh ₂, C(CF₃)₂, C₆H₁₀) led to formation of an equilibrium mixture containing the unsymmetrical [2]catenanes [{X(4-C₆H₄OCH₂-C≡CAu)₂(μ- Ph₂PZPPh₂)}{X′(4-C₆H₄OCH ₂C=CAu)₂(μ-Ph₂PZPPh₂)], as identified by NMR spectroscopy. The complexes with Z = (CH₂) ₄ exist in solution predominantly as the macrocycles and so do not form analogous mixed diacetylide complexes. When the hinge group contained a prochiral carbon center (X = CHMe, CMePh, 1,1-indanylidene), only achiral macrocycles [X(4-C₆H₄OCH₂C≡CAu) ₂(μ-Ph₂PZPPh₂)] were formed in solution when Z = (CH₂)₄, but mixtures containing both achiral macrocycles and chiral [2]catenane were formed when Z = (CH₂) ₃. In several cases, the solid-state structures of the isolated complexes were not representative of the structures in solution, with macrocycles being dominant in solution and [2]catenanes formed preferentially during crystallization.

Full text of DOI:10.1021/om050588o

5004
Organometallics 2005, 24, 5004-5014
Selectivity in the Self-Assembly of Organometallic
Gold(I) Rings and [2]Catenanes
Nicolle C. Habermehl, Michael C. Jennings, Christopher P. McArdle,
Fabian Mohr, and Richard J. Puddephatt*
Department of Chemistry, University of Western Ontario, London ON, N6A 5B7 Canada
Received July 13, 2005
The selectivity of formation of organometallic rings or [2]catenanes [{X(4-C6H4OCH2-
CtCAu)2(µ-Ph2PZPPh2)}n], n )1 or 2, respectively, has been studied as a function of the
hinge group X and the diphosphine ligand [X ) O, S, SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10;
Z ) (CH2)m with m ) 2-5]. When Z ) (CH2)3, mixing of pairs of compounds with different
C2v-symmetrical hinge groups (X, X′ ) SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10) led to formation
of an equilibrium mixture containing the unsymmetrical [2]catenanes [{X(4-C6H4OCH2-
CtCAu)2(µ-Ph2PZPPh2)}{X′(4-C6H4OCH2CtCAu)2(µ-Ph2PZPPh2)], as identified by NMR
spectroscopy. The complexes with Z ) (CH2)4 exist in solution predominantly as the
macrocycles and so do not form analogous mixed diacetylide complexes. When the hinge
group contained a prochiral carbon center (X ) CHMe, CMePh, 1,1-indanylidene), only achiral
macrocycles [X(4-C6H4OCH2CtCAu)2(µ-Ph2PZPPh2)] were formed in solution when Z )
(CH2)4, but mixtures containing both achiral macrocycles and chiral [2]catenane were formed
when Z ) (CH2)3. In several cases, the solid-state structures of the isolated complexes were
not representative of the structures in solution, with macrocycles being dominant in solution
and [2]catenanes formed preferentially during crystallization.
Introduction
and dissociation.4-6 Mass spectrometry, even with soft
ionization methods, is less reliable since the mechanical
link in most catenanes involving organometallic or
coordination complex functionality is easily broken.
There has been great interest in acetylide complexes
of gold, which have interesting chemical and photo-
physical properties, and so many gold(I) and gold(III)
acetylides, with simple and complex architectures, have
been characterized.7,8 Diacetylide ligands in combination
with diphosphine ligands are known to give macrocycles
or polymers, depending on the geometry and flexibility
of the component ligands, and the macrocycles may
undergo further self-assembly to yield [2]catenanes and
even a doubly braided [2]catenane (Scheme 1).3,9-13
The formation by self-assembly of inorganic cat-
enanes, rather than simple macrocyclic complexes, often
proceeds under thermodynamic control, whereby the
presence of kinetically labile coordinate bonds allows
“error-correcting”. Under these conditions, high yields
of catenanes can be obtained provided that secondary
bonding interactions between the two mechanically
interlocked rings are great enough to overcome the
associated unfavorable entropy effects.1 Secondary bond-
ing effects used to promote catenation include hydrogen-
bonding, π-π interactions, and metallophilic interac-
tions.1-3 The structures of catenanes can be determined
in the solid state by X-ray crystallography and in
solution by NMR and ESI-MS or MALDI-MS tech-
niques. The NMR method typically relies on the obser-
vation of significant differences in chemical shifts in the
1H NMR spectra between the catenane and the simple
ring, and the method can be used to monitor the
equilibria and kinetics involved in catenane formation
(4) Hunter, C. A. J. Am. Chem. Soc. 1992, 114, 5303.
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K. J. Am. Chem. Soc. 1998, 120, 611. (b) Hori, A.; Yamashita, K.;
Fujita, M. Angew. Chem., Int. Ed. 2004, 43, 5016. (c) Fujita, M.;
Ibukuro, F.; Seki, H.; Kamo, O.; Imanari, M.; Ogura, K. J. Am. Chem.
Soc. 1996, 118, 899.
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G. Organometallics 2005, 24, 2764. (b) Pornestchenko, I. E.; Polyansky,
D. E.; Castellano, F. N. Inorg. Chem. 2005, 44, 3412. (c) Chui, S. S.
W.; Ng, M. F. Y.; Che, C. M. Chem. Eur. J. 2005, 11, 1739. (d) Cheung,
K. L.; Yip, S. K.; Yam, V. V. W. J. Organomet. Chem. 2004, 689, 4451.
(e) Yip, S. K.; Cheng, E. C. C.; Yuan, L. H.; Zhu, N. Y.; Yam, V. V. W.
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M. G. Coord. Chem. Rev. 2004, 248, 725. (g) Mohr, F.; Puddephatt, R.
J. J. Organomet. Chem. 2004, 689, 374. (h) Ferrer, M.; Mounir, M.;
Rodriguez, L.; Rossell, O.; Coco, S.; Gomez-Sal, P.; Martin, A. J.
Organomet. Chem. 2005, 690, 2200. (i) Hogarth, G.; Alvarez-Falcon,
M. M. Inorg. Chim. Acta 2005, 358, 1386.
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Chim. Acta 2005, 358, 1429. (b) Schuster, O.; Schmidbaur, H. Orga-
nometallics 2005, 24, 2289. (c) Mendez, L. A.; Jimenez, J.; Cerrada,
E.; Mohr, F.; Laguna, M. J. Am. Chem. Soc. 2005, 127, 852. (d) Yam,
V. W. W.; Wong, K. M. C.; Hung, L. L.; Zhu, N. Y. Angew. Chem., Int.
Ed. 2005, 44, 3107.
* To whom correspondence should be addressed. E-mail: pudd@
uwo.ca.
(1) (a) Swiegers, G. F.; Malefetse, T. J. Chem. Rev. 2000, 100, 3483.
(b) Leininger, S.; Olenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100, 853.
(c) Philp, D.; Stoddart, J. F. Angew. Chem., Int. Ed. Engl. 1996, 35,
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Mobian, P.; Pomeranc, D.; Sauvage, J.-P. Eur. J. Org. Chem. 2004,
1627.
(3) (a) McArdle, C. P.; Irwin, M. J.; Jennings, M. C.; Puddephatt,
R. J. Angew. Chem., Int. Ed. 1999, 38, 3376. (b) McArdle, C. P.; Vittal,
J. J.; Puddephatt, R. J. Angew. Chem., Int. Ed. 2000, 39, 3819. (c)
McArdle, C. P.; Jennings, M. C.; Vittal, J. J.; Puddephatt, R. J. Chem.
Eur. J. 2001, 7, 3572. (d) McArdle, C. P.; Irwin, M. J.; Jennings, M.
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10.1021/om050588o CCC: $30.25 © 2005 American Chemical Society
Publication on Web 09/14/2005

Self-Assembly of Organometallic Gold(I) Rings
Organometallics, Vol. 24, No. 21, 2005 5005
Table 1. X-ray Structures of Alkynylgold(I) Rings
and [2]Catenanes
[{X(4-C6H4OCH2CtCAu)2(µ-Ph2PZPPh2)}n] (key: R
) ring, C ) [2]catenane, DC ) doubly braided
[2]catenane), as a Function of the Hinge Group X
and Spacer Group Za
Scheme 1. Equilibrium between Ring, Double
Ring, and [2]Catenane
X/Z ) (CH2)n
n ) 2b
n ) 3
n ) 4
n ) 5
CH2
C
C (3)
CHMe
C
CMe2
C(CF3)2
CH(4-C6H4Br)
CPh2
Cy
CO
R (3)c
C (3)
C (3)
C
C (12)
R
DC (3)
C (12)
C (3)
R (10)
R
O
S
R (3)
R (3)
Rd
SO2
R (11)e
R (10)d
R (13)g
R (13)g
C (11)
C (10)
R (11)
ketalf
OCH2CH2O
1,4-C6H4(CMe2)2
R (13)
a Bold entries indicate structures from this work. References
for known structures are given in parentheses. b Data are given
for Z ) (CH2)2 and also, when specified, for Z ) CC, trans-CHdCH,
and Fe(C5H4)2. c Z ) CC and (CH2)2. d Z ) CC. e Z ) CC and
Fe(C5H4)2. f ketal ) C{OCH2CH(CH2Br)O}. g Z ) trans-CHdCH.
