Luminescent binuclear gold(I) ring complexes

Article abstract of DOI:10.1021/om000528c

Cyclic digold(I) complexes, containing bridging diphosphine and diacetylide ligands and with 15- to 22-membered rings, are reported. Oligomeric complexes [C₆H₄(OCH₂CqqCAu)₂]_n were prepared from AuCl(S

Full text of DOI:10.1021/om000528c

Organometallics 2000, 19, 5063-5070
5063
Lu m in escen t Bin u clea r Gold (I) Rin g Com p lexes
William J . Hunks, Mary-Anne MacDonald, Michael C. J ennings, and
Richard J . Puddephatt*
Department of Chemistry, University of Western Ontario, London, Canada N6A 5B7
Received J une 21, 2000
Cyclic digold(I) complexes, containing bridging diphosphine and diacetylide ligands and
with 15- to 22-membered rings, are reported. Oligomeric complexes [C6H4(OCH2CtCAu)2]n
were prepared from AuCl(SMe2) and o-, m-, or p-bis(propargyloxy)benzene and then reacted
with the diphosphines Ph2P(CH2)nPPh2 (n ) 1-6) to give the corresponding ring complexes
[C6H4(OCH2CtCAu)2{µ-Ph2P(CH2)nPPh2}]. Alternatively, a two-step procedure in which the
soluble isocyanide complex [p-C6H4(OCH2CtCAuCNtBu)2] was prepared, followed by
displacement of the isocyanide ligands by the diphosphine, could be used. The complexes
[m-C6H4(OCH2CtCAu)2(µ-Ph2PCH2PPh2)], [m-C6H4(OCH2CtCAu)2{µ-Ph2P(CH2)5PPh2}],
[p-C6H4(OCH2CtCAu)2{µ-Ph2P(CH2)3PPh2}], and [p-C6H4(OCH2CtCAu)2{µ-Ph2P(CH2)5-
PPh2}] have been characterized by X-ray structure determinations. The ring complexes are
emissive at room temperature and may exhibit either red or blue shifts between solution
and the solid state.
In tr od u ction
(CtCR)(L)]4 and diphosphines [Au2(CtCR)2(µ-L-L)]5
are among the most stable organogold complexes, and
so it is possible to design more complex structures based
on alkynylgold(I) chemistry. Since propargyl derivatives
of bisphenols form linear polymers that were among the
first photoconducting polymers,6 and gold-substituted
propargyl groups have been used to form stable metal-
rimmed calixarenes,7 propargylgold(I) units have con-
siderable promise.
The preference for gold(I) complexes to adopt a two-
coordinate linear geometry makes it an ideal metal for
the formation of either linear chains or large macro-
cycles.8 Several polymeric alkynylgold(I) complexes have
been synthesized using rigid linear bis(ethynyl)arene
ligands.9 Kinked linear polymers were formed with
bridging diphosphines, whereas rigid-rod polymers were
formed with linear diisocyanoarene ligands.9 With 1,3,5-
tris(ethynyl)benzene, cross-linked polymers are formed.9c
The linear bis(ethynyl)arene ligands can also yield
macrocyclic gold rings on reaction with short bite
diphosphines such as bis(diphenylphosphino)methane,
Many gold(I) complexes display interesting photo-
chemistry, often giving room-temperature emission in
the visible region.1 In particular, alkynylgold(I) com-
plexes with tertiary phosphine ligands have been stud-
ied intensely for their room-temperature emission and
nonlinear optical (NLO) properties and their rich pho-
tochemistry.2 Organometallic macrocycles based on
metal acetylides have properties suggesting potential
applications in electronic devices.3 Alkynylgold(I) com-
plexes with tertiary phosphine donors of formula [Au-
(1) (a) Forward, J . M.; Fackler, J . P., J r.; Assefa, Z. In Optoelectronic
Properties of Inorganic Compounds; Roundhill, D. M., Fackler, J . P.,
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K. K. Organometallics 1996, 15, 1734. (m) Irwin, M. J .; Vittal, J . J .;
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10.1021/om000528c CCC: $19.00 © 2000 American Chemical Society
Publication on Web 10/21/2000

5064 Organometallics, Vol. 19, No. 24, 2000
Hunks et al.
Sch em e 1
and it is thought that aurophilic attractions (typical
distances and bond energies of 2.75-3.40 Å and 7-11
kcal/mol, respectively)10 control conformations and,
hence, the preference for rings over chains, in such
cases.11,12 There are many smaller 8- to 10-membered
cyclic dinuclear gold(I) complexes with bidentate phos-
phines, thiols, ylides, or dialkyldithiocarbamates,13 and
complexes with 14-membered rings are known with
dithiol and diphosphine ligands,14 but attempts to
prepare larger rings using butanedithiol resulted in the
formation of polymers.14c Large alkynylgold(I) ring
complexes can interpenetrate by self-assembly to give
catenane structures.15
From the above discussion, it is clear that the
combination of two gold(I) centers and two bidentate
ligands can give a range of ring or polymeric structures,
but that more work is required before confident predic-
tions of the resultant structures can be made. This
paper reports gold(I) complexes with flexible angular
diacetylide and diphosphine ligands. It was anticipated
that assembly of these angular components might yield
either unusual ring structures or zigzag one-dimen-
sional polymers with interesting properties. The reac-
tions gave 15- to 22-membered macrocyclic digold(I)
complexes with bridging diacetylide and diphosphine
ligands, Ph2P(CH2)nPPh2 (n ) 1-6), whose structures
and photophysical properties are described.
Sch em e 2
Resu lts a n d Discu ssion
Syn th esis of New Com p lexes. Following the es-
tablished route to oligomeric alkynylgold(I) complexes
of the form [Au(CtCR)]n,4,9 the reaction of 2 equiv of
[AuCl(SMe2)] and base with the flexible diethynyl arene
bifunctional ligands Ar(OCH2CtCH)2 gave the oligo-
meric digold(I) diacetylide complexes [(AuCtCCH2-
OArOCH2CtCAu)n], 1,Ar ) o-C6H4; 9, Ar ) m-C6H4;
17, Ar ) p-C6H4), as shown in Schemes 1-3. The
complexes were obtained as air-stable, light-sensitive,
insoluble deep yellow powders, which were character-
ized by IR and elemental analysis and by conversion to
more soluble derivatives. Oligomeric gold acetylides are
potentially shock sensitive and should be handled with
Sch em e 3
(9) (a) Puddephatt, R. J . J . Chem. Soc., Chem. Commun. 1998, 1055.
(b) J ia, G.; Puddephatt, R. J .; Scott, J . D.; Vittal, J . J . Organometallics
1993, 12, 3565. (c) Irwin, M. J .; Manojlovic´-Muir, L.; Muir, K. W.;
Puddephatt, R. J . J . Chem. Soc., Chem. Commun. 1997, 219. (d) Irwin,
M. J .; J ia, G.; Payne, N. C.; Puddephatt, R. J . Organometallics 1996,
15, 51. (e) J ia, G.; Payne, N. C.; Vittal, J . J .; Puddephatt, R. J .
Organometallics 1993, 12, 4771. (f) J ia, G.; Puddephatt, R. J .; Vittal,
J . J . J . Organomet. Chem. 1993, 449, 211. (g). MacDonald, M.-A.;
Puddephatt, R. J .; Yap, G. P. A. Organometallics 2000, 19, 2194.
(10) (a) Kaltsoyannis, N. J . Chem. Soc., Dalton Trans. 1997, 1. (b)
Pyykko¨, P.; Li, J .; Runeberg, N. Chem. Phys. Lett. 1994, 218, 133. (c)
Schmidbaur, H. Gold Bull. 1990, 23, 11. (d) Mingos, D. M. P. J . Chem.
