Synthesis of luminescent alkynyl gold metalaligands containing 2,2′-bipyridine-5-yl and 2,2′:6′,2″-terpyridine-4-yl donor groups

Article abstract of DOI:10.1021/om7009123

[AuCl(SMe₂)] reacts with HC≡CR (R = bpyl = 2,2′-bipyridine-5-yl (1), phtpyl = phenyl-4-(2,2′: 6′,2″-terpyridine-4-yl) (2)) and NEt₃ (1:1:3) to afford the polymers [Au(C≡CR)]_n (R = bpyl (3), phtpyl (4)). The new alkyne HC≡Cphccbpyl (5, phccbpyl = 4-C₆H₄C≡ CbPyl) has been prepared by Sonogashira coupling of 4-Me₃SiC≡ CC₆H₄I and 1 followed by desilylation of the resulting alkyne 4-Me₃SiC≡Cphccbpyl. The alkynyl Au(I) complexes [Au(C≡CR)L] (R = bpyl, L = PPh₃ (6), PTol₃ (7, Tol = 4-MeC₆H₄), PEt₃ (8); R = phtpyl, L = XyNC (9), PPh₃ (10); R = phccbpyl, L = PPh₃ (11)) have been prepared by reacting: (1) 3 or 4 with L or (2) the corresponding alkyne 1,2, or 5 with [Au(acac)(PPh₃)] (acac = acetylacetonato). The reaction of 3 or 4 with diphosphines gives [(Au(C≡CR) }₂(μPh ₂P(CH₂)_XPPh₂)] (R = bpyl, x = 1 (12), 2 (13), 4 (14), 10 (15); R = phtpyl, x = 10 (16)). ESI mass spectrometric studies show that complexes 12-14 are in equilibrium with the salts [Au ₃(C≡Cbpyl)₂(μPh₂P(CH₂) _xPPh₂)₂][Au(C≡Cbpyl)₂], although only when x = 1 (17) was a significant concentration of the salt detected by NMR spectroscopy and isolated. The anionic complexes PPN[Au(C≡CR)₂] (R = bpyl (18), phtpyl (19), or phccbpyl (20)) have been prepared by reaction of the corresponding alkynes with PPN[Au(acac)₂]. Complexes 6, 10, 13, 14, 17, and 18 have been characterized by single-crystal X-ray diffraction studies. The alkynyl complexes are luminescent at room temperature, displaying dual emissions.

Full text of DOI:10.1021/om7009123

646
Organometallics 2008, 27, 646–659
Synthesis of Luminescent Alkynyl Gold Metalaligands Containing
2,2′-Bipyridine-5-yl and 2,2′:6′,2′′-Terpyridine-4-yl Donor Groups
José Vicente,*,# Juan Gil-Rubio,*,# Natalia Barquero,# Peter G. Jones,† and Delia Bautista‡
Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química,
UniVersidad de Murcia, E-30071 Murcia, Spain, Institut für Anorganische and Analytische Chemie,
Technische UniVersität Braunschweig, Postfach 3329, 38023 Braunschweig, Germany, and SAI,
UniVersidad de Murcia, E-30071 Murcia, Spain
ReceiVed September 12, 2007
[AuCl(SMe2)] reacts with HCtCR (R ) bpyl ) 2,2′-bipyridine-5-yl (1), phtpyl ) phenyl-4-(2,2′:
6′,2′′-terpyridine-4-yl) (2)) and NEt3 (1:1:3) to afford the polymers [Au(CtCR)]n (R ) bpyl (3), phtpyl
(4)). The new alkyne HCtCphccbpyl (5, phccbpyl ) 4-C6H4CtCbpyl) has been prepared by Sonogashira
coupling of 4-Me3SiCtCC6H4I and
1 followed by desilylation of the resulting alkyne
4-Me3SiCtCphccbpyl. The alkynyl Au(I) complexes [Au(CtCR)L] (R ) bpyl, L ) PPh3 (6), PTol3 (7,
Tol ) 4-MeC6H4), PEt3 (8); R ) phtpyl, L ) XyNC (9), PPh3 (10); R ) phccbpyl, L ) PPh3 (11)) have
been prepared by reacting: (1) 3 or 4 with L or (2) the corresponding alkyne 1, 2, or 5 with [Au(acac)(PPh3)]
(acac ) acetylacetonato). The reaction of 3 or 4 with diphosphines gives [{Au(CtCR)}2(µ-
Ph2P(CH2)xPPh2)] (R ) bpyl, x ) 1 (12), 2 (13), 4 (14), 10 (15); R ) phtpyl, x ) 10 (16)). ESI mass
spectrometric studies show that complexes 12–14 are in equilibrium with the salts [Au3(CtCbpyl)2(µ-
Ph2P(CH2)xPPh2)2][Au(CtCbpyl)2], although only when x ) 1 (17) was a significant concentration of
the salt detected by NMR spectroscopy and isolated. The anionic complexes PPN[Au(CtCR)2] (R )
bpyl (18), phtpyl (19), or phccbpyl (20)) have been prepared by reaction of the corresponding alkynes
with PPN[Au(acac)2]. Complexes 6, 10, 13, 14, 17, and 18 have been characterized by single-crystal
X-ray diffraction studies. The alkynyl complexes are luminescent at room temperature, displaying dual
emissions.
sensors or optical devices and is strongly influenced by the
presence of aurophilic interactions.10 Several examples of
luminescent chemosensors containing Au(I)-alkynyl units have
been described.11,12 In these systems, the alkynyl ligands contain
a crown ether, a calixarene, or a calix crown host, which
interacts with metal ions, giving rise to a detectable perturbation
of the luminescence of the Au-alkynyl unit.
Introduction
Au(I) alkynyl complexes1–4 have generated much interest
associated with their use in the synthesis of organometallic rigid
oligomers, polymers,3,5,6 molecular triangles,7 macrocycles, and
catenanes.8,9 Another interesting feature of these complexes is
their luminescence, which can be employed for the design of
Ethynyl-substituted oligopyridines or -phenanthrolines have
been used as conjugated linking units in the synthesis of
polynuclear complexes, some of which display interesting
photophysical or electrochemical properties.13,14 Metalaligands
containing [Au]CtCRL (RL ) 1,10-phenanthroline-x-yl (x )
* Corresponding author. Tel and fax: 34 968 364143. E-mail: jvs1@
um.es (J.V.), jgr@um.es (J.G.-R.). Web address: http://www.um.es/gqo/.
# Grupo de Química Organometálica, Universidad de Murcia.
† Technische Universität Braunschweig.
‡ SAI, Universidad de Murcia.
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10.1021/om7009123 CCC: $40.75
2008 American Chemical Society
Publication on Web 02/05/2008

Luminescent Alkynyl Gold Metalaligands
Organometallics, Vol. 27, No. 4, 2008 647
Chart 1
Scheme 1
3,15 516), pyridine-x-yl (x ) 2, 4)17–19), or [Au2]{µ-(CtC)2RL
(RL ) pyridine-3,5-diyl)13 units have been recently reported,
as have several heteronuclear complexes where the RL group
2+ 20
is coordinated to Ru(bpy)2
,
ReCl(CO)3,16,21 Re(CO)3-
(bpy)+,18 Au(PTol3)+, or PtCl(PPh3)2
.
The photophysical
+ 13
properties of some of these complexes have been studied in
detail.15,16,18–21
high yield as yellow solids (Schemes 1 and 2). The low
solubility of 3 and 4 precluded their characterization by NMR
in solution and the preparation of single crystals for an X-ray
structural determination. The structural analysis by ab initio
XRPD, which has recently proved successful in the determi-
nation of the structures of group 11 metal acetylides,22 was not
possible because of the amorphous character of 3 and 4. In their
IR spectra, the ν(tC-H) bands of the starting alkynes are
absent and the ν(CtC) mode appears as weak bands at 2106
and 2112 cm-1, respectively, which fall into the usual range
for terminal σ-coordinated alkynyls. ν(CtC) bands at a lower
frequency, which could indicate a π-coordination of the CtC
bond,22–24 were not observed. On the basis of these data, oligo-
or polymeric structures based on AuCtCbpy or AuCtCphtpyl
units linked by Au-N bonds can be tentatively proposed for 3
and 4, respectively. The insolubility of this type of complexes
prevents recrystallization and, in some cases, prevents obtaining
good analytical data.4,13 However, elemental analyses (C, H,
N, and Cl for 4) suggest the formulation of the present
complexes as 3 · (H2O)0.5 and 4 · H2O · (HCl)0.4. Both species,
HCl and H2O, can be trapped by the N atoms not involved in
Au-N bonds.