For the compounds [{X(4-C6H4OCH2CtCAu)2(µ-Ph2-
PZPPh2)}n], the nature of the hinge group X in the
diacetylide ligand and the length of the spacer group Z
in the diphosphine ligand are important factors in
determining if the macrocycle (R, n ) 1) or [2]catenane
(C, n ) 2) will be dominant, while the double ring (DR,
n ) 2, Scheme 1) may be present as a minor product in
solution. In this diacetylide-diphosphine-digold(I) sys-
tem, the formation of [2]catenanes has been limited to
the cases with a hinge group X which forms a single-
atom bridge, and with medium-sized spacer groups Z
) (CH2)3 or (CH2)4.3,9-12 For shorter spacer groups Z )
CtC, trans-HCdCH, or (CH2)2, the simple macrocyclic
complexes (n ) 1), which are formed by [1+1] self-
assembly of the digold(I) diacetylide with the diphos-
phine ligand, are always isolated. In these cases in
which the hinge group X forms a single-atom bridge, it
seems that the 23-membered rings are too small to allow
interpenetration to give [2]catenanes.3 Longer spacer
groups Z ) (CH2)5, which give 26-membered rings when
X is a single-atom bridge, and longer hinge groups also
favor the formation of simple macrocycles (Table 1).10,11,13
For example a 28-membered ring is formed when X )
1,4-C6H4(CMe2)2 and Z ) trans-CHdCH.13 Compounds
that form 26- to 28-membered macrocycles do not
catenate; instead, they tend to form loose side-by-side
dimers in the solid state, in which a phenyl group of
each macrocycle penetrates the cavity of the other.10,11,13
These experimental studies show that crystalline [2]-
catenanes can be formed when X is a single-atom bridge
and Z ) (CH2)3 or (CH2)4. They arise by interpenetration
of the 24- or 25-membered macrocycles and can be
considered to be formed by [2+2] self-assembly of the
digold(I) diacetylide and diphosphine components. Even
in this optimum situation, the [2]catenanes are not
always formed, as summarized in Table 1. The orienta-
tion of the aryl groups of the diacetylide ligand with
respect to the C-X-C plane (termed the aryl twist
angle, Θ, which is determined largely by the nature of
the hinge group X) is a subtle factor that can determine
if a [2]catenane can be prepared. The formation of a [2]-
catenane is favored when Θ ) 45-90° but not when Θ
) ca. 0°, since the in-plane aryl group then blocks the
cavity and disfavors the interpenetration needed for [2]-
catenane formation. The case with Θ ) ca. 0° is found
with hinge groups X that can π-bond to the aryl groups
(X ) O, S, CdO, CdNR), and [2]catenanes are less
favored in these cases than when X ) CH2, CHR, CR2
(R ) alkyl or aryl), SO2, or a ketal, C(OR)2 (Table
1).3,9-12 The doubly braided [2]catenane crystallizes
selectively in the case where Z ) (CH2)4 and X )
cyclohexylidene, C6H10.3 When [2]catenanes are formed,
the binding between the macrocycles is considered to
involve some combination of aurophilic attractions and
aryl-aryl attractions.3
The solid-state structures are not necessarily main-
tained in solution, because the lability of the gold-
phosphorus bond allows equilibration between the
macrocyclic (R, DR, Scheme 1), [2]catenane, and other
isomeric forms. In solution, the gold(I) compounds with
Z ) (CH2)3 typically exist as a mixture of topological
isomers including the simple ring (formed by [1+1] self-
assembly), the [2]catenane and double ring (each formed
by [2+2] self-assembly), and a hexamer of unknown
structure (formed by [6+6] self-assembly), and the
equilibrium has been studied in detail in the case with
Z ) (CH2)3 and X ) CMe2 by 1H and 31P NMR
spectroscopy.3d Slow crystallization of the equilibrating
mixture gave the pure gold(I) [2]catenane as determined
by single-crystal X-ray structure determination. The
gold(I) compounds with Z ) (CH2)4 show only one
species in solution, as observed by 1H and 31P NMR
spectroscopy, and it has been assumed that this is the
isomer observed in the solid state, as summarized in
Table 1.3,10-12 This paper describes new evidence,
(9) Puddephatt, R. J. Coord. Chem. Rev. 2001, 216-217, 313.
(10) Mohr, F.; Eisler, D. J.; McArdle, C. P.; Atieh, K.; Jennings, M.
C.; Puddephatt, R. J. J. Organomet. Chem. 2003, 670, 27.
(11) Mohr, F.; Jennings, M. C.; Puddephatt, R. J. Eur. J. Inorg.
Chem. 2003, 217.
(12) McArdle, C. P.; Van, S.; Jennings, M. C.; Puddephatt, R. J. J.
Am. Chem. Soc. 2002, 124, 3959.
(13) Hunks, W. J.; Lapierre, J.; Jenkins, H. A.; Puddephatt, R. J. J.
Chem. Soc., Dalton Trans. 2002, 2885. (b) Hunks, W. J.; Jennings, M.
C.; Puddephatt, R. J. Z. Naturforsch. 2004, 59b, 1488.

5006 Organometallics, Vol. 24, No. 21, 2005
Habermehl et al.
Scheme 2a
Figure 1. Structure of complex 10 (X ) S, Z ) CC),
showing association of the macrocycles through aurophilic
bonding: (a) view along the chain direction and (b) view
down the chain direction.
a
C6H10 ) cyclohexylidene; C9H8 ) 1,1-indanylidene.
obtained from ligand-exchange studies and from the
synthesis of new compounds with prochiral centers at
the hinge group, that indicates that the complexes with
Z ) (CH2)4 exist in solution predominantly as the simple
ring, even though they may crystallize as the pure [2]-
catenanes, and that the complexes with Z ) (CH2)3
can form unsymmetrical [2]catenanes of the form
[{X(4-C6H4OCH2CtCAu)2(µ-Ph2PZPPh2)}{X′(4-C6H4-
OCH2CtCAu)2(µ-Ph2PZPPh2)], when diacetylides with
different hinge groups X and X′ are present.
Results
Figure 2. View of the structure of complex 3b (X ) CPh2,
Z ) (CH2)4). Selected bond distances (Å) and angles (deg):
Au(1)-P(1) 2.276(2); Au(2)-P(2) 2.279(2); Au(1)-C(1) 2.020-
(7); Au(2)-C(7) 2.009(7); C(1)-C(2) 1.161(9); C(7)-C(6)
1.177(9); P(1)-Au(1)-C(1) 174.8(2); P(2)-Au(2)-C(7) 174.3-
(2); Au(1)-C(1)-C(2) 176.8(8); Au(2)-C(7)-C(6) 175.4(7);
C(1)-C(2)-C(3) 178(1); C(7)-C(6)-C(5) 177.1(8).
Synthesis of Gold(I) Compounds. The gold(I)
complexes 1a-11 (Scheme 2) were prepared by general
methods established previously.3,9-12 The bis(phenols)
X(4-C6H4OH)2 were converted first to the propargyl
ethers X(4-C6H4OCH2CtCH)2 and then to the oligo-
meric digold(I) diacetylides [{X(4-C6H4OCH2CtCAu)2}n],
which were insoluble in organic solvents, but which gave
the soluble complexes [X(4-C6H4OCH2CtCAu)2(µ-Ph2-
PZPPh2)] on reaction with suitable diphosphine ligands.
In the case of X ) C(CF3)2, the oligomeric digold(I)
diacetylide derivative could not be isolated, so the
diphosphine complexes were prepared by reaction of the
complexes [Au2Cl2(µ-Ph2PZPPh2)] [Z ) (CH2)3, (CH2)4]
with silver trifluoroacetate (2 equiv) to give the corre-
sponding trifluoroacetate complexes [(AuO2CCF3)2(µ-
Ph2PZPPh2)],14 which were then treated with triethyl-
amine and the bis(alkyne) to give the corresponding
complexes [(CF3)2C(4-C6H4OCH2CtCAu)2(µ-Ph2PZPPh2)].
The complexes with hinge group CHMe were also
prepared by this method. Most complexes studied in this
work have spacer groups Z ) (CH2)3 or (CH2)4, since
these are most likely to form [2]catenanes, but the
structures of some complexes with smaller and larger
spacer groups were determined for comparison pur-
poses. The numbering system for the macrocycles is
shown in full in Scheme 2, and the corresponding [2]-
catenanes are denoted with an asterisk. Thus, for
example, 1b and 1b* refer to the macrocycle and [2]-
catenane respectively having X ) CH2 and Z ) (CH2)4.
Characterization of the Complexes in the Solid
State. The structures of several macrocycles (3b, 10,
and 11) and [2]catenanes (1a*, 4b*, and 7a*) were
determined in order to probe the secondary bonding
forces in the solid state, to provide a benchmark for
studying the structures in solution, and, by comparison
to earlier structure determinations (Table 1), to under-
stand how substituent effects control the selectivity in
forming macrocycles or [2]catenanes in the solid state.
Structures of the Macrocyclic Complexes. The
structures of macrocycles 10, 3b, and 11 are shown in
Figures 1-3 and illustrate how the structures vary as
the ring size increases from 23 to 25 and 26, respec-
tively. The structure of 10 (X ) S, Z ) CtC, Figure 1)
shows the presence of macrocycles organized into poly-
(14) Brandys, M.-C.; Jennings, M. C.; Puddephatt, R. J. J. Chem.
Soc., Dalton Trans. 2000, 4601.

Self-Assembly of Organometallic Gold(I) Rings
Organometallics, Vol. 24, No. 21, 2005 5007
Figure 4. View of the structure of [2]catenane complex
1a* (X ) CH2, Z ) (CH2)3). Selected bond distances (Å) and
angles (deg): Au(1)-Au(4) 3.3212(5); Au(2)-Au(3) 3.2937-
(6); Au(1)-P(1) 2.272(2); Au(2)-P(2) 2.271(2); Au(3)-P(3)
2.276(2); Au(4)-P(4) 2.277(2); Au(1)-C(11) 2.005(9); Au-
(2)-C(21) 1.990(8); Au(3)-C(31) 1.980(9); Au(4)-C(41)
2.000(8); P(1)-Au(1)-C(11) 171.4(3); P(2)-Au(2)-C(21)
169.8(3); P(3)-Au(3)-C(31) 173.1(3); P(4)-Au(4)-C(41)
173.1(3); Au(1)-C(11)-C(12) 173.6(9); Au(2)-C(21)-C(22)
172.2(9); Au(3)-C(31)-C(32) 173.3(8); Au(4)-C(41)-C(42)
174.2(9); C(11)-C(12)-C(13) 174(1); C(21)-C(22)-C(23)
174(1); C(31)-C(32)-C(33) 174(1); C(41)-C(42)-C(43) 177-
(1).