Soc., Dalton Trans. 1996, 561.
(11) Irwin, M. J .; Rendina, L. M.; Vittal, J . J .; Puddephatt, R. J . J .
Chem. Soc., Chem. Commun. 1996, 1281.
(12) Schmidbaur, H.; Wohlleben, A.; Wagner, F.; Orama, O.; Hutt-
ner, G. Chem. Ber. 1977, 110, 1748.
(13) Schmidbaur, H., Ed. Gold: Progress in Chemistry, Biochemistry
and Technology; Wiley: Chichester, 1999.
(14) (a) Khan, Md. N. I.; Wang, S.; Fackler, J . P., J r. Inorg. Chem.
1989, 28, 3579. (b) Da´vila, R. M.; Elduque, A.; Grant, T.; Staples, R.
J .; Fackler, J . P., J r. Inorg. Chem. 1993, 32, 1749. (c) Narayanaswamy,
R.; Young, M. A.; Parkhurst, E.; Ouellette, M.; Kerr, M. E.; Ho, D. M.;
Elder, R. C.; Bruce, A. E.; Bruce, M. R. M. Inorg. Chem. 1993, 32, 2506.
(15) (a) Mingos, D. M. P.; Yau, J .; Menzer, S.; Williams, D. J . Angew.
Chem., Int. Ed. Engl. 1995, 34, 1894. (b) McArdle, C. P.; Irwin, M. J .;
J ennings, M. C.; Puddephatt, R. J ., Angew. Chem., Int. Ed. 1999, 38,
3376.
care. The alkyne ν(CC) vibrations appear at 2000, 2009,
and 2006 cm-1 in 1, 9, and 17, shifted to lower frequency
by approximately 100 cm-1 from the free ligands (2105,
2122, and 2122 cm-1, respectively). This large decrease

Luminescent Binuclear Gold(I) Ring Complexes
Organometallics, Vol. 19, No. 24, 2000 5065
in ν(CtC) provides evidence for donation of electron
density through π-bonding to an adjacent gold(I) center.
Therefore, the complexes are presumed to be coordina-
tion polymers involving η1 and η2 alkyne coordination
to gold(I), analogous to structures proposed for (phen-
ylethynyl)gold(I)16 and established for the gold(I) cat-
enane [{Au(CtCtBu)}6]2.15a
The soft donor ligand triphenylphosphine or tert-butyl
isocyanide readily replaced the weak gold-alkyne
π-bonds in 1, 9, or 17 to form complexes that are soluble
in dichloromethane (Schemes 1-3).16 Since the products
of reaction of 1, 9, and 17 with diphosphine ligands were
also soluble, they are likely to exist as rings rather than
polymers in all cases (Schemes 1-3). Since complex 20
(Scheme 3) was sparingly soluble, it was more readily
prepared by displacement of the tert-butyl isocyanide
ligands from complex 19 with the diphosphine ligand
(Scheme 3).9e This was also the preferred route to
complex 22, since the direct reaction of 17 with
Ph2P(CH2)3PPh2 occurred with partial decomposition to
metallic gold.
F igu r e 1. Molecular structure of [m-C6H4(OCH2CtCAu)2-
(µ-Ph2PCH2PPh2)], 11.
The products with phosphine or isocyanide ligands
shown in Schemes 1-3 were isolated as colorless to pale
yellow air-stable solids. They dissolve most readily in
chlorinated solvents, but react slowly with replacement
of the alkynylgold groups by chlorogold groups.17 Thus,
the diphosphine complexes slowly decompose in di-
chloromethane solution, and more rapidly in chloroform,
to give [(AuCl)2(µ-Ph2P(CH2)nPPh2)], and this can be a
problem in growing single crystals of the alkynyl-
gold(I) complexes.
Str u ctu r a l Ch a r a cter iza tion . The soluble com-
plexes were characterized by elemental analysis, by
their 1H and 31P NMR and IR spectra, and, in some
cases, by X-ray structure determinations. The complexes
display a weak IR absorption band at ca. 2120-2140
cm-1 corresponding to the ν(CtC) stretch. The isocya-
nide complex 19 gave ν(CtC) ) 2138 and ν(CtN) )
2226 cm-1, and the isocyanide stretch is shifted ap-
proximately 100 cm-1 to higher wavenumber from the
free ligand, indicating only weak π-back-bonding from
gold(I).18 In the 1H NMR spectra, the methylene protons
of the propargyl groups appear as singlets in the region
δ 4.7-4.9 ppm. The room-temperature 31P NMR spec-
trum of the complexes with diphosphine ligands display
sharp singlets in the region 33-40 ppm, indicating a
symmetrical arrangement of P-Au-CtC groups in
solution: two gold(I) centers are bridged by a diphos-
phine and a diacetylide ligand in each case. The related
triphenylphosphine complexes 2, 10, and 18 have open
structures, and in the 31P NMR spectra, they give
singlet resonances in the range δ 42-43 ppm. Low-
temperature 31P NMR spectra were recorded for com-
plexes 12 and 13 to test for fluxionality, but no changes
were observed in the spectra at -80 °C.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 11a
Au(1)-C(1)
Au(2)-C(14)
C(1)-C(2)
C(2)-C(3)
C(3)-O(4)
O(4)-C(5)
Au(1)-Au(2)
1.98(2)
1.93(3)
1.19(3)
1.55(3)
1.43(3)
1.34(3)
3.049(1)
Au(1)-P(1)
Au(2)-P(2)
C(13)-C(14)
C(12)-C(13)
C(12)-O(11)
O(11)-C(10)
2.270(6)
2.298(7)
1.28(4)
1.47(4)
1.50(2)
1.37(3)
C(1)-Au(1)-P(1)
P(1)-Au(1)-Au(2)
C(14)-Au(2)-Au(1)
C(2)-C(1)-Au(1)
O(4)-C(3)-C(2)
O(4)-C(5)-C(6)
172.1(7) C(1)-Au(1)-Au(2)
82.5(2) C(14)-Au(2)-P(2)
96.4(7) P(2)-Au(2)-Au(1)
101.5(7)
175.0(7)
88.5(2)
172(2)
120(2)
112(2)
177(2)
112(1)
113(2)
C(1)-C(2)-C(3)
C(5)-O(4)-C(3)
C(8)-C(10)-O(11)
C(10)-O(11)-C(12) 119(2)
C(13)-C(12)-O(11) 115(2)
C(13)-C(14)-Au(2) 169(2)
108.8(8) P(2)-C(15)-P(1) 109(1)
C(14)-C(13)-C(12) 174(2)
C(15)-P(1)-Au(1)
C(15)-P(2)-Au(2)
116.8(8)
a
Symmetry transformations used to generate equivalent at-
oms: -x, -y + 1, -z.
The molecular structure of [m-C6H4(OCH2CtC-Au)2-
(µ-dppm)], 11, is shown in Figure 1, and selected bond
lengths and angles are presented in Table 1. There are
two independent molecules in the unit cell, but their
structural parameters are very similar, so only one will
be described. The 16-membered ring occurs in a highly
twisted, extended chair conformation, with torsion
angles C-Au-Au-C ) 41.6° and P-Au-Au-P ) 34.0°.