Herein we report the synthesis and characterization of a family
of metalaligands [Au]CtCbpyl, [Au]CtCphtpyl, or [Au]Ct
Cphccbpyl (see Chart 1). Owing to their strong coordination
ability and luminescence, these compounds are potential can-
didates for use as chemosensors. In addition, they can be used
as building blocks for the synthesis of new heterometallic
oligomers and polymers by reaction with metal ions.
Results and Discussion
Synthesis of Complexes. The reaction between HCtCR (R
) bpyl (1), phtpyl (2)) (see Chart 1) and [AuCl(SMe2)] affords
the corresponding [Au(CtCR)]n (R ) bpyl (3), phtpyl (4)) in
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O.; Echegoyen, L.; Newkome, G. R. Chem. Commun. 2005, 713. Tzalis,
D.; Tor, Y. J. Am. Chem. Soc. 1997, 119, 852. Pautzsch, T.; Klemm, E.
Macromolecules 2002, 35, 1569. Harriman, A.; Hissler, M.; Ziessel, R.;
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M.; Kalsani, V.; Bats, J. W. Inorg. Chem. 2005, 44, 4115. Khan, M. S.;
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R. H.; Kohler, A.; Feeder, N.; Teat, S. J. J. Chem. Soc., Dalton Trans.
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2004, 33, 210.
The new alkyne HCtCphccbpyl (5, phccbpyl ) C6H4Ct
Cbpyl) was prepared by palladium-catalyzed coupling of
Me3SiCtCC6H4I-4 and 1, followed by desilylation of the
resulting alkyne Me3SiCtCphccbpyl. The mononuclear com-
plexes [Au(CtCR)L] (R ) bpyl, L ) PR′3, R′ ) Ph (6), tol
(7, tol ) 4-MeC6H4), Et (8); R ) phtpyl, L ) XyNC (9, Xy )
2,6-dimethylphenyl); Schemes 1 and 2) were prepared in good
yields by reacting 3 or 4 with the corresponding neutral ligand.
Alternatively, complexes 6 and [Au(CtCR)(PPh3)] (R ) phtpyl
(10), phccbpyl (11), Schemes 2 and 3) were obtained by the
(16) Pometschenko, I. E.; Polyansky, D. E.; Castellano, F. E. Inorg.
Chem. 2005, 44, 3412.
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S.; Boutton, C.; Persoons, A.; Heath, G. A.; Hockless, D. C. R.;
LutherDavies, B.; Samoc, M. J. Chem. Soc., Dalton Trans. 1997, 4167.
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P.; Martín, A. J. Organomet. Chem. 2005, 690, 2200.
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2004, 689, 4451.
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1739.
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M. F.; Solans, X. J. Organomet. Chem. 2003, 678, 82.
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R. J. Organometallics 2000, 19, 5063.
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Onaka, S. Chem. Commun. 2002, 590.
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Puddephatt, R. J. Chem.-Eur. J. 2002, 8, 723. MacDonald, M. A.;
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2004, 689, 2905.

648 Organometallics, Vol. 27, No. 4, 2008
Vicente et al.
Scheme 2
Figure 1. Molecular structure of 6 (50% thermal ellipsoids).
Scheme 3
“acac method”,2,25 i.e., by reacting the alkynes 1, 2, and 5 with
[Au(acac)(PPh3)]. Complexes 6–10 were characterized by
analytical and spectroscopical means and, in the case of 6 and
10, by X-ray diffraction studies (Figures 1 and 2).
The dinuclear complexes [{Au(CtCbpyl)}2(µ-Ph2P(CH2)x-
PPh2)] (x ) 1 (12), 2 (13), 4 (14), 10 (15)) (Scheme 1) were
obtained in good yields by reacting 3 with the corresponding
diphosphines. Similarly, [{Au(CtCphtpyl)}2(µ-Ph2P(CH2)10-
PPh2)] (16) was obtained by reacting 4 with Ph2P(CH2)10PPh2.
Their analytical, IR, and NMR spectroscopical data in CDCl3
solution are in agreement with the proposed structures, which
were confirmed for 13 and 14 by single-crystal X-ray diffraction
studies (Figures 3 and 4). However, in complex 12 a solvent
dependence of the NMR spectra was observed. Thus, its 31P{1H}
NMR spectrum in CDCl3 at room temperature shows the
expected singlet at 32.1 ppm (Figure 5), but in (CD3)2CO at 20
°C, two different sets of signals appear: a singlet at 32.7 ppm,
corresponding to 12, and two broad multiplets due to a new
species 17 (Figure 5). These multiplets become sharper on
lowering the temperature to 0 °C or by measuring the spectrum
in a higher field NMR spectrometer. This part of the spectrum
can be reproduced by computer simulation assuming an AA′XX′
spin system (see Supporting Information). On raising the
Figure 2. (Top) Molecular structure of 10 (50% thermal ellipsoids).
(Bottom) Clustering of C-H · · · Au (thin dashed bonds) and
C-H · · · π contacts (thick dashed bonds) at the P-Au-CtC center
of compound 10. For symmetry operators, see Supporting
Information.
temperature (60 °C), all signals coalesce into a unique, broad
signal. In addition, the room-temperature 1H NMR spectrum in
CDCl3 shows the signal of the PCH2P protons as a triplet by
coupling with two equivalent P nuclei, as expected for 12.
However, in (CD3)2CO, at 20 °C, a broad signal is observed,
which at T < –40 °C splits into two multiplets from 17 and a
(25) Vicente, J.; Chicote, M. T. Coord. Chem. ReV. 1999, 195, 1143.
Vicente, J.; Chicote, M. T.; Saura-Llamas, I. J. Chem. Soc., Dalton Trans.
1990, 1941.

Luminescent Alkynyl Gold Metalaligands
Organometallics, Vol. 27, No. 4, 2008 649
Figure 3. (Top) Molecular structure of 13 (50% thermal ellipsoids).
(Bottom) C-H · · · Au (thin dashed bonds), C-H · · · π, and Au · · · Au
contacts (thick dashed bonds) in compound 13. For symmetry
operators, see Supporting Information. Only interactions to the
parent molecule (thick continuous bonds) are shown; other mol-
ecules are generated by the 21 screw axis.
Figure 5. 31P{1H} NMR spectra (162.3 MHz) of complexes 12
and 17. Solvent/temperature (°C): CDCl3/25 (A); CD3COCD3/60
(B); CD3COCD3/20 (C); CD3COCD3/0 (D).
Figure 4. (Top) Structure of 14 (30% thermal ellipsoids). (Bottom)
View of the chain structure showing the Au · · · Au interactions, the
H atoms have been omitted, and only the ipso carbons of the Ph
groups are shown.
Figure 6. (Top) Structure of the cation of 17 (50% thermal ellipsoids
for Au and P; the C and N atoms were isotropically refined). (Bottom)
View of the relative disposition of cations and anions.
triplet from 12. A similar behavior was observed in CD3CN,
DMF, or a CD3OD/CDCl3 mixture. It can be concluded from
the NMR data that, in polar solvents, complex 12 is in
equilibrium with 17. Slow evaporation of a solution of 12 in
acetone gave single crystals suitable for an X-ray diffraction
study. However, the crystals consisted not of 12 but instead of
the complex [Au3(CtCbpyl)2(µ-dppm)2][Au(CtCbpyl)2] (dppm
) 1,2-bis(diphenylphosphino)methane; Figure 6), whose ex-
pected NMR spectra agree with those of the new species 17
found in polar solvent solutions of 12 (Scheme 4). The 13C NMR
spectrum measured in (CD3)2CO shows the expected signals
for a mixture of 12 and 17 (see Experimental Section).