Figure 3. Views of the structure of complex 11 [X ) O, Z
) (CH2)5]: (a) individual macrocycle showing the large
cavity; (b) interactions between neighboring molecules,
showing the cavity partially occupied by a phenyl group
from below and an aryl group from above, and showing
some of the intra- and inter-macrocycle C-H‚‚‚Au interac-
tions (only the phenyl groups that are involved in forming
close CH‚‚‚Au contacts are shown, for clarity).
complexes with Z ) (CH2)4 that form simple ring
structures (Table 1) are Θ ) 83° and 2° for X ) O and
Θ ) 83° and 1° for X ) S.3 There are also some short
intramolecular CH‚‚‚Au contacts, indicated by dashed
lines in Figure 2 [Au(1)‚‚‚H(11B) ) 2.88 Å, Au(2)‚‚‚H(9A)
) 2.97 Å, Au(2)‚‚‚H(7AA) ) 2.89 Å], that are close to
the sum of the van der Waals radii [Au‚‚‚H ) 2.86 Å].
It is not obvious if these represent bonding interactions
since the sterically open AuCC units will naturally be
involved in close contacts. There are also some inter-
molecular CH‚‚‚Au contacts, which are not shown. For
example Au(1) has three short CH‚‚‚Au contacts in the
range 2.94-3.03 Å.
The molecular structure of the 26-membered macro-
cyclic complex 11 is shown in Figure 3. The ring is larger
than in 3b, and the transannular distance Au(1)‚‚‚Au-
(2) ) 8.57 Å is correspondingly larger, but the rings
again pack side-by-side. A significant difference from
3b is that there are several close Au‚‚‚H contacts, which
probably contribute to the intermolecular forces.17 Some
of these are shown in Figure 3b. For example, Au(1B)
and Au(2A) each have four Au‚‚‚H distances close to the
sum of the van der Waals radii of 2.86 Å [Au(1B)‚‚‚
H(19A) 2.77; Au(1B)‚‚‚H(32E) 3.00; Au(1B)‚‚‚H(1FB)
3.03; Au(1B)‚‚‚H(34E) 3.14 Å; Au(2A)‚‚‚H(2BA) 2.91; Au-
(2A)‚‚‚H(2IA) 2.92; Au(2A)‚‚‚H(1KA) 2.92; Au(2A)‚‚‚
H(2HA) 3.08 Å]. There are also aryl‚‚‚aryl secondary
bonds, but the closest intermolecular distance Au(1)‚‚‚
Au(1A) ) 5.77 Å, indicating the absence of aurophilic
bonding. The aryl twist angles in complex 11 are Θ )
47° and 28°.
meric chains through aurophilic bonding15 and is similar
to that determined earlier with X ) SO2 and Z ) CtC
[X ) S: Au‚‚‚Au ) 3.0599(4) Å, CSC ) 100.6(3)°, Θ )
50°, 76°; X ) SO2: Au‚‚‚Au ) 3.1819(3) Å, CSC ) 104.7-
(3)°, Θ ) 80°, 80°].11 The largest differences are the
angle CSC at the hinge atom and the aryl twist angles
Θ, both of which are affected by the lone pairs of
electrons on sulfur in complex 10. The short spacer
group Z ) CtC, with the associated transannular
distance Au‚‚‚Au ) 6.19 Å in complex 10, does not allow
catenation to occur.
The molecular structure of the 25-membered macro-
cyclic complex 3b is shown in Figure 2. The ring is large
enough for catenation, with the transannular distance
Au(1)‚‚‚Au(2) ) 7.73 Å, but the closest contact with a
neighboring molecule occurs in a “side-by-side” contact.
The main intermolecular forces appear to arise from
aryl‚‚‚aryl secondary bonds; the closest intermolecular
distance Au(1)‚‚‚Au(1A) ) 5.33 Å and shows that there
is no aurophilic bonding. The absence of catenation in
3b can be attributed, at least in part, to the orientation
of the four aryl groups around the carbon “hinge atom”.
Tetraarylmethanes typically have approximate S4 sym-
metry,16 in which the ideal aryl twist angles Θ will be
90° and 0°, and the 0° angle is unfavorable for catena-
tion.3 The structure of 3b deviates slightly from ideal
pseudo-S4 symmetry, with aryl twist angles Θ ) 66° and
17° for the phenylene groups, but the orientation with
one small value of the aryl twist angle is unfavorable
for catenation and so the simple ring structure of Figure
2 is observed. The aryl twist angles in analogous
Structures of the [2]Catenanes. The structure of
the [2]catenane complex 1a* [X ) CH2, Z ) (CH2)3] is
shown in Figure 4. The complex is comprised of two
(15) (a) Pyykko, P. Chem. Rev. 1997, 97, 597. (b) Schmidbaur, H.;
Cronje, S.; Djordjevic, B.; Schuster, O. Chem. Phys. 2005, 311, 151.
(16) (a) Knop, O.; Rankin, K. N.; Cameron, T. S.; Boyd, R. J. Can.
J. Chem. 2002, 80, 1351. (b) Hutchings, M. G.; Andose, J. D.; Mislow,
K. J. Am. Chem. Soc. 1975, 97, 4553.
(17) (a) Wong, W.-Y.; Choi, K.-H.; Lu, G.-L.; Shi, J.-X.; Lai, P.-Y.;
Chan, S.-M.; Lin, Z. Organometallics 2001, 20, 5446. (b) Vicente, J.;
Chicote, M.-T.; Alvarez-Falcon, M. M.; Fox, M. A.; Bautista, D.
Organometallics 2003, 22, 4792. (c) Bardaji, M.; Jones, P. G.; Laguna,
A. J. Chem. Soc., Dalton Trans. 2002, 3624.

5008 Organometallics, Vol. 24, No. 21, 2005
Habermehl et al.
Figure 5. View of the structure of the chiral [2]catenane
7a* (X ) CHMe, Z ) (CH2)3). Selected bond distances (Å)
and angles (deg): Au(1)-Au(4) 3.3314(4); Au(2)-Au(3)
3.3622(4); Au(1)-P(1) 2.2756(18); Au(2)-P(2) 2.2787(18);
Au(3)-P(3) 2.2742(18); Au(4)-P(4) 2.2666(18); Au(1)-C(11)
1.994(8); Au(2)-C(21) 1.989(7); Au(3)-C(31) 1.988(7); Au-
(4)-C(41) 2.004(7); P(1)-Au(1)-C(11) 174.1(2); P(2)-Au-
(2)-C(21) 173.3(2); P(3)-Au(3)-C(31) 171.2(2); P(4)-Au-
(4)-C(41) 168.9(2); Au(1)-C(11)-C(12) 174.1(6); Au(2)-
C(21)-C(22) 175.5(7); Au(3)-C(31)-C(32) 172.3(7); Au(4)-
C(41)-C(42) 170.5(7); C(11)-C(12)-C(13) 177.5(8); C(21)-
C(22)-C(23) 177.7(8); C(31)-C(32)-C(33) 174.8(9); C(41)-
C(42)-C(43) 173.2(9).
Figure 6. Views of the structure of [2]catenane 4b* (X )
C(CF3)2, Z ) (CH2)4): above, showing the shortest Au‚‚‚
Au contact; below, showing the intra- and inter-macrocycle
C-H‚‚‚Au interactions (fluorine atoms and several phenyl
groups are omitted, for clarity). Selected bond distances (Å)
and angles (deg): Au(1)-P(1) 2.283(3); Au(2)-P(2) 2.281-
(3); Au(3)-P(3) 2.276(4); Au(4)-P(4) 2.272(3); Au(1)-C(11)
2.01(1); Au(2)-C(21) 1.99(2); Au(3)-C(31) 2.00(2); Au(4)-
C(41) 1.99(1); P(1)-Au(1)-C(11) 176.2(4); P(2)-Au(2)-
C(21) 172.2(5); P(3)-Au(3)-C(31) 178.8(3); P(4)-Au(4)-
C(41) 172.5(4); Au(1)-C(11)-C(12) 174(1); Au(2)-C(21)-
C(22) 170(1); Au(3)-C(31)-C(32) 176(1); Au(4)-C(41)-
C(42) 168(1).
interlocked 24-membered rings, with inter-macrocycle
aurophilic bonding indicated by the distances Au(1)-
Au(4) ) 3.3212(5) Å and Au(2)-Au(3) ) 3.2937(6) Å.
The gold atoms in each macrocycle are separated by
distances Au(1)‚‚‚Au(3) ) 6.45 Å and Au(2)‚‚‚Au(4) )
6.62 Å. The aryl twist angles Θ ) 78° and 71° in one
macrocycle and Θ ) 89° and 69° in the other are in the
range that favors catenation.3
The structure of the [2]catenane complex 7a* [X )
CHMe, Z ) (CH2)3] is shown in Figure 5 and is similar
to that of 1a*. The [2]catenane complex is chiral because
there are two prochiral CHMe groups in each unit, but
there is crystallographic disorder of the R and S
enantiomers (disorder of the Me and H units of each
CHMe group); only one component of the disorder is
shown in Figure 5. The aurophilic bonding in 7a* is
indicated by the distances Au(1)-Au(4) ) 3.3314(4) Å
and Au(2)-Au(3) ) 3.3622(4) Å. The transannular
gold‚‚‚gold separations are Au(1)‚‚‚Au(3) ) 6.44 Å and
Au(2)‚‚‚Au(4) ) 6.64 Å.