The ring must be very flexible, with rapid ring inversion,
since equivalence of both the CH2O and CH2P2 protons
is observed in the 1H NMR spectrum of 11. The two gold
atoms in 11 are held in close proximity by the bridging
bis(diphenylphosphino)methane ligand, with the in-
tramolecular d(Au‚‚‚Au) ) 3.049(1) Å, only slightly
longer than the P‚‚‚P bite distance of 3.003 Å. The Au-P
bonds are normal for CtC-Au-P coordination, Au(1)-
P(1) ) 2.270(6) Å and Au(2)-P(2) ) 2.298(7) Å, but
longer than in many gold(I) phosphine complexes as a
consequence of the strong trans influence of the alkynyl
group.2,4 The gold-carbon distances are consistent with
other reported gold(I) acetylide complexes, with Au(1)-
C(1) ) 1.98(2) Å and Au(2)-C(14) ) 1.93(3) Å.2,4,9 The
X-ray structure determinations were carried out for
four of the digold(I) ring complexes, two based on the
meta complexes of Scheme 2 and two on the para
complexes of Scheme 3. No suitable single crystals of
the ortho complexes of Scheme 1 could be obtained.
(16) Coates, G. E.; Parkin, C. J . Chem. Soc. 1962, 3220.
(17) Payne, N. C.; Puddephatt, R. J .; Ravindranath, R.; Treurnicht,
I. Can. J . Chem. 1988, 66, 3176.
(18) Sarapu, A. C.; Fenske, R. F. Inorg. Chem. 1975, 14, 247.

5066 Organometallics, Vol. 19, No. 24, 2000
Hunks et al.
F igu r e 2. Molecular structure of [m-C6H4(OCH2CtCAu)2-
(µ-Ph2P(CH2)5PPh2)], 15.
F igu r e 3. Molecular structure of [p-C6H4(OCH2CtCAu)2-
(µ-Ph2P(CH2)3PPh2)], 22.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 15a
Au(1)-C(1)
Au(2)-C(14)
C(1)-C(2)
C(12)-C(13)
C(12)-O(11)
O(11)-C(9)
C(12)-O(11)#2
O(11)-C(9)#2
1.99(1)
1.98(1)
1.21(1)
1.59(3)
1.37(2)
1.41(2)
1.36(2)
1.43(2)
Au(1)-P(1)
Au(2)-P(2)
C(13)-C(14)
C(2)-C(3)
2.273(3)
2.270(3)
1.14(1)
1.51(2)
1.30(1)
1.40(2)
1.37(2)
1.42(2)
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 22a
Au(1)-C(1)
Au(3)-C(14)
C(1)-C(2)
2.03(2) Au(1)-P(1)
2.05(3) Au(3)-P(3)
1.13(3) C(13)-C(14)
1.40(3) C(2)-C(3)
1.57(5) C(3)-O(4)
2.261(7)
2.278(7)
1.21(3)
1.51(3)
1.44(2)
C(3)-O(4)
O(4)-C(5)
C(3)-O(4)#2
O(4)-C(5)#2
C(12)-C(13)
C(12)-O(11)
C(1)-Au(1)-P(1) 177.6(6)
C(14)-Au(3)-P(3) 176.3(7)
C(1)-Au(1)-P(1)
C(2)-C(1)-Au(1)
C(14)-C(13)-C(12) 167(2)
C(2)-C(3)-O(4)
C(3)-O(4)-C(5)
O(4)-C(5)-C(6)
C(2)-C(3)-O(4)#2
C(3)-O(4)-C(5)#2
O(4)-C(5)-C(6)#2
Au(1)-P(1)-C(15)
179.2(4) C(14)-Au(2)-P(2)
175(1)
169.6(4)
177(1)
170(1)
108(2)
125(2)
113(2)
Au(1)-P(1)-C(15)
C(2)-C(1)-Au(1)
116.8(8) Au(3)-P(3)-C(17)
174(2) C(1)-C(2)-C(3)
110.4(8)
166(2)
C(1)-C(2)-C(3)
C(13)-C(14)-Au(2)
C(13)-C(12)-O(11)
C(12)-O(11)-C(9)
O(11)-C(9)-C(8)
C(14)-C(13)-C(12) 170(3)
C(13)-C(14)-Au(3) 177(2)
C(13)-C(12)-O(11) 103(2)
C(12)-O(11)-C(10) 107(2)
111(1)
115(2)
103(2)
113(2)
137(2)
118(3)
C(2)-C(3)-O(4)
C(3)-O(4)-C(5)
O(4)-C(5)-C(6)
114(2)
114(2)
99(2)
O(11)-C(10)-C(9)
156(3)
C(13)-C(12)-O(11)#2 113(2)
C(12)-O(11)-C(9)#2
O(11)-C(9)-C(8)#2
119(3)
124(3)
108.6(4)
a
There are two independent molecules in the unit cell, only one
is described, since they are similar. Symmetry transformations
used to generate equivalent atoms: #1 -x + 4, -y, -z; #2 -x + 3,
-y, -z + 1.
114.4(3) Au(2)-P(2)-C(19)
a
Symmetry transformations used to generate equivalent at-
oms: #1 -x + 1, y, -z + 3/2; #2 -x + 5/2, -y + 1/2, -z + 1.
contact between gold atoms is 3.806 Å, so there are
neither intra- nor intermolecular Au‚‚‚Au attractions in
the structure of complex 15.
C-Au-P angles are slightly distorted from linearity
( P-Au-C ) 172.1(7)° and 175.0(7)°).
The molecular structure of [m-C6H4(OCH2CtC-Au)2-
{µ-Ph2P(CH2)5PPh2}], 15, is shown in Figure 2, and
selected bond lengths and angles given in Table 2. There
is disorder of the C6H4(OCH2)2 units, not shown in
Figure 2, in which the dioxyaryl group may fold to either
side of the diphosphine ligand; these disordered atoms
are shown joined by open bonds in Figure 2. Complex
15 has a distorted 20-membered ring structure. The
conformation of the diacetylide ligand is very different
from that observed in 11 (Figure 1), and this is clearly
to allow bridging by the bis(diphenylphosphino)pentane
ligand with its much greater bite distance compared to
bis(diphenylphosphino)methane. The intramolecular
nonbonding distances Au‚‚‚Au and P‚‚‚P are 7.73 and
8.07 Å, respectively. The torsion angle C-Au-Au-C )
23.5° (the angle between nonbonded CCAuP vectors)
indicates a lower degree of twist than in 11. The angle
Au(1)-C(1)tC(2) ) 175(1)° is approximately linear, but
Au(2)-C(14)tC(13) ) 170(1)° deviates from linearity.
Similarly, the angle C(1)-Au(1)-P(1) ) 179.2(4)° is
linear, but C(14)-Au(2)-P(2) ) 169.6(4)° is distorted
from linearity. Overall then, there is significant bowing
of the P(2)Au(2)C(14)C(13) unit, perhaps indicating
some ring strain is present. The closest intermolecular
The molecular structure of [p-C6H4(OCH2CtC-Au)2-
{µ-Ph2P(CH2)3PPh2}], 22, is shown in Figure 3, and
selected bond distances and angles are summarized in
Table 3. There are two independent but very similar
molecules in the unit cell. The 19-membered ring in 22
is more symmetrical than in 15, with a significantly
smaller dihedral angle C-Au-Au-C ) 8.5°. The coor-
dination about the gold(I) centers is close to linear, with
angles C-Au-P ) 177.6(6)° and 176.3(7)°, and the
angles CtC-Au ) 174(2)° and 177(2)° are also close to
linear. The intramolecular nonbonded distance Au‚‚‚Au
is 6.23 Å and P‚‚‚P is 5.65 Å.
The molecular structure of [p-C6H4(OCH2CtC-Au)2-
{µ-Ph2P(CH2)5PPh2}], 24, is shown in Figure 4, and
selected bond lengths and angles are presented in Table
4. Figure 4 shows that the 21-membered ring is skewed
but otherwise symmetrical; the dihedral angle C-Au-
Au-C ) 4.6° is much less than in 15 (23.5°). The
intramolecular nonbonding distances are Au‚‚‚Au ) 7.68
Å and P‚‚‚P ) 7.99 Å. The angles C-Au-P ) 177.0(3)
and 178.4(3) Å and CtC-Au ) 175(1)° and 177(1)° are
all close to linear.