The presence of the salt 17 in solution was also confirmed
by ESI MS spectroscopy, which showed the expected peaks
for the [Au3(CtCbpyl)2(µ-dppm)2]+ cation and the [Au(Ct
Cbpyl)2]- anion in positive and negative mode, respectively.
The ESI MS spectra of complexes 13 and 14 also show the
peaks corresponding to the ions [Au3(CtCbpyl)2{µ-Ph2P-
(CH2)nPPh2}2]+ (n ) 2 or 4) and [Au(CtCbpyl)2]-, in spite
of the fact that their NMR spectra showed at room temperature
only the singlet corresponding to the neutral dinuclear complexes
in CDCl3, Me2CO, or Me2CO/CDCl3 with no significant

650 Organometallics, Vol. 27, No. 4, 2008
Vicente et al.
Scheme 4
Scheme 5
chemical shift variation. This suggests that 13 and 14 are ionized
under the ESI-MS measurement conditions, but the concentra-
tion of the salt is too small to be detected by NMR spectroscopy.
The NMR spectra of 15 did not show signals for new species
when they were recorded in CD3CN instead of CDCl3 at room
temperature, and in its ESI-MS spectra the anion
[Au(CtCbpyl)2]- was detected, but the only cationic species
observed were [Au2(CtCbpyl){Ph2P(CH2)10PPh2}]+ and
[Au{Ph2P(CH2)10PPh2}2]+.
Scheme 6
In view of these results, we propose that an equilibrium
between 12 and 17 is established in solution (Scheme 4).
Complex 12 is the main species in CDCl3, but in more polar
solvents, the ionization process is favored, giving a mixture
where the main component is 17 (17:12 ) 1.3 in (CD3)2CO at
20 °C). When an acetone solution containing 12 and 17 was
evaporated to dryness and the solid residue was redissolved in
CDCl3, the main component turned out to be 12, showing that
the process is reversible. A similar ionization process could also
take place for 13 and 14, as shown by their ESI-MS spectra;
however, the amounts of ionic species formed in solution must
be very small because they are not observed by NMR. For
complex 15, the cationic trinuclear species was not detected by
ESI-MS. This suggest that dppm could stabilize the trinuclear
cation better than 1,2-bis(diphenylphosphino)ethane (dppe) and
1,4-bis(diphenylphosphino)butane (dppb), and it will not be
stable with 1,10-bis(diphenylphosphino)decane (dppd).
presence of a base has also been reported.27 The structural
characterization of these complexes was based on a single-
crystal X-ray study and ESI-MS measurements that showed the
expected masses for the cations and anions. However, their
1
reported H NMR spectra (CDCl3, 298 K) suggest a dynamic
behavior in solution similar to that between complexes 12 and
17, because in all cases except one, single sets of resonances
for the R and R′ groups and a triplet for the PCH2P protons
were observed. Finally, very few [{Au(CtCR)}2(µ-dppm)]
complexes have been described.28
The PPN[Au(CtCR)2] salts (R ) bpyl (18), phtpyl (19), and
phccbpyl (20)) were prepared by reaction of the alkyne 1, 2, or
5 with PPN[Au(acac)2] (Scheme 6).29 They were characterized
by spectroscopical and analytical means and also by an X-ray
diffraction analysis of 18 (Figure 8).
Crystallographic Studies. The structures of the complexes
6, 10, 13, 14, 17, and 18 have been determined by single-crystal
X-ray diffraction (Figures 1–4, 6, and 7). The structure of 14
involves two independent molecules, each with the gold atom
on an inversion center. In 17, there are two independent anions,
each with the gold atom on an inversion center. In 18, the gold
atom lies on a 2-fold axis. The Au-C and CtC distances and
X-Au-C and Au-CtC angles (Table 1) are in the usual
ranges for Au(I) alkynyl complexes.30
The interconversion between 12 and 17 could take place
(Scheme 5) by substitution of one of the phosphine donor groups
of 12 by a solvent molecule, followed by the transfer of an
alkynyl group from 12 to the intermediate B. The resulting ionic
species C would react with the [Au(CtCbpyl)(κ1-dppm)] (A)
intermediate to generate the trinuclear cation of the salt D,
which, by closing of the Au3 ring, would finally give the salt
17. According to this mechanism, the formation of 17 is favored
in donor solvents.
Some salts with structures similar to 17 have been previously
described. Thus, the reaction of [Au(CtCPh)]n with dppm has
been reported to give [Au3(CtCPh)2(µ-dppm)2][Au(CtCPh)2],
which was characterized by a single-crystal X-ray diffraction
study, but its structure in solution was not reported.26 The
isolation of a series of complexes of composition [Au3(Ct
CR′)2(µR2PCH2PR2)2][Au(CtCR′)2] by reaction of [Au2Cl2(µ-
R2PCH2PR2)] (R ) Ph, Tol, Cy, Me) with 1-alkynes in the
Au · · · Au Contacts. The crystal structures of 6, 10, and 18
do not show Au · · · Au contacts. Complex 13 forms infinite
(27) Yam, V. W. W.; Cheung, K. L.; Yip, S. K.; Cheung, K. K. J.
Organomet. Chem. 2003, 681, 196.
(28) Payne, N. C.; Ramachandran, R.; Puddephatt, R. J. Can. J. Chem.
1995, 73, 6. Bruce, M. I.; Hall, B. C.; Skelton, B. W.; Smith, M. E.; White,
A. H. J. Chem. Soc., Dalton Trans. 2002, 995.
(29) Vicente, J.; Chicote, M. T.; Abrisqueta, M. D.; Álvarez-Falcón,
M. M. J. Organomet. Chem. 2002, 663, 40.
(26) Che, C. M.; Yip, H. K.; Lo, W. C.; Peng, S. M. Polyhedron 1994,
13, 887.
(30) Cambridge Crystallographic Database 2006.

Luminescent Alkynyl Gold Metalaligands
Organometallics, Vol. 27, No. 4, 2008 651
Figure 8. Neighboring anions (top) and cations (bottom) in the
structure of compound 18. Weak interactions (see text) are indicated
by dashed lines.
Figure 7. (Top) C-H · · · (CtC) interactions within the cation of
compound 15. (Bottom) Clustering of five C-H · · · π (thick dashed
bonds) and two C-H · · · Au contacts (thin dashed bonds) between
the cation and one anion of 15. For symmetry operators, see
Supporting Information.
In complex 17, the structure of the cation [Au3(CtCbpyl)2(µ-
dppm)2]+ can be formally viewed as two AuCtCbpyl units
linked to an Au+ cation by two dppm ligands (Figure 6). The
alkynyl groups point to opposite sides of the Au3 plane.
Remarkably, in the Au3 triangle, the Au · · · Au distances between
Au atoms linked by a dppm ligand are longer (3.1938(3) and
3.3298(3) Å) than the other Au-Au distance (3.0217(3) Å).
Weak Hydrogen Bonds. Short C-H · · · Au4,6,7,9,37–39 and
C-H · · · π(CtCAu)38,40,41 contacts have been found in the
determined structures except for compound 6, where no H · · · Au
chains that are arranged in a parallel fashion (Figure 3) through
intermolecular short aurophilic contacts (3.0214(3) Å) via the
21 axis. The chains have a helical twist as a result of the
conformationoftheAu-P-C-C-P-Auunit(theAu-P · · · P-Au
dihedral angle is 70.6°). In contrast, in [Au2(CtC-Ph)2(µ-
dppe)]31 and [Au2Cl2(µ-dppe)],32 two molecules interact with
each other to form an isolated dimer.
One independent molecule of 14 is shown in Figure 4. The
PC4P chain is in a fully elongated form and the AuCtCbpyl
units are perpendicular to the P · · · P vector (90°, 88° in the two
molecules) in an anti configuration. Each molecule is linked to
two neighboring molecules by weak Au · · · Au interactions10,33
(3.6355(5) Å) to form infinite chains, which lie with Au · · · Au
vectors very approximately parallel (27°). A similar arrangement
has been found in [Au2X2(µ-dppb)] complexes (X ) I,34 SPh,35
STol,36), where the molecules are linked by short aurophilic
contacts.
(35) Onaka, S.; Yaguchi, M.; Yamauchi, R.; Ozeki, T.; Ito, M.; Sunahara,
T.; Sugiura, Y.; Shiotsuka, M.; Nunokawa, K.; Horibe, M.; Okazaki, K.;
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2005, 690, 57.