The [2]catenane complex 4b* [X ) C(CF3)2, Z )
(CH2)4] contains two interlocked 25-membered rings, as
shown in Figure 6. The CF3 substituents at the hinge
group are of intermediate size, but the aryl twist angles
are still in the range that favors catenation, with Θ )
50,46° and 46,43° for the component rings. The shortest
gold‚‚‚gold contact in 4b* is Au(2)‚‚‚Au(4) ) 3.697(1) Å,
which could represent a weak aurophilic secondary
bond. The other shortest nonbonded contacts are Au-
(1)‚‚‚Au(4) ) 5.18 Å and Au(3)‚‚‚Au(2) ) 5.35 Å, which
are clearly too long to represent Au‚‚‚Au bonds. The
transannular distances are Au(1)‚‚‚Au(2) ) 7.23 Å and
Au(3)‚‚‚Au(4) ) 7.07 Å, and these values are only
slightly different from the corresponding transannular
distance in 3b [7.73 Å], which forms a simple ring
complex. These observations are consistent with the
hypothesis that the aryl twist angle Θ has significant
influence in determining the preferred structure. There
are several short intra- and inter-macrocycle CH‚‚‚Au
contacts in the structure of complex 4b*, as shown in
Figure 6b. These appear to complement the aryl‚‚‚aryl
attractions in providing a driving force for catenation
in the absence of strong aurophilic bonding. Short
CH‚‚‚Au contacts have been noted in several gold(I)
complexes, but this appears to be the first case noted
in which it could stabilize one isomer with respect to
another.17
Structures of the Complexes in Solution. The
structures of the complexes in solution have been
1
studied by H and 31P NMR spectroscopy.
Table 2 summarizes the observed 31P NMR chemical
shifts (CD2Cl2, 25 °C) for the complexes studied. The
alkynylgold(I) compounds containing the diphosphine
ligand Ph2PZPPh2 with Z ) (CH2)3 typically equilibrate
in solution to give a mixture containing the macrocycle
1a-9a, the [2]catenanes 1a*-9a*, and less intense
peaks attributed to a double ring (DR, Scheme 1) and
a hexamer of unknown structure. Each gives a charac-
teristic resonance in the 31P NMR spectrum at room
temperature, and exchange between the [2]catenane
and the other forms takes days to reach equilibrium.3
The 31P NMR resonances appear in a narrow chemical
shift region for complexes with a variety of hinge
groups: δ ) 31.5-32.2 for the [2]catenane, δ ) 35.7-
36.0 for the macrocycle, and δ ) 34-35 (broad) for the
dimer and hexamer.3,10-12 The 31P NMR resonances for
the macrocycles are observed as singlets in all cases,
but the resonances of the [2]catenanes occur as singlets
for compounds containing a C2v-symmetric hinge group
(1a*-6a*) and as two closely spaced doublets for the
compounds containing a prochiral carbon at the hinge
group (7a*-9a*). A characteristic feature of the 1H
NMR spectra is a large upfield shift for the protons of
the diacetylide aryl groups in the [2]catenane compared

Self-Assembly of Organometallic Gold(I) Rings
Organometallics, Vol. 24, No. 21, 2005 5009
Table 2. 31P NMR Data for the Gold(I) [2]Catenanes and Macrocyclic Rings in Solution and the Structures
in Solid and Solution Phasesa
complex
X
Z
δ (catenane)
32.00
δ (ring)
solid (ref)b
1a*, 1a
1b*, 1b
2a*, 2a
2b*, 2b
3a*, 3a
3b
4a*, 4a
4b*, 4b
5a*, 5a
5b**, 5b
6a*, 6a
6b
CH2
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)4
(CH2)3
(CH2)3
(CH2)3
(CH2)3
(CH2)3
(CH2)3
35.98
38.93
35.89
39.00
35.78
38.91
35.69
38.81
35.92
39.05
35.91
38.79
35.98
38.98
35.84
38.90
35.86
38.93
1a*
CH2
1b* (3)
2a* (3)
2b* (3)
CMe2
CMe2
CPh2
CPh2
31.96
32.07
3b
C(CF3)2
C(CF3)2
C6H10
31.57
4b*
32.17
5a*
C6H10
5b** (3)c
6a* (11)
SO2
31.58
SO2
7a*, 7a
7b
8a*, 8a
8b
CHMe
CHMe
CMePh
CMePh
C9H8
31.97 (d), 32.10 (d)d
32.07 (d), 32.36 (d)d
31.92 (d), 32.01 (d)d
7a*
9a*, 9a
9b
C9H8
12
CMe2, CH2
CMe2, CPh2
CMe2, C(CF3)2
CMe2, C6H10
CMe2, SO2
SO2, C6H10
31.88, 32.15
32.00, 32.04
31.78, 31.95
32.04, 32.14
31.71, 31.83
31.86, 31.88
13
14
15
16
17
a Spectra obtained in CD2Cl2 solution. Resonances occur as singlets unless otherwise stated. b Structure from X-ray determination,
4
reference given if previously published. c Doubly braided [2]catenane. d “AB” multiplet, JPP ) 6 Hz.
to the macrocycle. For example, the C6H4 protons for
4a appeared at δ ) 7.11 and 7.36, whereas those for
4a* appeared at δ ) 6.24 and 6.89.
including 7b, were studied at temperatures down to
-90°, but no significant changes were observed. The
equilibrium between the macrocycle and the [2]catenane
in solution is evidently much faster and more strongly
favors the macrocycle when Z ) (CH2)4 than when Z )
(CH2)3, and freshly prepared solutions of the [2]cat-
enanes show only resonances for the simple macrocycle.
Further evidence for this new interpretation of the
solution data is given below.
Identification of Unsymmetrical [2]Catenanes
in Solution. The presence of labile gold-phosphorus
bonds in the complexes allows threading and unthread-
ing processes that interconvert the macrocycles and [2]-
catenanes in solution. The use of two different diphos-
phine ligands Ph2PZPPh2 (defined by the spacer groups
as Z and Z′) or two different dialkynyl ligands X(4-C6H4-
OCH2CC)2 (defined by the hinge groups as X and X′)
may then be expected to give mixtures of the sym-
metrical and unsymmetrical [2]catenanes in solution.
A previous report described studies using a single hinge
group X ) CMe2 and all combinations of pairs of
diphosphine ligands Ph2PZPPh2 with Z ) (CH2)2-
(CH2)5, but no mixed [2]catenanes [{Me2C(4-C6H4OCH2-
CCAu)2(µ-Ph2PZPPh2)}{Me2C(4-C6H4OCH2CCAu)2(µ-
Ph2PZ′PPh2)}] were detected.3 At the time, this result
was surprising, but it can now be rationalized since the
[2]catenane is probably present in solution in significant
concentration only when Z ) (CH2)3. A study of gold(I)
complexes with mixed dialkynyl groups and with a
single diphosphine ligand having Z ) (CH2)3 or (CH2)4
has now been made.
Using the NMR criteria established above, it is
possible to identify isomers in solution. All of the
complexes with Z ) (CH2)3 crystallized as the [2]-
catenanes 1a*-9a* and, when freshly dissolved, gave
characteristic [2]catenane NMR spectra. Over time,
equilibration with the simple macrocycle occurred. With
smaller hinge groups [X ) CH2, CMe2, C6H10, SO2,
CHMe], both macrocycle and [2]catenane were observed
at equilibrium, but with larger hinge groups [X ) CPh2,
C(CF3)2, CMePh], the equilibrium favored the macro-
cycle and the concentration of [2]catenane was too low
to be detected. The structure of 8a* (X ) CMePh) in
the solid state was confirmed to be the [2]catenane by
a partial structure determination.
The alkynylgold(I) compounds with the diphosphine
Ph2PZPPh2 with Z ) (CH2)4 each gave only one singlet
resonance in the 31P NMR spectrum in the region δ )
38.8-39.0 and only a single set of resonances for the
dialkynyl ligands. The simplest explanation is that the
solutions contain a single isomer, which has effective
mirror symmetry in all cases, and the implication then
is that the compounds are present as the macrocycles
in solution. It has previously been assumed that the
solution and solid-state structures are the same, but this
assumption now appears to be invalid.3,12 Thus, if the
complexes were present in solution as [2]catenanes, the
complexes, such as 7b* with X ) CHMe, should give
two resonances in the 31P NMR spectrum. An earlier
study of the complex with X ) CH(4-C6H4Br) showed
that, at very low temperatures, a trace of an “AB”
resonance appeared in the 31P NMR spectrum along
with the dominant singlet resonance.12 This observation
is now interpreted in terms of a dominant presence of
the macrocycle in solution, along with traces of the [2]-
catenane at very low temperature. The NMR spectra of
several of the complexes in Scheme 2 with Z ) (CH2)4,
Consider first the complexes having diphosphine
ligands Ph2PZPPh2, with Z ) (CH2)3, which have the
greatest tendency to catenate. Figure 7 shows the 31P
NMR spectrum of a solution prepared by mixing equimo-
lar amounts of complexes 2a* (X ) CMe2) and 5a* (X )
C6H10) in CD2Cl2 solution and allowing time for equili-
bration to occur. By comparison with the spectra of the
single-component complexes listed in Table 2, the broad

5010 Organometallics, Vol. 24, No. 21, 2005
Habermehl et al.
of catenanes is expected to be 2a*:5a*:15 ) 1:1:2, and
the intensities of the 31P NMR peaks are consistent with
the approximate statistical ratio in this case (Figure 7).
The unsymmetrical catenanes were observed in all
cases when solutions were prepared containing complex
2a* and another symmetrical [2]catenane 1a* (X )
CH2), 3a* (X ) CPh2), 4a* (X ) C(CF3)2), 5a* (X )
C6H10), or 6a* (X ) SO2) having Z ) (CH2)3 (Scheme 3).
However, the ratio of concentrations of [2]catenanes
defined by the combination of hinge groups XX:X′X′:XX′
) 1:1:2 was not always observed. It was noted earlier
that the [2]catenane complexes 3a* (X ) CPh2) and 4a*
(X ) C(CF3)2) dissociate slowly in solution and exist
predominantly as the simple rings 3a and 4a, respec-
tively, at equilibrium. The NMR spectrum of a solution
prepared from equimolar amounts of 2a* (X ) CMe2)
and 3a* (X ) CPh2) initially showed the presence of the
parent [2]catenanes and the corresponding ring com-
plexes 2a and 3a. After 4 h, the concentration of 3a*
had decreased almost to zero, but 2a* remained and the
unsymmetrical [2]catenane 13 was detected. The mixed
ligand [2]catenane 13 was still observed in solution after
2 weeks. From the peak intensities in the 31P NMR
spectra, the thermodynamic stability of the [2]catenanes
toward dissociation to the component macrocycles fol-
lows the sequence 2a* > 12 > 3a*, indicating that the
hinge group effect favoring catenation is Me2C > Ph2C.