Overall, the four structures show that the transan-
nular Au‚‚‚Au distance is largely controlled by the

Luminescent Binuclear Gold(I) Ring Complexes
Organometallics, Vol. 19, No. 24, 2000 5067
Ta ble 5. Lu m in escen ce Da ta for th e Com p lexes
complex
medium
excitation max, nm
emission max, nm
2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
350
350
350
350
350
350
350
350
350
350
350
350
350
350
391
349
357
367
343
366
337
365
347
363
345
362
345
362
354
350
372
350
357
370
345
338
350
369
346
364
347
396
535
440
535
455
485
530
485/540
455
540
450/575
540
460
535
460
426
426
477
446
443
439
437
442
424
439
414
440
423
442
437
433
488
454
463
451
466
451
426
449
415
450
424
452
3
4
5
6
7
8
F igu r e 4. Molecular structure of [p-C6H4(OCH2CtCAu)2-
(µ-Ph2P(CH2)5PPh2)], 24.
10
11
12
13
14
15
16
18
20
21
22
23
24
25
Ta ble 4. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 24a
Au(1)-C(1)
Au(2)-C(14)
C(1)-C(2)
C(2)-C(3)
C(3)-O(4)
O(4)-C(5)
2.03(1)
2.02(1)
1.15(1)
1.48(1)
1.44(1)
1.37(1)
Au(1)-P(1)
Au(2)-P(2)
C(13)-C(14)
C(12)-C(13)
C(12)-O(11)
O(11)-C(10)
2.282(3)
2.273(3)
1.15(1)
1.48(1)
1.45(1)
1.38(1)
C(1)-Au(1)-P(1)
C(2)-C(1)-Au(1)
177.0(3) C(14)-Au(2)-P(2)
175(1) C(1)-C(2)-C(3)
178.4(3)
177(1)
C(13)-C(14)-Au(2) 177(1)
C(14)-C(13)-C(12) 175(1)
C(2)-C(3)-O(4)
C(3)-O(4)-C(5)
O(4)-C(5)-C(6)
Au(1)-P(1)-C(15)
113.2(9) C(13)-C(12)-O(11) 111.4(9)
118.7(8) C(12)-O(11)-C(10) 116.6(8)
124(1)
O(11)-C(10)-C(8)
125(1)
110.2(3)
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
CH2Cl2
solid
112.6(3) Au(2)-P(2)-C(19)
d
Symmetry transformations used to generate equivalent at-
oms: #1 -x + 2, y, -z + 3/2; #2 -x + 1, y, -z + 3/2.
number of methylene spacers in the diphosphine ligand,
though the distance Au‚‚‚Au can be greater or less than
the P‚‚‚P separation, and that the diacetylide ligands
are sufficiently flexible to accommodate a wide range
of Au‚‚‚Au distances without creating excessive ring
strain. Only with the short-bite distance of the ligand
Ph2PCH2PPh2 is a transannular gold‚‚‚gold bonding
interaction invoked in the structure of complex 11, since
the analogous distances in 15, 22, and 24 are clearly
much too long for any bonding to be present.13 There
are no very close intermolecular Au‚‚‚Au contacts in any
of the structurally characterized complexes.
CH2Cl2
solid
CH2Cl2
Lu m in escen ce P r op er ties of th e Din u clea r Gold -
(I) Com p lexes. The photophysical properties of the
gold-acetylide macrocycles were studied and are sum-
marized in Table 5. All the dinuclear gold(I) complexes
synthesized exhibit luminescence at room temperature.
The luminescence spectra for the cyclic complexes as
solids in KBr and as solutions in CH2Cl2 display intense
emissions, whereas the open-ring triphenylphosphine
derivatives display only broad featureless emission
peaks of low intensity as solids. The emission spectra
for [m-C6H4(OCH2CtCAu)(µ-dppm)], 11, as a solid and
in solution are shown in Figure 5.
F igu r e 5. Emission spectra for [m-C6H4(OCH2CtCAu)2-
(µ-dppm)], 11, in solid (solid line) and CH2Cl2 solution
(dashed line).
Au‚‚‚Au interactions in the solid state has been reported
to lead to observation of a red shift in the emission band
when compared to the solution phase, and this is
thought to arise from greater involvement of the gold
Upon excitation at 340-400 nm, the gold(I)-acetylide
complexes in most cases display single broad emission
bands in the range 426-460 nm in solution and in the
region 414-540 nm in the solid state. In solution the
emission can be assigned as a triplet π-π* (CtC) or
triplet σ(AuC)-π* transition from AuCtC groups, or a
combination of both.1,2,20 The π*-orbital may be localized
on the alkynyl or an aryl group.1,2 The formation of
(19) Irwin, M. J .; Vittal, J . J .; Yap, G. P. A.; Puddephatt, R. J . J .
Am. Chem. Soc. 1996, 118, 13101.
(20) Bancroft, G. M.; Chan, T.; Puddephatt, R. J .; Tse, J . S. Inorg.
Chem. 1982, 21, 2946.

5068 Organometallics, Vol. 19, No. 24, 2000
Hunks et al.
solvents: it crystallized with NaCl. IR(Nujol): ν(CtC) 2000
cm-1 (w). Anal. Calcd for C12H8Au2O2‚NaCl: C, 22.6; H, 1.3.
Found: C, 22.7; H, 1.4.
d- and p-orbitals in the ground and excited state,
respectively.1,2 For the present complexes, the transan-
nular Au‚‚‚Au distance will be shortest in the complexes
with Ph2PCH2PPh2, and the red shifts from solution to
solid are 80 nm in 3 (ortho), 31 nm in 11 (meta), and 34
nm in 20 (para), suggesting a stronger interaction in
the ortho derivative 3, as would be expected. As the ring
size increases, no such intramolecular interactions are
possible and the solid state and solution spectra become
similar with the intraligand phosphorescence dominant.
In addition, the largest rings have emission maxima
similar to [Au(PPh3)(CtCPh)],2g with emission at 419
nm, supporting the view that the two AuCtC units are
essentially independent. In some cases, there is a blue
shift on going from solution to the solid state (complexes
4, 14, 15, 23-25), and complex 6 gives two emission
bands separated by 4830 cm-1. These data are consis-
tent with emission from exciplexes with solvent.21
[o-C6H4(OCH2CtCAu P P h 3)2], 2. A mixture of 1 (0.34 g,
0.59 mmol) and PPh3 (0.31 g, 1.18 mmol) in dichloromethane
(40 mL) was stirred for 30 min at room temperature. The
mixture was filtered, and to the resultant solution was added
pentane (100 mL). A pale yellow solid precipitated im-
mediately. The solid was collected by filtration and washed
with ether and pentane. Yield: 0.40 g, 62%. NMR (CD2Cl2):
δ(1H) 7.49 [m, 30H, Ph]; 7.10 [m, 2H, Ar]; 6.88 [m, 2H, Ar];
4.82 [s, 4H, OCH2]; δ(31P) 42.86 [s]. IR (Nujol): ν(CtC) 2131
cm-1. Anal. Calcd for C48H38Au2O2P2‚CH2Cl2: C, 49.6; H, 3.4.
Found: C, 49.9; H, 3.4.
[o-C6H4(OCH2CtC-Au )2(µ-d p p m )], 3. A mixture of 1
(0.41 g, 0.71 mmol) and dppm (0.27 g, 0.71 mmol) in dichloro-
methane (40 mL) was stirred for 30 min to give a cloudy
solution. The mixture was filtered, and pentane (100 mL) was
added to the resultant solution to precipitate a white solid.