(36) 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.
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Organometallics 2005, 24, 2411. Bardají, M.; Jones, P. G.; Laguna, A. J.
Chem. Soc., Dalton Trans. 2002, 3624. Vicente, J.; Singhal, A. R.; Jones,
P. G. Organometallics 2002, 21, 5887. Wong, W. Y.; Choi, K. H.; Lu,
G. L.; Shi, J. X.; Lai, P. Y.; Chan, S. M.; Lin, Z. Y. Organometallics 2001,
20, 5446. Barranco, E. M.; Crespo, O. M.; Gimeno, C.; Laguna, A.; Jones,
P. G.; Ahrens, B. Inorg. Chem. 2000, 39, 680.
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Soc., Dalton Trans. 1993, 2929.
(32) Bates, P. A.; Waters, J. M. Inorg. Chim. Acta 1985, 98, 125.
Egglestone, D. S.; Chodosh, D. F.; Girard, G. R.; Hill, D. T. Inorg. Chim.
Acta 1985, 108, 221.
(38) Vicente, J.; Chicote, M. T.; Abrisqueta, M. D.; Álvarez-Falcón,
M. M.; Ramirez de Arellano, M. C.; Jones, P. G. Organometallics 2003,
22, 4327.
(33) Hunks, W. J.; Jennings, M. C.; Puddephatt, R. J. Inorg. Chem. 2000,
39, 2699. Gussenhoven, E. M.; Fettinger, J. C.; Pham, D. M.; Malwitz,
M. M.; Balch, A. L. J. Am. Chem. Soc. 2005, 127, 10838. Bachman, R. E.;
Bodolosky-Betis, S. A.; Glennon, S. C.; Sirchio, S. A. J. Am. Chem. Soc.
2000, 122, 7146. Schneider, W.; Bauer, A.; Schmidbaur, H. J. Chem. Soc.,
Dalton Trans. 1997, 415.
(39) Vicente, J.; Chicote, M. T.; Álvarez-Falcón, M. M.; Jones, P. G.
Organometallics 2005, 24, 5956.
(40) Lu, W.; Zhu, N. Y.; Che, C. M. J. Am. Chem. Soc. 2003, 125,
16081. Che, C. M.; Chao, H. Y.; Miskowski, V. M.; Li, Y. Q.; Cheung,
K. K. J. Am. Chem. Soc. 2001, 123, 4985.
(41) Müller, T. E.; Mingos, D. M. P.; Williams, D. J. J. Chem. Soc.,
Chem. Commun. 1994, 1787. Alder, M. J.; Flower, K. R.; Pritchard, R. G.
J. Organomet. Chem. 2001, 629, 153.
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1997, 36, 5231.

652 Organometallics, Vol. 27, No. 4, 2008
Vicente et al.
Table 1. Bond Distances and Angles for Complexes 6, 10, 13, 14, 17, and 18
bond distances (Å)
Au-C
bond angles (deg)
complex
Au-P
CtC
Au-Au
X-Au-Y
Au-CtC
6
10
13
2.2724(9)
2.2729(5)
2.2737(12)
2.2812(13)
2.2719(18)
2.273(2)
2.004(3)
1.9995(19)
2.024(5)
2.024(5)
2.027(8)
2.036(10)
2.002(5)b
2.006(5)b
1.988(6)c
1.996(7)c
1.976(4)
1.201(5)
1.199(3)
1.192(7)
1.179(8)
1.145(9)
1.074(11)
1.214(7)b
1.199(7)b
1.209(8)c
1.199(9)c
1.209(6)
172.38(10)f
176.23(6)f
172.22(16)f
172.26(16)f
172.0(2)f
168.1(3)
176.39(18)
169.7(5)
177.1(5)
166.8(8)
175.2(10)
173.5(5)b
175.6(5)b
177.2(5)c
177.2(5)c
177.5(4)
3.0214(3)d
3.6355(5)d
14
17
178.6(3)f
2.2964(13)a
2.3023(13)a
2.2864(13)
2.2866(13)
3.1938(3)
3.3298(3)
3.0217(3)e
170.93(16)f
171.28(16)f
172.37(5)h
180.0(2)g,i
179.6(2)g
18
a For the mutually trans P atoms. b For the cation. c For the anion. d Intermolecular. e Between the Au atoms bonded to bpylCtC. f P-Au-C.
g C-Au-C. h P-Au-P. i By symmetry.
distance shorter than 3.13 Å was observed. Although the
interpretation of these contacts as weak hydrogen bonds should
be made very cautiously,39 the packing features described below
suggest that these interactions could be structurally significant,
particularly when several interactions of the same or of different
type act cooperatively.
For the following discussion, it should be noted that the C-H
bond lengths have been normalized to 1.08 Å. Contacts with
angles less than 130° have generally been excluded unless they
form part of multicenter or multicontact systems (see individual
discussion). Tables with the hydrogen bond distances and angles
are given as Supporting Information.
In compound 6, two C–H · · · N and three C-H · · · π interac-
tions were observed, which involve different symmetry operators
in all cases (see Supporting Information). The result is a complex
three-dimensional packing without easily identifiable features.
In complex 10, at first sight there seems to be no clearly
recognizable packing feature; indeed, the eight C-H · · · π(CtC)
interactions observed are all quite long and narrow-angled (see
Supporting Information). However, a closer inspection reveals
that the interactions are coupled, each C-H · · · Au with one or
two C-H · · · π(CtC) from the same ring to the adjacent triple
bond and with the same operator (Figure 2). Although believing
that such contacts are structurally significant, we have cautiously
pointed out the ease of assembling contacts at a linear and thus
sterically accessible gold(I) center.4,42 Nevertheless, the large
number of contacts in 10 remains impressive.
The molecules of 10 are assembled such that the terpyridyl
groups of neighboring molecules are approximately parallel.
There are recognizable π-stacking interactions from the ring
(N1,C21-C25) to itself at -x, 2-y, 2-z (rings exactly parallel,
intercentroid distance 3.73 Å, perpendicular distance 3.44 Å,
offset 1.4 Å) and to the ring (N2,C31-C35) at –1-x, 2-y, 2-z
(interplanar angle 9°, distances 3.78, 3.24, ca. 1.9 Å).
The structure of compound 13 shows again a wide variety
of contacts, many of which are rather long (see Supporting
Information). Closer inspection shows that about half of these,
from hydrogens of the diphenylphosphino groups, involve the
21 screw axis that also generates the Au · · · Au interactions
(Figure 3). These interactions may thus be regarded as acting
cooperatively.
There are three striking features of the packing in the structure
of compound 15:
(i) Some of the contacts are extremely short (H · · · N 2.40,
H · · · Au 2.69, H · · · ring centroid 2.30, H · · · triple bond 2.40 Å;
more details are given in the Supporting Information). This may
be promoted, at least in part, by favorable electrostatic interac-
tions between oppositely charged ions (“charge assistance”).
(ii) Three of the four methylene protons of dppm are involved
in short contacts (see Supporting Information). We have already
pointed out the marked tendency of these atoms to act as H
bond donors.43 The contacts H2A · · · (C3tC4) and H1A · · · (C5t
C6) act within the cation (Figure 7) and may well help to
determine or at least stabilize the configuration.
(iii) The extended and exposed linear sections of the anions,
particularly the anion involving Au5, lead to a clustering of
contacts at those regions (Figure 7).
Stacking interactions may be assumed between rings C41–46
and C111–116 within the cation (interplanar angle 7.8°, inter-
centroid distance 3.71 Å) and C91–96 and C101–106 via the
operator 1-x, 1-y, 1-z (parallel, distance 3.67 Å).
Compound 18. The anions pack parallel to each other to
form ribbons parallel to the z axis (Figure 8). Some of the
“weak” interactions between the anions, especially those of the
C-H · · · N type, are much longer than most of those discussed
for the other structures (see Supporting Information), but in total
they may serve to determine the anion substructure. Both
independent C-H · · · N contacts are connected across inversion
centers to form rings of graph set R (6).