A similar effect was observed in the equilibrium be-
tween 2a*, 4a*, and 14 (Scheme 3).
Figure 7. 31P NMR spectrum (162 MHz, CD2Cl2, 25 °C)
of an equilibrium mixture of macrocycles and [2]catenanes
2a/2a* (X ) X′ ) CMe2) and 5a/5a* (X ) X′ ) C6H10) to
give the mixed ligand [2]catenane 15 (X ) CMe2, X′ )
C6H10). The broad peaks marked † are assigned to the
double ring and hexamer isomers.
Scheme 3. Formation of Mixed Ligand
[2]Catenanes
In contrast to the above observations for complexes
with Z ) (CH2)3, no new resonances were observed in
the 1H or 31P NMR spectra of mixtures of pairs of
alkynylgold(I) complexes with diphosphine ligands Ph2-
PZPPh2 with Z ) (CH2)4. For example, the 31P NMR
spectrum of a solution obtained by dissolving equimolar
amounts of the solid [2]catenane complexes 1b* (X )
CH2) and 2b* (X ) CMe2) contained only two singlet
resonances at δ ) 38.93 and 39.00, which are assigned
to the dissociated macrocycles 1b and 2b. The spectrum
was unchanged after two weeks in solution. Similar
observations were made for mixtures of 2b* with 3b,
4b*, 5b** (this complex crystallizes as a doubly braided
[2]catenane),3 and 6b. These observations are not
consistent with the presence of [2]catenanes in solution,
but add support to the conclusion that the complexes
with Z ) (CH2)4 exist in solution almost exclusively as
the simple macrocyclic complexes, even though many
of them crystallize as the [2]catenanes.
Chiral [2]Catenanes. The use of C2v-symmetrically
substituted hinge groups X (1-6) results in gold(I)
macrocycles and [2]catenanes that are achiral. For each
of these achiral molecules, only a single resonance in
the 31P NMR spectrum is expected and observed since
the phosphorus atoms are in chemically equivalent
positions. When the hinge group X has a prochiral
carbon such as when X ) CHMe (7), CMePh (8), or 1,1-
indanylidene (9), the resulting gold(I) macrocycles are
still achiral, but the [2]catenanes are chiral with C2
symmetry. This results in nonequivalent phosphorus
atoms Pa and Pb within each ring and contrasts with
the case of the unsymmetrical [2]catenanes 12-17, in
which the nonequivalent phosphorus atoms Pa and Pb
are in the two different rings (Scheme 4). The chiral [2]-
catenanes exhibit axial chirality, similar to the allene
singlet resonance at δ ) 35.9 (Figure 7) is assigned to
the macrocycles 2a and 5a, which are formed by
reversible dissociation from the parent [2]catenanes and
which have accidentally degenerate chemical shifts.
Sharp singlet resonances at δ ) 31.96 and 32.17 are
assigned to the parent [2]catenanes 2a* and 5a*, and a
broad unresolved resonance at δ ) ca. 35.5 is assigned
to double-ring and hexamer species. Most importantly,
two new singlet resonances are observed at δ ) 32.04
and 32.14, and these are assigned to the unsymmetrical
[2]catenane 15, [{Me2C(C6H4OCH2CCAu)2(µ-Ph2-
PZPPh2)}{C6H10(C6H4OCH2CCAu)2(µ-Ph2PZPPh2)}], Z
) (CH2)3 (Scheme 3). If the equilibrium constants for
dissociation of 2a* and 5a* are equal and if the
redistribution between [2]catenanes is determined by
statistical factors only, the ratio of the concentrations

Self-Assembly of Organometallic Gold(I) Rings
Organometallics, Vol. 24, No. 21, 2005 5011
Scheme 4. (a) Unsymmetrical [2]Catenane with
Different Hinge Groups; (b and c) aR and aS
Enantiomers of the C2-Chiral [2]Catenane with a
Prochiral Hinge Group
Figure 8. 31P NMR spectrum of an equilibrium mixture
of the macrocycle 7a and the chiral [2]catenane 7a*.
a [2]catenane and, in some cases, a double ring (Scheme
1), by [4+4] self-assembly to give a doubly braided [2]-
catenane, or by less defined forms of self-assembly to
give higher oligomers or polymers.3,10-13,22 For com-
plexes [{X(4-C6H4OCH2CtCAu)2(µ-Ph2PZPPh2)}n], there
appear to be only small energy differences between
isomers, so tailoring of the ligands can lead to different
products. In this work, it is shown that systems can be
designed in which the [2]catenanes have nonequivalent
phosphorus atoms while the simple macrocycles do not,
and then the structures in solution can be studied by
using 31P NMR spectroscopy. The catenanes are unsym-
metrical if they contain two different diacetylide groups
[{X(4-C6H4OCH2CtCAu)2(µ-Ph2PZPPh2)}{X′(4-C6H4-
OCH2CtCAu)2(µ-Ph2PZPPh2)] or if the hinge group
contains a prochiral carbon center [{RR′C(4-C6H4-
OCH2CtCAu)2(µ-Ph2PZPPh2)}2]. By use of this struc-
tural probe, it is shown that many of the complexes with
Z ) (CH2)3 exist to a major extent as [2]catenanes in
solution but that the complexes with Z ) (CH2)4 exist
very largely as the simple macrocycles in solution. In
both cases, the crystalline samples may exist as [2]-
catenanes. Thus, the initial assumption3 that larger
rings would be more likely to give [2]catenanes is
disproved. Instead, there is a “Goldilocks” effect in which
the 24-membered rings with Z ) (CH2)3 appear opti-
mum, and [2]catenanes are less favored with either
smaller or larger rings. The hinge group X has a
significant effect on the stability of the gold(I) [2]-
catenanes in solution. Sterically bulky substituents (X
) (CF3)2C or Ph2C) or substituents that can conjugate
to the aryl groups (X ) O, S, CdO) disfavor the
[2]catenane structure in solution compared to smaller
groups that do not π-bond (X ) CH2, CHMe, CMe2,
C6H10, SO2]. In cases in which the [2]catenane is present
in solution in only very low concentration, either the
simple macrocycle or the [2]catenane may crystallize
depending on the magnitude of the equilibrium constant
and the relative solubilities of the macrocycle and the
[2]catenane, but the [2]catenane is relatively favored in
the solid state through the entropy factor. Structural
studies indicate that the secondary bonding forces that
favor catenation can be any combination of aurophilic
attractions, aryl‚‚‚aryl attractions, and, possibly, CH‚‚
‚Au attractions. The aurophilic attractions are strongest
when Z ) (CH2)3, and the tight interlocking of the
component macrocycles with the diphosphine ligand
and spirane systems.18 The chiral axis passes diagonally
through the center of the [2]catenane, with the arrange-
ment of the R1 and R2 substituents determining the
configuration of the [2]catenane (stereochemical de-
scriptors aR and aS).18,19 The [2]catenanes reported
here, as well as the reported [2]catenane with X ) CH-
(4-C6H4Br),12 are not topologically chiral; each enanti-
omer can be transformed into the other by deformation
of the prochiral carbon atom in topological space.19,20
Previous examples of Euclidean chiral inorganic [2]-
catenanes have been based on pre-existing chiral ele-
ments in the rings, such as axially chiral binaphthyl
units.21
The gold(I) compounds containing a prochiral carbon
at the hinge group X and with Z ) (CH2)3 show three
resonances in their 31P NMR spectra: an AB multiplet
and a singlet (Table 2). For example, the gold(I) com-
pound with hinge group X ) CHMe (7a, 7a*) gave an
AB multiplet at δ ) 31.97 and 32.10 (4JPP ) 6 Hz) due
to the chiral [2]catenane 7a* and a singlet at δ ) 35.98
due to the macrocycle 7a (Figure 8). Similar observa-
tions were made for the other gold(I) compounds con-
taining a prochiral carbon at the hinge group, and data
are listed in Table 2. In contrast, when Z ) (CH2)4, all
complexes gave a singlet in the 31P NMR spectrum, as
expected if they exist as the achiral macrocycle only.
Discussion
The self-assembly process that occurs when digold(I)
diacetylide units and diphosphine ligands react together
can give isomers that form by [1+1] self-assembly to
give simple macrocycles, by [2+2] self-assembly to give
(18) Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of
Organic Compounds; Wiley-Interscience: New York, 1994; pp 1119-
1121.
(19) Schill, G. Catenanes, Rotaxanes, and Knots; Academic Press:
New York, 1971; pp 11-14, 17-18.
(20) (a) Walba, D. M. Tetrahedron 1985, 41, 3161. (b) Breault, G.
A.; Hunter, C. A.; Mayers, P. C. Tetrahedron 1999, 55, 5265.
(21) (a) Asakawa, M.; Ashton, P. R.; Boyd, S. E.; Brown, C. L.;
Menzer, S.; Pasini, D.; Stoddart, J. F.; Tolley, M. S.; White, A. J. P.;
Williams, D. J.; Wyatt, P. G. Chem. Eur. J. 1997, 3, 463. (b) Koizumi,
M.; Dietrich-Buchecker, C.; Sauvage, J.-P. Eur. J. Org. Chem. 2004,
770. (c) Burchell, T. J.; Eisler, D. J.; Puddephatt, R. J. J. Chem. Soc.,
Dalton Trans. 2005, 268.