The solid was collected by filtration and washed with ether
and pentane. The compound was recrystallized from CH2Cl2/
pentane. Yield: 0.52 g, 75%. NMR (CD2Cl2): δ(1H) 7.4-7.6 [m,
20H, Ph]; 7.11 [m, 2H, Ar]; 6.98 [m, 2H, Ar]; 4.73 [s, 4H,
OCH2]; 3.69 [sbr, 2H, dppm]; δ(31P) 40.17 [s]. IR (Nujol): ν-
(CtC) 2124 cm-1. Anal. Calcd for C37H30Au2O2P2: C, 46.2; H,
3.1. Found: C, 46.1; H, 3.1.
Con clu sion s
Previously, it was shown that polymeric gold(I) com-
plexes are formed by using rigid linear diacetylide and
diisocyanide ligands, but that the combination of linear
diacetylide and angular diphosphine ligands could give
either polymers or rings depending on the degree of
flexibility of the diphosphine used.2,9,11,19 It is clear from
the present work that binuclear gold complexes have a
strong preference for ring formation when both the
diacetylide and diphosphine ligands are flexible, as in
the compounds reported here. These new ring complexes
are luminescent at room temperature in solution and
as solid samples.
[o-C6H4(OCH2CtCAu )2(µ-d p p e)], 4. Prepared similarly to
3. Yield: 66%. NMR (CD2Cl2): δ(1H) 7.5-7.7 [m, 20H, Ph];
7.09 [m, 2H, Ar]; 6.88 [m, 2H, Ar]; 4.81 [s, 4H, OCH2]; 2.66
[sbr, 4H, dppe]; δ(31P) 40.09 [s]. IR (Nujol): ν(CtC) 2134 cm-1
.
Anal. Calcd for
C38H32Au2O2P2‚CH2Cl2: C, 44.1; H, 3.2.
Found: C, 44.4; H, 3.2.
[o-C6H4(OCH2CtCAu )2(µ-d p p p )], 5. 5 was prepared simi-
larly to 3. Yield: 82%. NMR (CD2Cl2): δ(1H) 7.5-7.8 [m, 20H,
Ph]; 6.95 [sbr, 4H, Ar]; 4.82 [s, 4H, OCH2]; 2.79 [sbr, 4H, dppp];
1.87 [sbr, 2H, dppp]; δ(31P) 37.49 [s]. IR (Nujol): ν(CtC) 2135
cm-1. Anal. Calcd for C39H34Au2O2P2: C, 47.3; H, 3.5. Found:
C, 46.8; H, 3.3.
Exp er im en ta l Section
[o-C6H4(OCH2CtC-Au )2(µ-d p p b)], 6. 6 was prepared
similarly to 3. Yield: 81%. NMR (CD2Cl2): δ (1H) 7.4-7.6 [m,
20H, Ph]; 6.91 [sbr, 4H, Ar]; 4.78 [s, 4H, OCH2]; 2.43 [sbr, 4H,
dppb]; 1.70 [sbr, 4H, dppb]; δ(31P) 37.25 [s]. IR (Nujol): ν(Ct
C) 2135 cm-1. Anal. Calcd for C40H36Au2O2P2‚CH2Cl2: C, 45.2;
H, 3.5. Found: C, 45.3; H, 3.8.
[o-C6H4(OCH2CtC-Au )2(µ-d p p p e)], 7. 7 was prepared
similarly to 3. Yield: 68%. NMR (CD2Cl2): δ(1H) 7.5-7.7 [m,
20H, Ph]; 6.87 [sbr, 4H, Ar]; 4.74 [s, 4H, OCH2]; 2.33 [sbr, 4H,
(dpppe)]; 1.61 [sbr, 6H, dpppe]; δ(31P) 39.65 [s]. IR (Nujol): ν-
(CtC) 2130 cm-1. Anal. Calcd for C41H38Au2O2P2‚0.5CH2Cl2:
C, 47.0; H, 3.7. Found: C, 47.6; H, 3.8.
[o-C6H4(OCH2CtC-Au )2(µ-d p p h )], 8. 8 was prepared
similarly to 3. Yield: 84%. NMR (CD2Cl2): δ(1H) 7.4-7.6 [m,
20H, Ph]; 6.84 [sbr, 4H, Ar]; 4.75 [s, 4H, CH2]; 2.23 [sbr, 4H,
dpph]; 1.28 [sbr, 8H, dpph]; δ(31P) 35.16 [s]. IR (Nujol): ν(Ct
C) 2134 cm-1. Anal. Calcd for C42H40Au2O2P2: C, 48.8; H, 3.9.
Found: C, 48.4; H, 3.8.
[m -C6H4(OCH2CtCAu )2]n , 9. To a solution of [AuCl(SMe2)]
(0.495 g, 1.70 mmol) in THF (20 mL)/MeOH (10 mL) was added
a solution of m-C6H4(OCH2CtCH)2 (0.160 g, 0.85 mmol) and
sodium acetate (0.211 g, 2.55 mmol) in THF (10 mL)/MeOH
(10 mL). The reaction mixture was stirred for 3 h to form a
yellow precipitate. The solid was collected by filtration, washed
with THF, MeOH, ether, and pentane, and dried. Yield: 0.456
g, 94%. The solid is insoluble in common organic solvents. IR
(Nujol): ν(CtC) 2009 (w) cm-1. Anal. Calcd for C12H8Au2O2:
C, 24.9; H, 1.4. Found: C, 25.5; H, 1.3.
[AuCl(SMe2)] and the bis(propynyloxy)benzene derivatives
were prepared by the literature methods.22,23 NMR spectra
were recorded using a Varian Gemini 300 MHz spectrometer,
with 1H NMR chemical shifts reported relative to TMS and
31P chemical shifts relative to an 85% H3PO4 external stan-
dard. IR spectra were recorded as Nujol mulls using a Perkin-
Elmer 2000 FTIR. Emission spectra were recorded at room
temperature, using a PTI LS 100 luminescence spectrometer
or a Fluorolog-3 spectrofluorimeter. For recording the emission
and excitation spectra, solutions were placed in quartz cu-
vettes, while solid samples were ground finely, in some cases
with added KBr. A 1 nm slit width was used for the solid
samples and a 3 nm slit width for the solutions. Several of
the complexes crystallized with solvent of crystallization that
could not be removed under vacuum at room temperature (see
X-ray data for example). The formulations given are consistent
with composition from NMR data as well as with analytical
data. CAUTION: some gold acetylides are shock sensitive:
they must be handled in small quantities using protective
equipment.
[o-C6H4(OCH2CtCAu )2], 1. A solution of o-C6H4(OCH2Ct
CH)2 (0.332 g, 1.78 mmol) and NaO2CMe (0.29 g, 1.78 mmol)
in THF (25 mL)/MeOH (15 mL) was added to a suspension of
[AuCl(SMe2)] (1.05 g, 3.56 mmol) in THF (100 mL), and the
resulting mixture was stirred for 3 h, yielding a bright yellow
precipitate. The mixture was filtered, and the yellow solid was
washed with THF, MeOH, and pentane and dried in vacuo.
Yield: 0.80 g, 78%. The solid is insoluble in common organic
[m -C6H4(OCH2CtCAu P P h 3)2], 10. PPh3 (0.320 g, 1.22
mmol) was added to a mixture of 8 (0.351 g, 0.61 mmol) in
CH2Cl2 (20 mL). The mixture was stirred for 3 h. Decolorizing
charcoal (100 mg) was added, the mixture was stirred for 15
min and filtered, and the product was precipitated as an off-
white solid by addition of pentane (100 mL). The solid was
collected by filtration, washed with ether and pentane, and
(21) Fu, W. F.; Chan, K. C.; Miskowski, V. M.; Che, C. M. Angew.