The structures of PPN[Au(CtCAr)2] (Ar ) C6H4X-4, X )
Me, NO2)39,44 also contain ribbons of anions, but linked by
Au · · · H contacts. In all cases the space group is C2/c, both
ions have 2-fold symmetry, and the cell contant c is ca. 15 Å.
Closer inspection shows that the cations form chains parallel
to the z axis (Figure 8), with two cations per axis translation,
in which neighboring ions are connected by two C-H · · · π
contacts (symmetry-related) from meta hydrogens. It may well
be that the large cations determine the packing to a great extent.
The anion and cation substructures are then linked by other weak
interactions (see Supporting Information).
Photophysical Studies. Absorption Spectra. The absorption
spectra of complexes containing the Au-CtCbpyl unit (6,
8–15, and 18) display two maxima at 316–324 and 329–332
nm (Table 2 and Figure 9). The spectra are very similar
throughout the series. In contrast, larger variations in the λmax
In compound 14 again there is a broad and heterogeneous
mixture of contacts (see Supporting Information), many of which
are borderline in terms of lengths and/or angles. In contrast to
13, there is also no concentration of contacts via any particular
operator; all four notably short contacts involve different
operators.
(43) Jones, P. G.; Ahrens, B. Chem. Commun. 1998, 2307.
(44) Vicente, J.; Chicote, M. T.; Abrisqueta, M. D.; de Arellano,
M. C. R.; Jones, P. G.; Humphrey, M. G.; Cifuentes, M. P.; Samoc, M.;
Luther-Davies, B. Organometallics 2000, 19, 2968.
(42) Friedrichs, S.; Jones, P. G. Z. Naturforsch. 2004, 59b, 1429.

Luminescent Alkynyl Gold Metalaligands
Organometallics, Vol. 27, No. 4, 2008 653
Table 2. UV–Visible Absorption and Emission Data for HCtCbpyl (1) and Its Au-Alkynyl Derivatives
absorptiona
emission
complex
λ
max/nm (10-4 ꢀ/dm3 mol-1 cm-1
)
medium (T/K)
λmax/nm (τ/µs)
1
6
258 (2.9), 300 (4.2)
316 (3.4), 330 (3.1)
CH2Cl2 (298)
CH2Cl2 (298)
solid (298)
CH2Cl2 (298)
solid (298)
355,b 374
391, 492,c 533c
392, 410,b 496, 536 (28, 184),d 557
390, 499, 532
8
316 (3.1), 329 (2.8)
396, 426, 497, 544 (16, 136),d 577b
525, 545, 572
solid (77)
n-PrCN (77)
CH2Cl2 (298)
MeCN (298)
solid (298)
CH2Cl2 (298)
solid (298)
n-PrCN (77)
CH2Cl2 (298)
solid (298)
CH2Cl2 (298)
solid (298)
490 (172), 520, 532
376, 398, 501, 533b
391, 500, 532b
12
13
318, (7.2), 332 (6.3)
316 (4.2), 330 (4.0)
418, 516,b 550, 592, 655
378, 397, 496,c 529d
393, 498, 541 (19, 158),d 557b
496 (194), 536
14
15
317 (5.9), 330 (5.5)
317 (10.5), 330 (9.7)
394, 492,c 527d
400, 420, 498, 539, 576b
393, 506, 546, 580b
402, 516,b 546, 578,b 650b
514, 538, 553,b 576b
497, 537, 554b
solid (77)
n-PrCN (77)
CH2Cl2 (298)
solid (298)
18
324 (4.1), 333b (3.9)
376, 390, 506, 539
400, 510 (76), 545
n-PrCN (77)
495 (244), 535
a Measured in CH2Cl2 solution at 298 K. b Shoulder. c Weak. d Double exponential decay.
Figure 9. Absorption spectra (CH2Cl2) of compounds 1, 6, 8, 13,
and 18.
Figure 10. Absorption spectra (CH2Cl2) of compounds 5, 11, and
20.
values of the lowest energy absorptions are observed on going
from the neutral 9-11 to the corresponding anionic complexes
19 and 20 (Table 2 and Figure 10). In all cases, the λmax values
are higher in the dialkynyl aurate(I) than in the neutral
complexes.
In accord with previously reported spectroscopic studies of
Au(I) alkynyl complexes,11,18,19,21,31,45,46 we tentatively propose
that the transitions involved are mostly of intraligand [πfπ*-
(CtCAr)] character with some participation of Au orbitals.
Hence, the red shift of the absorptions of 5, 11, and 20 with
respect to those of 1, 6, and 18, respectively, can be attributed
to the increase in π-electron delocalization on introducing a
CtCC6H4 group.
dual emissions, with higher energy maxima around 400 nm and
lower energy maxima around 500 nm or higher. When the
spectra are measured in deoxygenated CH2Cl2 at 298 K, the
higher energy emissions are more intense than those at lower
energy (Figure 11), except for complexes 8 and 19, where the
lower energy emissions are the most intense ones (Figure 12).
Measuring the spectra in nondeoxygenated CH2Cl2 solutions
gave rise to a significant decrease in the intensities of the lower
energy emissions. In the solid state at 298 K, the intensity of
both emissions is comparable, except for complexes 9–11 and
20, where no maxima at low energy appeared, but the higher
energy emission tailed up to 600 nm. At 77 K, in the solid state
n
or in glassy PrCN, the lower energy emissions are dominant
Emission Spectra. All complexes are emissive at room
temperature in solution, as well as in the solid state. They present
(Figures 12 and 13), except for complex 11. The low-energy
emission displays vibrational structure in most cases, but it was
not well resolved because of the broadness of the peaks, except
(45) Li, P.; Ahrens, B.; Choi, K. H.; Khan, M. S.; Raithby, P. R.; Wilson,
P. J.; Wong, W. Y. Cryst. Eng. Commun. 2002, 4, 405. Hong, X.; Cheung,
K. K.; Guo, C. X.; Che, C. M. J. Chem. Soc., Dalton Trans. 1994, 1867.
Yam, V. W. W.; Choi, S. W. K. J. Chem. Soc., Dalton Trans. 1996, 4227.
Lu, W.; Zhu, N. Y.; Che, C. M. J. Organomet. Chem. 2003, 670, 11. Li,
P.; Ahrens, B.; Feeder, N.; Raithby, P. R.; Teat, S. J.; Khan, M. S. Dalton
Trans. 2005, 874.
(46) Irwin, M. J.; Vittal, J. J.; Puddephatt, R. J. Organometallics 1997,
16, 3541. Wong, W. Y.; Liu, L.; Poon, S. Y.; Choi, K. H.; Cheah, K. W.;
Shi, J. X. Macromolecules 2004, 37, 4496.
n
for complexes 11 and 20, in glassy PrCN, at 77 K (Figure
13). The observed vibronic spacings in these conditions were
around 1100–1200, 1500–1600, 2100 and 2200 cm-1, which
can be assigned to aromatic ring and CtC vibrational modes.
The similarity of the emission spectra of different complexes
containing the same alkynyl ligand suggests that the involved
states are located mainly in the Au-alkynyl units. The difference

654 Organometallics, Vol. 27, No. 4, 2008
Vicente et al.
is known that, in [Au(CtCR)(PR3)] complexes, the AuPR3 unit
is able to efficiently enhance the emission from the triplet states
(phosphorescence) of the CtCR luminomophores.19,23,40,46,48
Therefore, we tentatively assign the emitting states to metal-
1
perturbed, alkynyl ligand based, IL [πfπ*] (higher energy
emission) and 3IL [πfπ*] (lower energy emission) states.
Lifetime measurements are in agreement with their respective
singlet and triplet character. Thus, the lifetime of the higher
energy emissions could not be accurately determined owing to
instrumental limitations, but we observed that the emissions
decayed completely after a few nanoseconds. In contrast, the τ
values of the lower energy emissions are in the microsecond
range (Tables 2–4). Finally, it should be noted that similar dual
emissions have been recently reported in the related complexes
[Au(CtCphenl)(PPh3)] (phenl ) 1,10-phenanthrolin-3-yl or
1,10-phenanthrolin-5-yl), [Au(CtCphenl)2]- (phenl ) 1,10-
phenanthrolin-3-yl), and [(PPh3)Au(CtCphenlCtC)Au(PPh3)]
(phenl ) 1,10-phenanthrolin-3,8-ylidene).15,16
Figure 11. Emission spectra (CH2Cl2, 298 K) of compounds 1, 6,
13, and 18.