5012 Organometallics, Vol. 24, No. 21, 2005
Habermehl et al.
spiro-C]; 75.39 [CtCH]; 78.69 [CtCH]; 114.07, 129.48, 140.29,
155.76 [C6H4]; 124.60, 125.91, 126.22, 126.75 [indan-aryl-CH];
143.63, 149.66 [indan-aryl-C]. EI-MS (m/z): calcd for C27H22O2
378.1619, found 378.1620.
[{Ph2C(4-C6H4OCH2CtCAu)2}n]. This was prepared from
Ph2C(4-C6H4OCH2CtCH)2 following an established procedure3
and isolated as a brown solid. Yield: 51%. IR (Nujol): ν(Ct
C) 2008 cm-1. Anal. Calcd for C31H22Au2O2: C, 45.38; H, 2.70.
Found: C, 45.30; H, 2.85.
Ph2P(CH2)3PPh2 appears to add both thermodynamic
and kinetic stability to the [2]catenane structure.
Experimental Section
General Procedures. NMR spectra were recorded by using
Varian Mercury 400 and Varian Inova 400 spectrometers. 1H
and 13C NMR chemical shifts are referenced to TMS, and 31P
NMR chemical shifts are reported relative to 85% H3PO4 as
external standard. IR spectra were recorded as KBr disks or
as Nujol mulls between NaCl plates using a Perkin-Elmer
2000 FT-IR spectrometer. High-resolution mass spectra were
measured by using a Finnigan MAT 8400 spectrometer. The
complexes [AuCl(SMe2)], [Au2Cl2(µ-Ph2PZPPh2)], with Z )
(CH2)3 or (CH2)4, and several known [2]catenane molecules
were prepared according to the literature.3,10-12,14 Reactions
involving gold compounds were protected from light by use of
darkened reaction flasks. Caution: Gold acetylides are po-
tentially explosive; they should be prepared in small quantities
and not subjected to shock.
The following were prepared similarly.
[{MePhC(4-C6H4OCH2CtCAu)2}n]: yellow solid. Yield:
83%. IR (Nujol): ν(CtC) 2008 cm-1. Anal. Calcd for C26H20-
Au2O2: C, 41.18; H, 2.66. Found: C, 40.79; H, 2.32.
[{C9H8(4-C6H4OCH2CtCAu)2}n]: C9H8 ) 1,1-indanylidene,
yellow solid. Yield: 82%. IR (Nujol): ν(CtC) 2014 cm-1. Anal.
Calcd for C27H20Au2O2: C, 42.10; H, 2.62. Found: C, 41.91;
H, 2.60.
[H2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2], 1a, and
[H2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2]2, 1a*. This
was prepared by reaction of the digold(I) diacetylide [{H2C(4-
C6H4OCH2CtCAu)2}n] with the diphosphine ligand Ph2P(CH2)3-
PPh2 according to the literature procedure3 and isolated as a
Ph2C(4-C6H4OCH2CtCH)2. This was prepared from the
diphenol Ph2C(4-C6H4OH)2 according to a general procedure
established previously23 and was isolated as a cream powder.
Yield: 97%. IR (KBr disk): ν(CtC) 2125 cm-1. NMR in
cream solid. Yield: 84%. IR (KBr disk): ν(CtC) 2130 cm-1
.
Anal. Calcd for C46H40Au2O2P2: C, 51.12; H, 3.73. Found: C,
51.38; H, 3.60. 1a*: NMR in CD2Cl2: δ(1H) 1.81 [br m, 4H,
PCH2CH2]; 2.45 [br m, 8H, PCH2]; 3.46 [s, 4H, CH2]; 4.61 [br,
8H, OCH2]; 6.07 [d, 8H, 3JHH ) 8 Hz, C6H4]; 6.67 [d, 8H, 3JHH
) 8 Hz, C6H4]; 7.42-7.75 [m, 40H, PPh]; δ(31P) 32.00 [s]. 1a:
NMR in CD2Cl2: δ(1H) 1.81 [br m, 2H, PCH2CH2]; 2.45 [br m,
4H, PCH2]; 3.83 [s, 2H, CH2]; 4.76 [s, 4H, OCH2]; 6.97 [d, 4H,
4
CDCl3: δ(1H) 2.52 [t, 2H, JHH ) 2 Hz, CtCH]; 4.66 [d, 4H,
4JHH ) 2 Hz, OCH2]; 6.85 [d, 4H, 3JHH ) 9 Hz, C6H4]; 7.10 [d,
4H, 3JHH ) 9 Hz, C6H4]; 7.16-7.24 [m, 10H, CPh2]; δ(13C) 53.72
[CPh2]; 55.73 [OCH2]; 75.45 [CtCH]; 78.63 [CtCH]; 113.53,
125.86, 127.38, 131.02, 132.12, 139.98, 147.00, 155.55 [C6H4
and Ph]. EI-MS (m/z): calcd for C31H24O2 428.1776, found
428.1767.
3
3JHH ) 8 Hz, C6H4]; 7.14 [d, 4H, JHH ) 8 Hz, C6H4]; 7.43-
7.75 [m, 20H, PPh]; δ(31P) 35.98 [s].
The following were prepared similarly.
The following were prepared similarly.
(F3C)2C(4-C6H4OCH2CtCH)2: yellow oil. Yield: 99%. IR
(Nujol mull): ν(CtC) 2126 cm-1. NMR in CDCl3: δ(1H) 2.56
[t, 2H, 4JHH ) 2 Hz, CtCH]; 4.71 [d, 4H, 4JHH ) 2 Hz, OCH2];
[Ph2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2], 3a, and
[Ph2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2]2, 3a*: re-
crystallized from CH2Cl2/pentane to give white needles.
Yield: 86%. IR (KBr disk): ν(CtC) 2132 cm-1. Anal. Calcd
for C58H48Au2O2P2: C, 56.50; H, 3.92. Found: C, 56.22; H, 3.51.
3a*: NMR in CD2Cl2: δ(1H) 1.85 [br, 4H, PCH2CH2]; 2.48 [br,
8H, PCH2]; 4.58 [s, 8H, OCH2]; 6.10 [d, 8H, 3JHH ) 9 Hz, C6H4];
3
3
6.97 [d, 4H, JHH ) 9 Hz, C6H4]; 7.33 [d, 4H, JHH ) 9 Hz,
C6H4]; δ(13C) 55.67 [OCH2]; 63.52 [m, JCF ) 25 Hz, C(CF3)2];
2
75.90 [CtCH]; 78.06 [CtCH]; 114.32, 126.21, 131.42, 157.70
[C6H4]; 124.29 (q, 1JCF ) 284 Hz, CF3]. EI-MS (m/z): calcd for
C21H14F6O2, 412.0897, found 412.0891.
3
6.73 [d, 8H, JHH ) 9 Hz, C6H4]; 7.08-7.29 [m, 20H, CPh];
MeHC(4-C6H4OCH2CtCH)2: yellow liquid. Yield: 65%. IR
(Nujol mull): ν(CtC) 2121 cm-1. NMR in CDCl3: δ(1H) 1.61
[d, 3H, 3JHH ) 7 Hz, CHMe); 2.53 [t, 2H, 4JHH ) 2 Hz, CtCH];
7.37-7.59 [m, 40H, PPh]; δ(31P) 32.07 [s]. 3a: NMR in CD2-
Cl2: δ(1H) 1.85 [br m, 2H, PCH2CH2]; 2.50 [m, 4H, PCH2]; 4.78
3
[s, 4H, OCH2]; 6.99 [d, 4H, JHH ) 8 Hz, C6H4]; 7.13 [d, 4H,
3
4
4.09 [q, 1H, JHH ) 7 Hz, CHMe]; 4.67 [d, 4H, JHH ) 2 Hz,
OCH2]; 6.92 [d, 4H, 3JHH ) 9 Hz, C6H4]; 7.16 [d, 4H, 3JHH ) 9
Hz, C6H4); δ(13C) 22.14 [CHMe]; 43.07 [CHMe]; 55.73 [OCH2];
75.36 [CtCH]; 78.69 [CtCH]; 114.61, 128.41, 139.65, 155.72
[C6H4]. EI-MS (m/z): calcd for C20H18O2 290.1306, found
290.1314.
3JHH ) 8 Hz, C6H4]; 7.18-7.24 [m, 10H, CPh]; 7.43-7.59 [m,
20H, PPh]; δ(31P) 35.78 [s].
[Ph2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)4PPh2], 3b:
cream solid. Yield: 76%. IR (KBr disk): ν(CtC) 2132 cm-1
.
Anal. Calcd for C59H50Au2O2P2: C, 56.83; H, 4.04. Found: C,
56.47; H, 3.80. NMR in CD2Cl2: δ(1H) 1.76 [br s, 4H, PCH2CH2];
MePhC(4-C6H4OCH2CtCH)2: cream solid. Yield: 74%. IR
2.38 [br s, 4H, PCH2]; 4.78 [s, 4H, OCH2]; 6.99 [d, 4H, 3JHH
)
(KBr disk): ν(CtC) 2118 cm-1. NMR in CDCl3: δ(1H) 2.16 [s,
3
9 Hz, C6H4]; 7.14 [d, 4H, JHH ) 9 Hz, C6H4]; 7.18-7.26 [m,
10H, CPh]; 7.44-7.64 [m, 20H, PPh]; δ(31P) 38.91 [s].
[C6H10(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2], 5a, and
[C6H10(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2]2, 5a*:
4
3H, CMePh]; 2.53 [t, 2H, JHH ) 2 Hz, CtCH]; 4.68 [d, 4H,
4JHH ) 2 Hz, OCH2]; 6.89 [d, 4H, 3JHH ) 9 Hz, C6H4]; 7.04 [d,
3
4H, JHH ) 9 Hz, C6H4]; 7.11 [m, 2H, CMePh]; 7.18-7.30 [m,
3H, CMePh]; δ(13C) 30.59 [CMePh]; 51.24 [CMePh]; 55.71
[OCH2]; 75.42 [CtCH]; 78.65 [CtCH]; 113.96, 129.65, 142.25,
155.61 [C6H4]; 125.87, 127.79, 128.55, 149.33 [CMePh]. EI-
MS (m/z): calcd for C26H22O2 366.1619, found 366.1618.