Chem., Int. Ed. 1999, 38, 2783.
(22) Tamaki, A.; Kochi, J . K. J . Organomet. Chem. 1974, 64, 411.
(23) Simon, D. Z.; Brookman, S.; Beliveau, J .; Salvador, R. L. J .
Pharm. Sci. 1977, 66, 431.

Luminescent Binuclear Gold(I) Ring Complexes
Organometallics, Vol. 19, No. 24, 2000 5069
dried. Yield: 0.556 g, 82%. NMR (CD2Cl2): δ(1H) 7.4-7.6 [m,
min and filtered, and the solvent removed under vacuum. The
residue was washed with pentane. A crystalline white powder
was obtained. Yield: 0.229 g, 89%. NMR(CD2Cl2): δ(1H) 6.88
[s, Ar]; 4.69 [s, OCH2]; 1.53 [s, 18H, t-Bu]. IR (Nujol): ν(CtN)
3
30H, Ph]; 7.20 [t, 1H, J ) 7.8 Hz, H5]; 6.60 [m, 3H, H2, H4,
H6]; 4.76 [s, 4H, OCH2]; δ(31P) 42.96 [s]. IR (Nujol): ν(CtC)
2136 cm-1. Anal. Calcd for C48H38Au2O2P2: C, 52.3; H, 3.5.
Found: C, 52.4; H, 3.4.
2226 cm-1, ν(CtC) 2138 cm-1. Anal. Calcd for C22H26
-
Au2N2O2: C, 35.5; H, 3.5; N, 3.8. Found: C, 34.9; H, 3.5; N,
3.7.
[m -C6H4(OCH2CtCAu )2(µ-d p p m )], 11. A solution of dppm
(0.107 g, 0.27 mmol) in CH2Cl2 (10 mL) was added to a
suspension of 8 (0.157 g, 0.27 mmol) in CH2Cl2 (10 mL). The
mixture was stirred for 3 h, and the product was isolated as
above. Yield: 0.219 g, 85%. NMR (CD2Cl2): δ(1H) 7.4-7.8 [m,
[p-C6H4(OCH2CtCAu )2(µ-d p p m )], 20. To a solution of
complex 19 (0.257 g, 0.345 mmol) in CH2Cl2 (10 mL) was added
a solution of dppm (0.133 g, 0.345 mmol) in CH2Cl2 (5 mL).
The mixture was stirred for 3 h, treated with decolorizing
charcoal (100 mg), and filtered, and the product was precipi-
tated with pentane (100 mL), collected by filtration, and
washed with acetone, ether, and pentane. Yield: 0.195 g, 59%.
NMR (nitrobenzene-d5/CD2Cl2): δ(1H) 7.0-7.7 [m, 20H, Ph];
4.82 [s, 4H, OCH2]; 3.81 [sbr, 2H, dppm]; δ(31P) 32.86 [s]. IR-
(Nujol): ν(CtC) 2123 cm-1. Anal. Calcd for C37H30Au2O2P2‚
0.25CH2Cl2: C, 45.5; H, 3.1. Found: C, 45.5; H, 3.1.
3
20H, Ph]; 7.10 [t, 1H, J ) 7.8 Hz, H5]; 6.50 [m, 3H, H2, H4,
H6], 4.85 [s, 4H, OCH2]; 3.57 [t, 2H, 2J (HP) ) 11.4 Hz, dppm];
δ(31P) 33.63 [s]. IR (Nujol): ν(CtC) 2132 cm-1. Anal. Calcd
for C37H30Au2O2P2: C, 46.2; H, 3.1. Found: C, 45.8; H, 2.9.
[m -C6H4(OCH2CtCAu )2(µ-d p p e)], 12. 12 was prepared
similarly to 11. Yield: 77%. NMR (CD2Cl2): δ(1H) 7.1-7.7 [m,
21H, Ph and H5 of Ar]; 6.50 [m, 2H, H2, H5]; 4.83 [s, 4H, OCH2];
2.50 [sbr, dppe]; δ(31P) 34.43 [s). IR (Nujol): ν(CtC) 2131 cm-1
.
Anal. Calcd for C38H32Au2O2P2: C, 46.7; H, 3.3. Found: C, 47.5;
H, 3.4.
[p-C6H4(OCH2CtC-Au )2(µ-d p p e)], 21. A solution of dppe
(0.107 g, 0.27 mmol) in CH2Cl2 (10 mL) was added to a
suspension of 17 (0.157 g, 0.27 mmol) in CH2Cl2 (10 mL). The
mixture was stirred for 3 h. The product was isolated as above.
Yield: 0.286 g, 85%. NMR (CD2Cl2): δ(1H) 7.4-7.6 [m, 20H,
Ph]; 6.95 [s, 4H, Ar]; 4.73 [s, 4H, OCH2]; 2.6 [sbr, 4H, dppe];
δ(31P) 39.96 [s]. IR(Nujol): ν(CtC) 2131 cm-1. Anal. Calcd for
[m -C6H4(OCH2CtCAu )2(µ-d p p p )], 13. 13 was prepared
similarly to 11. Yield: 86%. NMR (CD2Cl2): δ(1H) 7.4-7.7 [m,
3
20H, Ph]; 7.15 [t, 1H, J ) 7.8 Hz, H5]; 6.55 [m, 3H, H2, H4,
H6]; 4.85 [s, 4H, OCH2]; 1.8 [sbr, 2H, dppp]; 2.7 [sbr, 4H, dppp];
δ(31P) 36.00[s]. IR (Nujol): ν(CtC) 2133 cm-1. Anal. Calcd for
C
38H32Au2O2P2: C,45.0; H,3.6. Found: C, 44.8; H, 3.3.
C
39H34O2P2Au2‚0.25C5H12: C, 48.0; H, 3.8. Found: C, 48.2; H,
3.3.
[m -C6H4(OCH2CtCAu )2(µ-d p p b)], 14. 14 was prepared
similarly to 11. Yield: 79%. NMR (CD2Cl2): δ(1H) 7.4-7.7 [m,
[p-C6H4(OCH2CtC-Au )2(µ-d p p p )], 22. 22 was prepared
similarly to 20. Yield: 72%. NMR (nitrobenzene-d5/CD2Cl2):
δ(1H) 7.3-7.6 [m, 20H, Ph]; 5.32 [s, 4H, OCH2]; 2.5 [sbr, 4H,
dppp]; 2.1 [sbr, 2H, dppp]; δ(31P) 33.75 [s]. IR(Nujol): ν(CtC)
2136 cm-1. Anal. Calcd for C39H34Au2O2P2: C, 47.3; H, 3.5.
Found: C, 47.0; H, 3.5.
3
3
20H, Ph]; 7.15 [t, 1H, J ) 8.2 Hz, H5]; 6.57 [dd, 2H, J ) 8.2
Hz, 4J ) 2.4 Hz, H4, H6]; 4.78 [s, 4H, OCH2]; 2.3 [sbr, 4H,
dppb]; 1.7 [sbr, 4H, dppb]; δ(31P) 37.05 [s]. IR(Nujol): ν(CtC)
2133 cm-1. Anal. Calcd for C40H36Au2O2P2‚0.25CH2Cl2: C, 46.5;
H, 3.6. Found: C, 46.7; H, 3.4.