Concluding Remarks. A series of Au(I) alkynyl complexes
containing the 2,2′-bipyridine-5-yl or 2,2′:6′,2′′-terpyridine-4-
yl groups have been prepared and structurally characterized.
An exchange process between the dinuclear complex [Au2(Ct
Cbpyl)2(µ-dppm)] (12) and the salt [Au3(CtCbpyl)2(µ-
dppm)2][Au(CtCbpyl)2] (17) has been observed in solution.
The salt is the main component in solutions of highly polar
solvents, while the dinuclear complex is virtually the only
species present in CDCl3. The crystal structures of the complexes
[Au2(CtCbpyl)2(µ-PPh2(CH2)xPPh2)] (x ) 2 (13) and 4 (14))
display Au · · · Au interactions that give rise to the formation of
chains. All prepared complexes are luminescent at room
temperature and display dual emissions that are assigned to
metal-perturbed alkynyl ligand based transitions. These com-
pounds are potential candidates for use as chemosensors or, by
reaction with metal ions, as building blocks for the synthesis
of new heterometallic oligomers and polymers. Studies of their
Figure 12. Emission spectra of 19.
reactivity toward transition metal cations, in particular with Fe2+
,
are in progress and will be reported in due course.
Experimental Section
GeneralConsiderations. ThepreparationofcompoundsIC6H4Ct
CSiMe3-4,49 1, 2,50 PPN[Au(acac)2] (PPN+ ) (Ph3PdNdPPh3)+),
[Au(acac)(PR3)]51 (R ) Ph, Tol), and [AuCl(SMe2)]52 was carried
out as previously described. Other reagents were obtained from
commercial sourcessCNXy (Fluka), Ph2P(CH2)nPPh2, n ) 1
(dppm, Fluka), 2 (dppe, Aldrich), and 4 (dppb, Fluka)sand used
without further purification. All manipulations were carried out
under an air atmosphere and at room temperature unless otherwise
stated. Tetrahydrofuran, toluene, and Et2O were distilled over
sodium-benzophenone; CH2Cl2 was distilled over CaH2 and bubbled
before use with N2 to remove traces of HCl.
Infrared spectra were recorded in the range 4000-200 cm-1
on a Perkin-Elmer 16F PC FT-IR spectrometer with Nujol mulls
between polyethylene sheets. C, H, N, and S analyses were
carried out with Carlo Erba 1108 and LECO CHS-932 microana-
lyzers. NMR spectra were measured on Bruker Avance 200, 300,
400, and 600 instruments. 1H chemical shifts were referenced
to residual CHCl3 (7.26 ppm) or CHD2COCD3 (2.05 ppm).
Figure 13. Emission spectra of 20.
in the Stokes shifts of both emissions, the quenching of the lower
energy emissions by oxygen, and its decrease in solution at room
temperature suggest that both emissions are different in char-
acter. Studies of the photophysics of 5-ethynyl-2,2′-bipyridines
have shown that they display strong fluorescence at 345–414
nm and very weak phosphorescence at 505–550 nm.47 In our
case, the positions of the high-energy emissions are close to
the emission maxima of the free alkynes 1, 2, and 5 (374, 362,
and 379 nm, respectively, in CH2Cl2, at 298 K). In addition, it
(48) Chao, H. Y.; Lu, W.; Li, Y. Q.; Chan, M. C. W.; Che, C. M.;
Cheung, K. K.; Zhu, N. Y. J. Am. Chem. Soc. 2002, 124, 14696. Lu, W.;
Xiang, H. F.; Zhu, N. Y.; Che, C. M. Organometallics 2002, 21, 2343.
(49) Hsung, R. P.; Chidsey, C. E. D.; Sita, L. R. Organometallics 1995,
14, 4808.
(50) Grosshenny, V.; Romero, F. M.; Ziessel, R. J. Org. Chem. 1997,
62, 1491.
(51) Vicente, J.; Chicote, M. T. Inorg. Synth. 1998, 32, 172.
(52) Tamaki, A.; Kochi, J. K. J. Organomet. Chem. 1974, 64, 411.
(47) Birckner, E.; Grummt, U.-W.; Göller, A. H.; Pautzsch, T.; Egbe,
D. A. M.; Al-Higari, M.; Klemm, E. J. Phys. Chem. A 2001, 105, 10307.

Luminescent Alkynyl Gold Metalaligands
Organometallics, Vol. 27, No. 4, 2008 655
Table 3. UV–Visible Absorption and Emission Data for HCtCphtpyl (2) and Its Au-Alkynyl Derivatives
absorptiona
max/nm (10-4 ꢀ/dm3 mol-1 cm-1
256 (2.3), 284 (3.7), 315b (0.8)
emission
complex
λ
)
medium (T/K)
λmax/nm (τ/µs)
2
CH2Cl2 (298)
362
409, 440b
9
233 (5.4), 250 (5.3), 266 (3.8), 289b (4.9), 306b (5.8), 320 (6.3)
CH2Cl2 (298)
solid (298)
n-PrCN (77)
CH2Cl2 (298)
solid (298)
418, 489,c 523d
403, 447, 491,b 523b
370,c 486 (449), 520
378, 492,c 524d
10
235 (8.2), 304b (6.9), 314 (7.2)
392, 444
n-PrCN (77)
CH2Cl2 (298)
solid (298)
CH2Cl2 (298)
solid (298)
362, 427, 485 (875), 518
16
19
233 (10.4), 305b (8.7), 315 (9.0)
391, 504,c 533c
399, 509 (11, 93),d 537
403, 506, 537
232 (11.9), 276 (6.3), 287 (6.5), 342 (9.1)
403, 509, 541 (8.9, 94)d
399,c 496 (519), 530
n-PrCN (77)
a Measured in CH2Cl2 solution at 298 K. b Shoulder. c Weak. d Double exponential decay.
Table 4. UV–Visible Absorption and Emission Data for HCtC-C6H4-CtCbpyl (5) and Its Au-Alkynyl Derivatives
absorptiona
emission
complex
λ
max/nm (10-4 ꢀ/dm3 mol-1 cm-1
)
medium (T/K)
λmax/nm (τ/µs)
5
11
324 (2.1), 345 (1.6)
CH2Cl2 (298)
CH2Cl2 (298)
Solid (298)
n-PrCN (77)
CH2Cl2 (298)
solid (298)
379, 393b
400
320b (2.5), 339 (3.2), 359 (2.7)
417, 430
400, 535 (1099), 569,c 584,c 606c
20
356 (4.6), 371 (4.8)
427, 541,c 577b,c
430
n-PrCN (77)
389, 535, 571, 584, 606,c 627,c 649,b,c669b,c
a Measured in CH2Cl2 solution at 298 K. b Shoulder. c Weak.
Table 5. Crystal Data for 6, 10, 13, 14, 17, and 18.