1,1-Indanylidene(4-C6H4OCH2CtCH)2: orange oil.
Yield: 0.88 g (70%). IR (Nujol mull): ν(CtC) 2122 cm-1. NMR
in CDCl3: δ(1H) 2.51 [t, 2H, 4JHH ) 2 Hz, CtCH]; 2.76 [t, 2H,
3JHH ) 6 Hz, indan-CH2]; 2.86 [t, 2H, 3JHH ) 6 Hz, indan-CH2];
cream solid. Yield: 89%. IR (KBr disk): ν(CtC) 2130 cm-1
.
Anal. Calcd for C51H48Au2O2P2: C, 53.32; H, 4.21. Found: C,
53.69; H, 4.08. 5a*: NMR in CD2Cl2: δ(1H) 1.29 [br s, 12H,
C6H10]; 1.82 [m, 4H, PCH2CH2]; 1.97 [br s, 8H, C6H10]; 2.46
3
[m, 8H, PCH2]; 4.61 [br m, 8H, OCH2]; 6.09 [d, 8H, JHH ) 9
Hz, C6H4]; 6.77 [d, 8H, 3JHH ) 9 Hz, C6H4]; 7.39-7.58 [m, 40H,
PPh]; δ(31P) 32.17 [s]. 5a: NMR in CD2Cl2: δ(1H) 1.47 [br, 6H,
C6H10]; 1.82 [br m, 2H, PCH2CH2]; 2.24 [br s, 4H, C6H10]; 2.46
4
3
4.66 [d, 4H, JHH ) 2 Hz, OCH2]; 6.87 [d, 4H, JHH ) 8 Hz,
3
[br m, 4H, PCH2]; 4.75 [s, 4H, OCH2]; 6.97 [d, 4H, JHH ) 9
3
4
C6H4]; 7.03 [dd, 1H, JHH ) 7 Hz, JHH ) 2 Hz, indan-C6H4];
Hz, C6H4]; 7.23 [d, 4H, 3JHH ) 9 Hz, C6H4]; 7.39-7.58 [m, 20H,
PPh]. δ(31P) ) 35.92 [s].
3
7.08 [d, 4H, JHH ) 8 Hz, C6H4]; 7.16-7.22 [m, 2H, indan-
3
4
C6H4]; 7.27 [dd, 1H, JHH ) 6 Hz, JHH ) 2 Hz, indan-C6H4];
[MePhC(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2], 8a,
and [MePhC(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2]2,
8a*: cream solid. Yield: 83%. IR (KBr disk): ν(CtC) 2132
cm-1. Anal. Calcd for C53H46Au2O2P2: C, 54.37; H, 3.96.
Found: C, 54.86; H, 3.88. 8a*: NMR in CD2Cl2: δ(1H) 1.80
δ(13C) 30.51, 43.71 [indan-CH2]; 55.76 [OCH2]; 60.55 [indan-
(22) Irwin, M. J.; Vittal, J. J.; Puddephatt, R. J. Organometallics
1997, 16, 3541.
(23) Morgan, P. W. Macromolecules 1970, 3, 536.

Self-Assembly of Organometallic Gold(I) Rings
Organometallics, Vol. 24, No. 21, 2005 5013
Table 3. Crystallographic Data and Experimental Parameters for X-ray Structure Determinations
1a*‚2CH2Cl2
7a*‚CH2Cl2
4b*‘
3b‚1/2Cl(CH2)2Cl
10‚2CH2Cl2
11‚MeCN
formula
fw
C
47H42Au2Cl2O2P2
C
48H44Au2Cl2O2P2
C
49H40Au2F6O2P2
C
59.5H51Au2Cl0.5O2P2 C46H36Au2Cl4O2P2S C49H45Au2NO3P2
1165.58
200
1179.60
150
1230.68
150
1271.60
150
1250.48
150
1151.73
150
0.71073
triclinic
P1h
T, K
λ, Å
0.71073
monoclinic
P2(1)/n
12.6303(2)
22.1259(5)
30.8281(5)
90
0.71073
monoclinic
P2(1)/n
12.5812(2)
22.3998(3)
31.2783(4)
90
0.71073
triclinic
P1h
0.71073
triclinic
P1h
0.71073
monoclinic
P2(1)/c
15.1745(3)
14.0174(4)
21.8130(5)
90
cryst syst
space group
a, Å
11.7901(4)
13.3497(5)
30.933(1)
93.601(2)
95.965(2)
110.796(2)
4500.7(3)
4
11.5787(2)
11.8408(3)
18.8233(4)
93.407(2)
93.663(1)
96.339(1)
2553.9(1)
2
13.1872(5)
13.3599(6)
14.2729(3)
65.537(2)
70.290(2)
81.152(2)
2154.5(1)
2
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
96.8120(10)
90
97.7630(10)
90
105.383(1)
90
8554.3(3)
8
8734.0(2)
8
4473.5(2)
4
Z
dcalcd, g cm-3
µ, mm-1
F(000)
no. of reflns
1.810
1.794
1.816
1.654
1.857
1.775
7.090
6.945
6.646
5.869
6.946
6.919
4496
4560
2368
1241
2400
1116
62 619
121 572
15 406/0/850
2.55-25.03
0.980
35 844
24 675
50 067
23 187
no. of data/restr/params 19 299/0/895
12 818/0/1003
2.66-23.26
1.021
11 706/3/498
2.57-27.51
1.029
13 009/6/466
2.67-30.06
0.999
9831/0/448
2.65-27.51
0.949
θ range, deg
2.59-27.49
0.952
0.058, 0.142
GOF on F2
R, Rw (I > 2σ(I))
0.040, 0.084
0.053, 0.105
0.047, 0.103
0.058, 0.144
0.045, 0.104
[s, 6H, CMePh]; 1.86 [br m, 4H, PCH2CH2]; 2.36 [br m, 8H,
PCH2]; 4.62 [br s, 8H, OCH2]; 6.22 [t, 8H, 3JHH ) 8 Hz, C6H4];
6.67-6.72 [m, 12H, C6H4 and CMePh]; 7.09-7.58 [m, 46H,
4H, 3JHH ) 8 Hz, C6H4]; 7.29 [d, 4H, 3JHH ) 8 Hz, C6H4]; 7.45-
7.65 [m, 20H, PPh]; δ(31P) 39.55 [s].
[O(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)5PPh2)], 11: cream
solid. Yield: 80%. IR (KBr disk): ν(CtC) 2132 cm-1. Anal.
Calcd for C47H42Au2O3P2: C, 50.82; H, 3.81. Found: C, 50.49;
H, 3.73. NMR in CD2Cl2: δ(1H) 1.60 [br, 6H, CH2]; 2.38 [br,
4H, PCH2]; 4.75 [s, 4H, OCH2]; 6.95 [d, 4H, 3JHH ) 8 Hz, C6H4];
4
CMePh and PPh]; δ(31P) 32.07, 32.36 [AB multiplet, JPP ) 6
Hz]. 8a: NMR in CD2Cl2: δ(1H) 1.82 [br m, 2H, PCH2CH2];
2.13 [s, 3H, CMePh]; 2.48 [br m, 4H, PCH2]; 4.77 [s, 4H, OCH2];
3
3
6.99 [d, 4H, JHH ) 9 Hz, C6H4]; 7.03 [d, 4H, JHH ) 9 Hz,
C6H4]; 7.09 [d, 1H, CMePh]; 7.15-7.27 [m, 4H, CMePh]; 7.42-
7.58 [m, 20H, PPh]; δ(31P) 35.84 [s].
3
7.06 [d, 4H, JHH ) 8 Hz, C6H4]; 7.40-7.69 [m, 20H, PPh]; δ-
(31P) 37.45 [s].
[MePhC(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)4PPh2], 8b:
[(CF3)2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2)], 4a,
and [(CF3)2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2)]2,
4a*. To a solution of [Au2Cl2(µ-Ph2P(CH2)3PPh2)] (0.505 g,
0.576 mmol) in CH2Cl2 (20 mL) was added AgO2CCF3 (0.254
g, 1.15 mmol). The mixture was stirred for 2 h, then filtered
through Celite into a cooled (-78 °C) solution of (CF3)2C(4-
C6H4OCH2CtCH)2 (0.237 g, 0.576 mmol) and triethylamine
(3.2 mL) in CH2Cl2 (40 mL). The reaction mixture was stirred
at -78 °C for 2 h, then for a further 1 h with the cold bath
removed. Water (50 mL) was added, then the organic phase
was separated, dried (MgSO4), and filtered. The filtrate was
concentrated (∼8 mL), then pentane (80 mL) was added. The
resulting light orange solid was isolated by filtration, then
washed with pentane and ether. Recrystallization from CH2-
Cl2/pentane gave white needles. Yield: 0.538 g (77%). IR (KBr
disk): ν(CtC) 2133 cm-1. Anal. Calcd for C48H38Au2F6O2P2:
C, 47.38; H, 3.15. Found: C, 46.90; H, 2.85. 4a*: NMR in CD2-
Cl2: δ(1H) 1.83 [br m, 4H, PCH2CH2]; 2.49 [br m, 8H, PCH2];
cream solid. Yield: 81%. IR (KBr disk): ν(CtC) 2132 cm-1
.
Anal. Calcd for C54H48Au2O2P2: C, 54.74; H, 4.08. Found: C,
54.48; H, 3.73. NMR in CD2Cl2: δ(1H) 1.72 [br s, 4H, PCH2CH2];
2.11 [s, 3H, Me]; 2.35 [br s, 4H, PCH2]; 4.77 [s, 4H, OCH2];
6.97-7.25 [m, 13H, CPh and C6H4]; 7.42-7.63 [m, 20H, PPh];
δ(31P) 38.90 [s].
[C9H8(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2], 9a, and
[C9H8(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2]2, 9a*: cream
solid. Yield: 79%. IR (KBr disk): ν(CtC) 2132 cm-1. Anal.