[p-C6H4(OCH2CtC-Au )2(µ-d p p b)], 23. 23 was prepared
similarly to 21. Yield: 74%. NMR (CD2Cl2): δ(1H) 7.4-7.7 [m,
20H, Ph]; 6.96 [s, 4H, Ar]; 4.76 [s, 4H, OCH2]; 2.4 [sbr, 4H,
dppb]; 1.6 [sbr, 4H, dppb]; δ(31P) 37.76 [s]. IR(Nujol): ν(CtC)
2131 cm-1. Anal. Calcd for C40H36Au2O2P2: C, 47.8; H, 3.6.
Found: C, 47.9; H, 3.5.
[p-C6H4(OCH2CtC-Au )2(µ-d p p p e)], 24. 24 was prepared
similarly to 21. Yield: 76%. NMR (CD2Cl2): δ(1H) 7.4-7.7 [m,
20H, Ph]; 7.00 [s, 4H, Ar]; 4.78 [s, 4H, OCH2]; 2.3 [sbr, 8H,
dpppe], 1.6 [sbr, 2H, dpppe]; δ(31P) 38.70 [s]. IR(Nujol): ν(Ct
C) 2133 cm-1. Anal. Calcd for C41H38Au2O2P2: C, 48.3; H, 3.8.
Found: C, 48.1; H, 3.8.
[p-C6H4(OCH2CtC-Au )2(µ-d p p h )], 25. 25 was prepared
similarly to 21. Yield: 76%. NMR (CD2Cl2): δ(1H) 7.4-7.7 [m,
20H, Ph]; 6.98 [s, 4H, Ar]; 4.78 [s, 4H, OCH2]; 2.4 [sbr, 8H,
dpph]; 1.5 [sbr, 4H, dpph]; δ(31P) 36.68 [s]. IR(Nujol): ν(CtC)
2131 cm-1. Anal. Calcd for C42H40Au2O2P2: C, 48.8; H, 3.9.
Found: C, 48.3; H, 3.8.
X-r a y Str u ctu r e Deter m in a tion of 11. Crystals of [(m-
C6H4(OCH2CCAu)2(µ-Ph2P(CH2)PPh2)]‚1/4ether; 1/2CH2Cl2 were
grown by slow diffusion of diethyl ether into a solution in
dichloromethane. A colorless needle was mounted on a glass
fiber. Data were collected at low temperature (-73 °C) using
a Nonius Kappa-CCD diffractometer using COLLECT (Nonius,
1998) software. The unit cell parameters were calculated and
refined from the full data set. Crystal cell refinement and data
reduction were carried out using the Nonius DENZO package.
The data were scaled using SCALEPACK (Nonius, 1998), and
no other absorption corrections were applied; Friedel pairs
were kept separate. The crystal data and refinement param-
eters are listed in Table 6. The reflection data were consistent
with a triclinic space group P1h, with two molecules in the
asymmetric unit. The SHELXTL 5.1 (Sheldrick, G. M., Madi-
son, WI) program package was used to solve the structure by
direct methods, followed by successive difference Fouriers. The
diphenylphosphino groups were modeled isotropically with
phenyl groups as regular hexagons (AFIX 66). However, the
diacetylide ligand was less well behaved and the atoms C1,
C9, and C21 were kept isotropic. All remaining non-hydrogen
atoms in the molecule were refined with anisotropic thermal
parameters. The hydrogen atoms were calculated geometri-
[m -C6H4(OCH2CtC-Au )2(µ-d p p p e)], 15. 15 was prepared
similarly to 11. Yield: 72%. NMR (CD2Cl2): δ(1H) 7.4-7.7 [m,
3
4
20H, Ph]; 7.19 [t, 1H, J ) 8.2 Hz, H5]; 6.65 [d, 1H, J ) 2.2
3
4
Hz, H2]; 6.59 [dd, 2H, J ) 8.1 Hz, J ) 2.3 Hz, H4, H6]; 4.79
[s, 4H, OCH2]; 2.3 [sbr, 6H, dpppe]; 1.5 [sbr, 4H, dpppe]; δ-
(31P) 38.10 [s]. IR(Nujol): ν(CtC) 2133 cm-1. Anal. Calcd for
C
41H38Au2O2P2: C, 48.3; H, 3.8. Found: C, 47.9; H, 3.8.
[m -C6H4(OCH2CtCAu )2(µ-d p p h )], 16. 16 was prepared
similarly to 11. Yield: 72%. NMR (CD2Cl2): δ(1H) 7.4-7.7 [m,
3
4
20H, Ph]; 7.17 [t, 1H, J ) 8.2 Hz, H5]; 6.67 [d, 1H, J ) 2.2
3
4
Hz, H2]; 6.58 [dd, 2H, J ) 8.2 Hz, J ) 2.0 Hz, H4, H6]; 4.76
[s, 4H, OCH2]; 2.3 [sbr, 8H, dpph]; 1.5 [sbr, 4H, dpph]; δ(31P)
36.17 [s]. IR(Nujol): ν(CtC) 2133 cm-1. Anal. Calcd for C42H40
-
Au2O2P2: C, 48.8; H, 3.9. Found: C, 48.7; H, 3.8.
[p-C6H4(OCH2CtC-Au )2]n , 17. To a solution of [AuCl-
(SMe2)] (0.495 g, 1.70 mmol) in THF (20 mL)/MeOH (10 mL)
was added a solution of p-C6H4(OCH2CtCH)2 (0.160 g, 0.85
mmol) and sodium acetate (0.211 g, 2.55 mmol) in THF (10
mL)/MeOH (10 mL). The reaction mixture was stirred for 3 h,
forming a yellow precipitate. The solid was collected by
filtration, washed with THF, MeOH, ether, and pentane, and
dried. Yield: 0.413 g, 84%. IR(Nujol): 2006 (w) cm-1. Anal.
Calcd for C12H8Au2O2: C, 24.9; H, 1.4. Found: C, 24.6; H, 1.2.
[p-C6H4(OCH2CtCAu P P h 3)2], 18. PPh3 (0.090 g, 0.345
mmol) was added to a mixture of 17 (0.100 g, 0.172 mmol) in
CH2Cl2 (20 mL). The mixture was stirred for 3 h. Decolorizing
charcoal (100 mg) was added, the mixture was stirred for 15
min and filtered, and the product was precipitated by addition
of pentane (100 mL), collected by filtration, washed with ether
and pentane, and dried. Yield: 0.146 g, 77%. NMR (CD2Cl2):
δ(1H) 7.4-7.6 [m, 30H, Ph]; 6.92 [s, 4H, Ar]; 4.72 [s, 4H, OCH2];
δ(31P) 42.23 [s]. IR (Nujol): ν(CtC) 2134 cm-1. Anal. Calcd
for C48H38O2P2Au2‚0.25CH2Cl2: C, 51.6; H, 3.4. Found: C, 51.5;
H, 3.2.
[p-C6H4(OCH2CtCAu CtNtBu )2], 19. tert-Butyl isocyanide
(0.080 mL, 0.689 mmol) was slowly added to a suspension of
complex 17 (0.200 g, 0.345 mmol) in CH2Cl2 (10 mL) under
nitrogen. The mixture was stirred for 1 h, then decolorizing
charcoal (100 mg) was added. The mixture was stirred for 10

5070 Organometallics, Vol. 19, No. 24, 2000
Ta ble 6. Cr ysta l Da ta for Com p lexes 11, 15, 22, a n d 24
Hunks et al.