6
10
13 · 2C2H4Cl2
14 · ½C4H10O
17
18
formula
cryst size (mm3)
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
ꢀ (deg)
γ (deg)
V (Å3)
C30H22AuN2P
C41H29AuN3P
C54H46Au2Cl4N4P2 C54H47Au2N4O0.5P2 C98H72Au4N8P4 C60H44AuN5P2
0.19 × 0.12 × 0.12 0.28 × 0.21 × 0.15 0.28 × 0.17 × 0.07 0.30 × 0.12 × 0.04 0.35 × 0.1 × 0.1 0.25 × 0.15 × 0.05
triclinic
triclinic
monoclinic
P21/c
triclinic
P1
triclinic
P1
monoclinic
C2/c
j
j
j
j
P1
P1
10.0469(4)
10.6781(4)
13.1309(5)
76.667(2)
68.524(2)
68.910(2)
1215.14(8)
2
8.6401(4)
9.4232(4)
19.5947(8)
85.165(2)
86.406(2)
85.237(2)
1581.69(12)
2
15.8653(11)
14.3420(8)
22.9292(14)
90
104.006(4)
90
13.5520(14)
14.0520(16)
15.1890(16)
69.737(5)
66.133(5)
66.901(5)
13.0631(16)
15.8893(8)
20.2091(8)
104.761(4)
93.429(4)
90.574(4)
4047.6(3)
2
25.492(3)
12.3916(12)
15.1409(15)
90
103.802(2)
90
5062.2(5)
4
2371.8(4)
2
4644.7(8)
4
Z
λ (Å)
0.71073
1.745
620
0.71073
1.662
780
0.71073
1.770
2616
0.71073
1.702
1182
0.71073
1.865
2184
0.71073
1.564
2192
F(calc) (Mg m-3
F(000)
)
T (K)
100(2)
6.141
100(2)
4.737
173(2)
6.105
133(2)
6.288
0.23–0.77
1.50–26.37
-16 e h e 16
-17 e k e 17
-18 e l e 18
38 801
133(2)
7.361
100(2)
3.284
µ (mm-1
)
transmissions
θ range (deg)
index ranges
0.38–0.53
1.68–28.08
-13 e h e 13
-13 e k e 13
-17 e l e 17
14 233
0.35–0.54
2.09–26.37
-10 e h e 10
-11 e k e 11
-24 e l e 24
17 430
0.40–0.67
1.32–30.04
-22 e h e 22
-20 e k e 20
-32 e l e 32
95 857
0.40–0.67
1.33–30.51
-18 e h e 18
-22 ′ k e 22
-28 e l e 28
92 816
0.49–0.85
1.65–26.37
-31 e h e 31
-15 e k e 15
-18 e l e 18
25 052
no. of reflns collected
no. of indep reflns
Rint
5450
0.0237
6421
0.0139
14 798
0.0744
9665
0.0776
24 553
0.0398
4752
0.0440
abs corr
refinement method
semiempirical from equivalents
face-indexing
semiempirical from equivalents
full-matrix least-squares on F2
no. of data/restraints/params 5450/24/307
6421/0/415
1.088
0.0147
0.0370
14798/127/595
1.034
0.0369
0.0961
9665/0/541
0.847
0.0478
0.0868
2.115 and –1.222
24553/196/500
1.037
0.0398
0.1004
4752/304/308
1.254
0.0372
GOF on F2
1.122
0.0255
0.0585
R1a
wR2b
0.0808
largest diff peak (e Å-3
)
1.329 and -0.685 0.672 and -0.462 1.704 and –1.216
2.624 and –1.466 1.462 and -1.236
a R1 ) ∑|Fo| - |Fc|/∑|Fo| for reflections with I > 2σ(I). b wR2 ) [∑[w(Fo - Fc ) ]/∑[w(Fo2)2]0.5 for all reflections; w-1 ) σ2(F2) + (aP)2 + bP,
2
2 2
where P ) (2Fc + Fo2)/3 and a and b are constants set by the program.
2
13C{1H} spectra were referenced to CDCl3 (77.1 ppm). 19F and
31P{1H} NMR spectra were referenced to external CFCl3 (0 ppm)
and H3PO4 (0 ppm). The temperature values in NMR experiments
were not corrected. Abbreviations used: v ) virtual; br ) broad;
) 2 (dppm) or y ) 3 (dppe). NMR simulations were performed
with the gNMR (version 5.0.5.0) program. Melting points were
determined on a Reichert apparatus in an air atmosphere.
UV–visible absorption spectra were recorded on a Unicam UV
500 spectrometer in 1 cm path length quartz cuvettes. Steady state
x
(x+y)
N ) JPC
+
J , where x ) 2 (C2, Ph) or 3 (C3, Ph) and y
PC

656 Organometallics, Vol. 27, No. 4, 2008
Vicente et al.
3
3
excitation and emission spectra were measured on a Jobin Yvon
Fluorolog 3-22 spectrofluorimeter with a 450 W xenon lamp,
double-grating monochromators, and a Hamamatsu R-928P pho-
tomultiplier. The solutions for luminescence measurements were
deoxygenated by bubbling N2 or by four freeze–pump–thaw cycles
and placed inside 1 cm path length quartz fluorescence cuvettes
(298 K) or quartz tubes (77 K) under an atmosphere of N2. Low-
temperature measurements were carried out in an optical Dewar
sample holder filled with liquid N2 or using an Oxford Instruments
OptistatDN cryostat and ITC503 temperature controller. The solid
samples were placed between quartz coverslips or, for low-
temperature measurements, were ground with added KBr and placed
into 5 mm quartz NMR tubes. Phosphorescence lifetimes were
measured using an incorporated Jobin Yvon FL-1040 phosphorim-
eter. The excitation source was a pulsed Xenon lamp, with a pulse
full-width half-maximum of 3 µs. Solutions for τ measurements
were rigorously degassed by no less than four freeze–pump–thaw
cycles. A (10% error is estimated for the given τ values.
(d, JHH ) 9.0 Hz, 1 H, H3′), 8.41 (d, JHH ) 8.2 Hz, 1 H, H3),
3 4 3
7.93 (dd, JHH ) 8.2 Hz, JHH ) 2.2 Hz, 1 H, H4), 7.82 (td, JHH
) 7.8 and JHH ) 1.8 Hz, 1H, H4′), 7.52–7.48 (m, 4 H, C6H4),
4
7.31 (ddd, 3JHH ) 7.5 and 4.8 Hz, 4JHH ) 1.2 Hz, 1 H, H5′), 3.20
(s, 1 H, tC-H). 13C{1H} NMR (50.3 MHz, CDCl3): δ 155.4 (C2′),
155.0 (C2), 151.6 (C6), 149.3 (C6′), 139.4 (C4), 137.0 (C4′), 132.2
(CH, C6H4), 131.6 (CH, C6H4), 124.0 (C5′), 123.0 (quaternary,
C6H4), 122.5 (quaternary, C6H4), 121.4 (C3′), 120.4 (C3), 120.0
(C5), 92.9 (bpylCtC), 88.3 (bpylCtC), 83.1 (CtCH), 79.2
(CtCH). HRMS (EI) exact mass: 280.1001 (M+), calcd for
C20H12N2 280.1000.
[Au(CtCbpyl)(PPh3)] (6). Method A. A suspension of 3 (196
mg, 0.52 mmol) in CH2Cl2 (30 mL) was treated with PPh3 (137
mg, 0.52 mmol) and stirred for 30 min. The resulting solution was
concentrated under vacuum to about 1 mL and treated with
n-pentane (20 mL) to give a colorless precipitate, which was filtered
off, washed with Et2O (3 × 5 mL), and dried under vacuum. Yield:
300 mg, 90%. Mp: 139–144 °C (dec). Anal. Calcd for
C30H22AuN2P: C, 56.43; H, 3.47; N, 4.39. Found: C, 56.17; H, 3.79;
Ph2P(CH2)10PPh2 (dppd). This was prepared by a literature
method.53 1H NMR (200.1 MHz, CDCl3): δ 7.47–7.30 (m, 20 H,
Ph), 2.40 (m, 4 H, CH2P), 1.54–1.22 (m, 16 H, CH2). 13C{1H}
N, 4.29. IR (Nujol, cm-1): ν(CtC) 2108. H NMR (300.1 MHz,
1
CDCl3): δ 8.80 (br s, 1 H, H6), 8.66 (d, 3JHH ) 4.5 Hz, 1 H, H6′),
1
3
3
NMR (50.3 MHz, CDCl3): δ 138.8 (d, JPC ) 14.2 Hz, C1, Ph),
8.37 (d, JHH ) 8.1 Hz, 1 H, H3′), 8.30 (d, JHH ) 8.1 Hz, 1 H,
2
H3), 7.89 (dd, 3JHH ) 8.4, 4JHH ) 2.1 Hz, 1 H, H4), 7.78 (td, 3JHH
132.7 (d, JPC ) 18.2 Hz, C2, Ph), 128.4 (s, C4, Ph), 128.3 (d,
3
3JPC ) 6.9 Hz, C3, Ph), 31.2 (d, JPC ) 12.8 Hz, PCH2CH2CH2),
4
) 8.1 Hz, JHH 1.8 Hz, 1 H, H4′), 7.60–7.43 (m, 15 H, Ph), 7.26
29.4 (s, CH2), 29.2 (s, CH2), 28.0 (d, 1JPC ) 10.6 Hz, PCH2), 25.9
(d, 2JPC ) 15.8 Hz, PCH2CH2). 31P{1H} NMR (81.0 MHz, C6D6):
δ -15.5 (s). HRMS (FAB) exact mass: 511.2684 (MH+), calcd
for C34H41P2: 511.2691.