Calcd for C54H46Au2O2P2: C, 54.83; H, 3.92. Found: C, 54.64;
H, 3.88. 9a*: NMR in CD2Cl2: δ(1H) 2.28 [m, 8H, PCH2]; 2.50
3
[m, 8H, PCH2CH2 and indan-CH2]; 2.62 [t, 4H, JHH ) 7 Hz,
3
indan-CH2]; 4.51 [br s, 8H, OCH2]; 6.16 [m, 8H, JHH ) 8 Hz,
3
3
C6H4]; 6.71 [d, 8H, JHH ) 8 Hz, C6H4]; 6.95 [d, 2H, JHH ) 6
Hz, indan-C6H4]; 7.10-7.13 [m, 4H, indan-C6H4]; 7.15 [m, 2H,
indan-C6H4]; 7.21-7.46 [m, 40H, PPh]; δ(31P) 31.92, 32.01 [AB
multiplet, JPP ) 6 Hz]. 9a: NMR in CD2Cl2: δ(1H) 1.82 [m,
4
3
2H, PCH2CH2]; 2.49 [m, 4H, PCH2]; 2.76 [t, 2H, 3JHH ) 6 Hz,
indan-CH2]; 2.84 [t, 2H, 3JHH ) 6 Hz, indan-CH2]; 4.75 [s, 4H,
OCH2]; 6.84 [t, 1H, 3JHH ) 8 Hz, indan-C6H4]; 7.00 [d, 4H, 3JHH
) 9 Hz, C6H4]; 7.10 [m, 5H, C6H4 and indan-C6H4]; 7.19 [m,
1H, indan-C6H4]; 7.25 [m, 1H, indan-C6H4]; 7.41-7.59 [m, 20H,
PPh]; δ(31P) 35.86 [s].
4.50 [s, 8H, OCH2]; 6.24 [d, 8H, JHH ) 9 Hz, C6H4]; 6.89 [d,
8H, 3JHH ) 9 Hz, C6H4]; 7.21-7.39 [m, 40H, PPh]; δ(31P) 31.57
[s]. 4a: NMR in CD2Cl2: δ(1H) 1.86 [br m, 2H, PCH2CH2]; 2.54
3
[br m, 4H, PCH2]; 4.81 [s, 4H, OCH2]; 7.11 [d, 4H, JHH ) 9
Hz, C6H4]; 7.36 [d, 4H, 3JHH ) 9 Hz, C6H4]; 7.43-7.63 [m, 20H,
PPh]; δ(31P) ) 35.69 [s].
The following were similarly prepared.
[C9H8(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)4PPh2], 9b:
cream solid. Yield: 77%. IR (KBr disk): ν(CtC) 2132 cm-1
.
[(CF3)2C(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)4PPh2)], 4b:
light orange solid. Yield: 80%. IR (KBr disk): ν(CtC) 2133
cm-1. Anal. Calcd for C49H40Au2F6O2P2: C, 47.82; H, 3.28.
Found: C, 47.40; H, 2.99. NMR in CD2Cl2: δ(1H) 1.75 [br s,
4H, PCH2CH2]; 2.37 [br m, 4H, PCH2]; 4.83 [s, 4H, OCH2]; 7.13
Anal. Calcd for C55H48Au2O2P2: C, 55.19; H, 4.04. Found: C,
54.84; H, 3.92. NMR in CD2Cl2: δ(1H) 1.76 [br s 4H, PCH2CH2];
3
2.37 [br s, 4H, PCH2]; 2.75 [t, 2H, JHH ) 6 Hz, indan-CH2];
2.81 [t, 2H, 3JHH ) 6 Hz, indan-CH2]; 4.76 [s, 4H, OCH2]; 6.83-
3
3
3
6.89 [m, 1H, indan-C6H4]; 6.99 [d, 4H, JHH ) 9 Hz, C6H4];
[d, 4H, JHH ) 9 Hz, C6H4]; 7.36 [d, 4H, JHH ) 9 Hz, C6H4];
3
7.43-7.63 [m, 20H, PPh]; δ(31P) 38.81 [s].
7.04-7.09 [m, 1H, indan-C6H4]; 7.12 [d, 4H, JHH ) 9 Hz,
C6H4]; 7.17-7.19 [m, 1H, indan-C6H4]; 7.24-7.26 [m, 1H,
indan-C6H4]; 7.44-7.52 [m, 12H, PPh]; 7.59-7.64 [m, 8H,
PPh]; δ(31P) 38.93 [s].
[S(4-C6H4OCH2CtCAu)2(µ-Ph2PCtCPPh2], 10: cream
solid. Yield: 73%. IR (KBr disk): ν(CtC) 2135 cm-1. Anal.
Calcd for C44H32Au2O2P2S: C, 48.90; H, 2.98. Found: C, 48.71;
H, 3.08. NMR in CD2Cl2: δ(1H) 4.78 [s, 4H, OCH2]; 6.99 [d,
[MeHC(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2)], 7a,
and [MeHC(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)3PPh2)]2,
7a*: cream solid. Yield: 61%. IR (KBr disk): ν(CtC) 2130
cm-1. Anal. Calcd for C47H42Au2O2P2: C, 51.57; H, 3.87.
Found: C, 51.26; H, 3.56. 7a*: NMR in CD2Cl2: δ(1H) 1.33
3
[d, 6H, JHH ) 7 Hz, CHMe]; 1.82 [br m, 4H, PCH2CH2]; 2.44
3
[br m, 8H, PCH2]; 3.67 [q, 2H, JHH ) 7 Hz, CHMe]; 4.62 [br,

5014 Organometallics, Vol. 24, No. 21, 2005
Habermehl et al.
8H, OCH2]; 6.09 [d, 8H, 3JHH ) 8 Hz, C6H4]; 6.70 [d, 8H, 3JHH
) 8 Hz, C6H4]; 7.43-7.55 [m, 40H, PPh]; δ(31P) 31.97, 32.10
Mo KR radiation with COLLECT (Nonius B.V., 1998) software.
The unit cell parameters were calculated and refined from the
full data set. Crystal cell refinement and data reduction were
carried out with the DENZO (Nonius B.V., 1998) package. The
data were scaled using SCALEPACK (Nonius B.V., 1998). The
SHELXTL-NT (G. M. Sheldrick, Madison, WI) package was
used to solve the structures, followed by successive difference
Fourier transformations, and refined with full-matrix least-
squares on F2. Non-hydrogen atoms were refined anisotropi-
cally, unless otherwise specified. The hydrogen atoms were
calculated geometrically, riding on their respective carbon
atoms. Crystal data and refinement parameters are listed in
Table 3.
7a*. The molecule showed disorder at the hinge group
CHMe and the associated aryl groups. One was modeled as a
65/35 and the other as a 57/43 isotropic mixture.
3b. The 1,2-dichloroethane solvent molecule, which was
located on a symmetry element, was disordered and modeled
at half-occupancy. The distances were fixed as C-C ) 1.50 Å
and C-Cl ) 1.70 Å.
4
[AB multiplet, JPP ) 6 Hz]. 7a: NMR in CD2Cl2: δ(1H) 1.59
3
[d, 3H, JHH ) 7 Hz, CHMe]; 1.82 [br m, 2H, PCH2CH2]; 2.46
3
[br m, 4H, PCH2]; 4.06 [q, 1H, JHH ) 7 Hz, CHMe]; 4.76 [s,
4H, OCH2]; 6.98 [d, 4H, 3JHH ) 9 Hz, C6H4]; 7.17 [d, 4H, 3JHH
) 9 Hz, C6H4]; 7.43-7.63 [m, 20H, PPh]; δ(31P) 35.98 [s].
[MeHC(4-C6H4OCH2CtCAu)2(µ-Ph2P(CH2)4PPh2)], 7b:
cream solid. Yield: 63%. IR (KBr disk): ν(CtC) 2132 cm-1
.
Anal. Calcd for C48H44Au2O2P2: C, 52.00; H, 4.00. Found: C,
3
51.68; H, 3.90. NMR in CD2Cl2: δ(1H) 1.57 [d, 3H, JHH ) 7
Hz, CHMe]; 1.72 [br, 4H, PCH2CH2]; 2.33 [br m, 4H, PCH2];
4.04 [q, 1H, 3JHH ) 7 Hz, CHMe]; 4.76 [s, 4H, OCH2]; 6.99 [d,
4H, 3JHH ) 9 Hz, C6H4]; 7.18 [d, 4H, 3JHH ) 9 Hz, C6H4]; 7.42-
7.61 [m, 20H, PPh]; δ(31P) 38.98 [s].
Mixed Ligand [2]Catenanes. A mixture of complexes 2a*
(5 mg, X ) CMe2) and 5a* (5.1 mg, X ) C6H10) was dissolved
in CD2Cl2 (0.5 mL) in an NMR tube. The 1H and 31P NMR
spectra were obtained immediately and then periodically over
a period of 1 week, until equilibrium was reached. The 31P
NMR spectrum at equilibrium is shown in Figure 7, and data
for the mixed ligand [2]catenane 15 (X ) CMe2, X′ ) C6H10)
are listed in Table 2. The other reactions were studied
similarly and data are in Table 2.
X-ray Crystal Structure Determinations. Crystals of
1a*‚2CH2Cl2, 4b*, and 7a*‚CH2Cl2, were grown by slow
diffusion of pentane or petroleum ether into a solution of the
corresponding complex in CH2Cl2. Similarly, crystals of 10‚
2CH2Cl2 were obtained from CH2Cl2/ether, and crystals of 3b‚
1/2Cl(CH2)2Cl and 11 from 1,2-C2H4Cl2/MeCN. Data were
collected by using a Nonius Kappa-CCD diffractometer with
Acknowledgment. We thank the National Science
and Engineering Research Council (Canada) for finan-
cial support. R.J.P. thanks the Government of Canada
for a Canada Research Chair.
Supporting Information Available: Tables of X-ray data
in cif format are available free of charge via the Internet at
http://pubs.acs.org.
OM050588O