11
15
22
24
empirical formula
fw
C
38.50H33.50Au2ClO2‚25P2
C41.63H31.25Au2O2P2
1019.29
C40.38H34Au2Cl10.25O2P2
1015.91
C43H40Au2Cl4O2P2
1023.48
1186.42
temp
200(2) K
0.71073 Å
triclinic
P1h
295(2) K
296(2) K
200(2) K
wavelength
cryst syst
space group
unit cell dimens
0.71073 Å
0.71073 Å
triclinic
P1h
0.71073 Å
monoclinic
monoclinic
C2/c
C2/c
a ) 13.5631(11) Å
b ) 16.2617(9) Å
c ) 18.7032(17) Å
R ) 74.015(4)°
â ) 69.063(4)°
γ ) 66.952(4)°
3500.9(5) Å3
4
a ) 14.3314(5) Å
b ) 27.2257(10) Å
c ) 21.8460(8) Å
â ) 94.136(2)°
a ) 12.8486(7) Å
b ) 13.7164(5) Å
c ) 20.9796(11) Å
R ) 86.079(3)°
â ) 89.858(3)°
γ ) 89.958(3)°
3688.7(3) Å3
4
a ) 30.0723(10) Å
b ) 11.8721(4) Å
c ) 26.4185(9) Å
â ) 110.706(2)°
volume
Z
density (calcd)
abs coeff
F(000)
crystal size
θ range for data
collection
index ranges
8501.7(5) Å3
8
8822.7(5) Å3
8
1.942 Mg/m3
8.573 mm-1
1950
1.593 Mg/m3
6.999 mm-1
3880
1.829 Mg/m3
8.083 mm-1
1938
1.786 Mg/m3
6.993 mm-1
4560
0.50 × 0.22 × 0.20 mm3
2.58 to 25.00°
0.22 × 0.20 × 0.18 mm3
1.76 to 28.29°
0.12 × 0.10 × 0.09 mm3
2.17 to 24.41°
0.15 × 0.08 × 0.02 mm3
2.55 to 25.04°
-15e h e 15,
-19e k e 19,
-21 e l e 22
16 599
-19 e h e 19,
-35 e k e 36,
-29 e l e 29
-14 e h e 14,
-15 e k e 15,
0 e l e 24
0 e h e 35,
0 e k e 14,
-31 e l e 29
39 761
no. of reflns collected
no. of ind reflns
completeness to θ )
abs corr
max. and min. transmn
refinement method
47 214
34 698
7607 [R(int) ) 0.098]
25.00° 61.7%
SCALEPACK
0.2789 and 0.0995
full-matrix
10 528 [R(int) ) 0.1440]
11 850 [R(int) ) 0.0620]
7789 [R(int) ) 0.0960]
25.04° 99.7%
SCALEPACK
0.8557 and 0.4202
full-matrix
28.29° 99.6%
24.41° 97.7%
SCALEPACK
0.3656 and 0.3081
full-matrix
INTEGRATION
0.5266 and 0.4363
full-matrix
least-squares on F2
7607/4/468
least-squares on F2
10528/43/424
least-squares on F2
11850/7/343
least-squares on F2
7789/0/479
no. of data/restraints/
params
goodness-of-fit on F2
final R indices [I>2σ(I)]
1.001
0.996
0.846
1.048
R1 ) 0.0828,
wR2 ) 0.2123
R1 ) 0.1308,
wR2 ) 0.2347
2.258 and -2.533 e Å-3
R1 ) 0.0691,
wR2 ) 0.1302
R1 ) 0.2141,
wR2 ) 0.1662
1.039 and -0.984 e Å-3
R1 ) 0.0382,
wR2 ) 0.0884
R1 ) 0.1424,
wR2 ) 0.1171
0.881 and -1.194 e Å-3
R1 ) 0.0512,
wR2 ) 0.1027
R1 ) 0.0911,
wR2 ) 0.1138
1.724 and -1.422 e Å-3
R indices (all data)
largest diff peak and hole
cally and were riding on their respective carbon atoms. The
ether was sitting on a special position and was modeled as
two isotropic halves with fixed bond lengths (C-O 1.35 Å; C-C
1.54 Å). The dichloromethane was modeled anisotropically. The
largest residual electron density peak (2.258 e/Å3) was associ-
ated with one of the gold atoms.
dered, and therefore two parts were refined in a 60/40 mixture.
The hydrogen atoms were calculated geometrically and were
riding on their respective carbon atoms. In addition to the two
dimers in the asymmetric unit, two solvent molecules were
found. The methylene chloride was found on a center of
symmetry and was modeled as isotropic atoms (1/4 occupancy)
with the C-Cl distance fixed at 1.65 Å. The THF was also
found on a center of symmetry and was modeled as five
isotropic carbon atoms (1/2 occupancy) with the C-C distance
fixed and allowed to refine to a value of 1.587 Å. No hydrogens
were incorporated into the solvent models. The largest residual
electron density peak (0.881 e/Å3) was associated with one of
the solvent molecules.
X-r ay Str u ctu r e Deter m in ation of 24. Crystals of [p-C6H4-
(OCH2CtCAu)2(µ-dpppe)]‚3CH2Cl2 were grown from slow dif-
fusion of pentane into a methylene chloride solution. A tiny,
colorless plate was mounted on a glass fiber. Data were
collected at low temperature (200 K) and treated as above. The
reflection data and systematic absences were consistent with
a monoclinic space group C2/c. One of the methylene chlorides
of solvation was modeled as a complete CH2Cl2 molecule; the
other two both had the carbon atoms on special positions. The
solvent hydrogen atoms were not incorporated into the model.
All non-hydrogen atoms were refined with anisotropic thermal
parameters. The hydrogen atoms were calculated geometri-
cally and were riding on their respective carbon atoms. The
largest residual electron density peak (1.724 e/Å3) was associ-
ated with one of the gold atoms.
X-r ay Str u ctu r e Deter m in ation of 15. Crystals of [m-C6H4-
(OCH2CtCAu)2(µ-dpppe)]‚1/4pentane were grown by slow
diffusion of pentane into a solution in dichloromethane. A
colorless needle was cut, and the resulting block was mounted
on a glass fiber. Data were collected at room temperature (22
°C) and data treated as above. The atoms O4 through C12 were
disordered and were modeled as two separate entities (60/40)
with isotropic thermal parameters and no hydrogens. The
moiety O4-O11 was constrained to be flat, and chemically
equivalent bonds were constrained to be equal. All remaining
non-hydrogen atoms were refined with anisotropic thermal
parameters. The hydrogen atoms were calculated geometri-
cally and were riding on their respective carbon atoms. The
pentane of solvation was sitting with one carbon on a center
of symmetry, and so only half of the molecule was located in
the difference map. The C-C bond distances were fixed. The
largest residual electron density peak (1.039 e/Å3) was associ-
ated with one of the gold atoms.
X-r a y Str u ctu r e Deter m in a tion of 22. Crystals of
[p-C6 H 4 (OCH 2 CCAu )2 (µ-P h 2 P (CH 2 )3 P P h 2 )]‚1/4CH 2 Cl2 ‚
1/2THF were grown by slow diffusion of a solution of
Ph2P(CH2)3PPh2 in tetrahydrofuran intoa solution of[p-C6H4(OCH2-
CCAuCNtBu)2] in dichloromethane. A colorless prism was
mounted on a glass fiber. Data were collected at 23 °C and
treated as above. The reflection data and systematic absences
were consistent with a triclinic space group P1h with two
distinct molecules in the asymmetric unit. Only the gold and
phosphorus atoms were refined anisotropically. The remaining
atoms were refined isotropically, and the phenyl rings were
refined as rigid hexagons. O11 and C12 were slightly disor-
Ack n ow led gm en t. We thank the NSERC (Canada)
for financial support and for a scholarship to W.H.
Su p p or tin g In for m a tion Ava ila ble: Tables of X-ray data
for the complexes. This material is available free of charge via
the Internet at http://pubs.acs.org.
OM000528C