(t, 3JHH ) 8.4 Hz, 1 H, H5′). 13C{1H} NMR (150.9 MHz, CDCl3):
δ 156.0, 153.4 (C2 and C2′), 152.6 (C6), 149.2 (C6′), 140.1 (C4),
2
2
137.7 (d, JCP ) 141.9 Hz, CtCAu), 136.9 (C4′), 134.4 (d, JPC
4
) 13.9 Hz, C2, Ph), 131.7 (d, JPC ) 1.8 Hz, C4, Ph), 129.6 (d,
[Au(CtCbpyl)]n (3). [AuCl(SMe2)] (327 mg, 1.11 mmol) and
NEt3 (0.46 mL, 3.33 mmol) were added to a solution of 1 (200
mg, 1.11 mmol) in CH2Cl2 (15 mL). The mixture was stirred for
30 min and concentrated to about half of its volume. MeOH (60
mL) was added and the resulting yellow-brownish precipitate was
filtered off, washed with acetone (3 × 5 mL), CH2Cl2 (3 × 5 mL),
and Et2O (3 × 5 mL), and dried under vacuum. Yield: 261 mg,
70%. Mp: 145 °C (dec). Anal. Calcd for C12H7AuN2: C, 38.32; H,
1.88; N, 7.45. Found: C, 37.13; H, 1.81; N, 7.19. IR (Nujol, cm-1):
ν(CtC) 2106. The insolubility of 3 prevented its characterization
by NMR spectroscopy in solution as well as its recrystallization.
[Au(CtCphtpyl)]n (4). This was prepared in the same way as
3 from [AuCl(SMe2)] (221 mg, 0.75 mmol), NEt3 (0.31 mL, 2.25
mmol), and 2 (250 mg, 0.75 mmol) in CH2Cl2 (26 mL). Yield:
309 mg, 79%. Mp: 169 °C (dec). Anal. Calcd for
C23H14AuN3 · (HCl)0.4: C, 50.79; H, 2.67; N, 7.73; Cl, 2.61. Found:
C, 49.12; H, 2.74; N, 7.35; Cl, 2.70. IR (Nujol, cm-1): ν(CtC)
2112. The insolubility of 4 prevented its characterization by NMR
spectroscopy in solution as well as its recrystallization.
1JPC ) 56.3 Hz, C1, Ph), 129.3 (d, 3JCP ) 11.3 Hz, C3, Ph), 123.5
(C5′), 122.1 (C5), 121.2 (C3′), 120.2 (C3), 100.9 (d, CtCAu, 3JCP
) 25.7 Hz). 31P{1H} (121.50 MHz, CDCl3): δ 42.6 (s).
Method B. A solution of 1 (90 mg, 0.50 mmol) in CH2Cl2 (15
mL) was treated with [Au(acac)(PPh3)] (279 mg, 0.50 mmol). The
mixture was stirred for 3 h at room temperature and concentrated
to about 1 mL under vacuum, and Et2O (20 mL) was added to
give a colorless precipitate, which was filtered off, washed with
Et2O (3 × 4 mL), and dried in Vacuo. Yield: 184 mg, 58%.
[Au(CtCbpyl){P(Tol)3}] (7). This was prepared in the same
way as 6 from 3 (151 mg, 0.40 mmol) and Tol3P (122 mg, 0.40
mmol) in CH2Cl2 (15 mL). Colorless solid. Yield: 184 mg, 68%.
Mp: 96–102 °C. Anal. Calcd for C33H28AuN2P: C, 58.24; H, 4.15;
N, 4.12. Found: C, 58.17; H, 4.09; N, 3.97. IR (Nujol, cm-1):
1
ν(CtC) 2112. H NMR (300.1 MHz, CDCl3): δ 8.80 (br s, 1 H,
H6), 8.66 (d, 3JHH ) 4.7 Hz, 1 H, H6′), 8.37 (d, 3JHH ) 8.1 Hz, 1
3
5
H, H3′), 8.30 (dd, JHH ) 8.2 Hz, JHH ) 0.7 Hz, 1 H, H3), 7.89
(dd, 3JHH ) 8.4 Hz, 4JHH ) 2.1 Hz, 1 H, H4), 7.78 (td, 3JHH ) 8.1
Hz, 4JHH ) 1.8 Hz, 1 H, H4′), 7.60–7.43 (m, 13 H, C6H4 and H5′),
2.40 (s, 9 H, Me). 13C{1H} NMR (100.8 MHz, CDCl3): δ 156.0
(C2′), 153.2 (C2), 152.5 (C6), 149.2 (C6′), 142.0 (s, C4, Ph), 140.0
HCtCphccbpyl (5). To a solution of 4-Me3SiCtCC6H4I (1124
mg, 4.03 mmol) in dry THF (40 mL) under nitrogen, 1 (725 mg,
4.03 mmol), trans-[PdCl2(PPh3)2] (283 mg, 0.403 mmol), CuI (123
mg, 0.64 mmol), and diisopropylamine (8 mL) were added. The
mixture was stirred for 23 h at room temperature, and the volatiles
were removed under vacuum. The residue was chromatographed
on silica gel using n-hexane/Et2O (3:1) as eluent. Evaporation of
the solvent gave bpyl-CtCC6H4CtCSiMe3-4 as a colorless solid,
which was desilylated by treatment with KF (468 mg, 8.05 mmol)
in MeOH (200 mL) overnight. The solvent was evaporated under
vacuum, the residue was extracted with CHCl3 (50 mL), and the
extract was dried over Na2SO4 and filtered. Evaporation of the
solution gave 5 as a colorless solid. Yield: 850 mg, 75%. Mp:
132–135 °C. Anal. Calcd for C20H12N2: C, 85.69; H, 4.31; N, 9.99.
Found: C, 85.34; H, 4.38; N, 10.01. IR (KBr, cm-1): ν(tC-H)
3274, ν(C6H4CtC) 2214, ν(CtCH) 2102. 1H NMR (600.1 MHz,
CDCl3): δ 8.81 (dd, 4JHH ) 2.1 Hz, 5JHH ) 0.5 Hz, 1 H, H6), 8.69
2
(C4), 136.8 (C4′), 134.2 (d, JPC ) 14.1 Hz, C2, Ph), 129.9 (d,
3JPC ) 11.7 Hz, C3, Ph), 126.6 (d, 1JPC ) 58.3 Hz, C1, Ph), 123.4
(C5′), 122.1 (s, C5), 121.1 (C3′), 120.1 (C3), 100.8 (s, CtCAu),
21.5 (Me). The signal of CtCAu was not observed. 31P{1H} NMR
(121.50 MHz, CDCl3): δ 40.5 (s).
[Au(CtCbpyl)(PEt3)] (8). This was prepared in the same way
as 6 from 3 (200 mg, 0.53 mmol) and PEt3 (118 µL, 0.80 mmol)
in CH2Cl2 (30 mL). Pale yellow solid. Yield: 190 mg, 73%. Mp:
112–120 °C (dec). Anal. Calcd for C18H22AuN2P: C, 43.73; H, 4.49;
N, 5.67. Found: C, 43.60; H, 4.36; N, 5.74. IR (Nujol, cm-1):
ν(CtC) 2106. 1H NMR (400.9 MHz, CDCl3): δ 8.78 (dd, 4JHH
)
5
3
4
2.1 Hz, JHH ) 0.9 Hz, 1 H, H6), 8.66 (ddd, JHH ) 4.8 Hz, JHH
) 1.7 Hz, 5JHH ) 0.9 Hz, 1 H, H6′), 8.36 (dd, 3JHH ) 7.9 Hz, 4JHH
) 1.0 Hz, 1 H, H3′), 8.28 (dd, 3JHH ) 8.3 Hz, 5JHH ) 0.9 Hz, 1 H,
3
4
3
4
5
H3), 7.87 (dd, JHH ) 8.4 Hz, JHH ) 2.1 Hz, 1 H, H4), 7.79 (td,
3JHH ) 7.6 Hz, 4JHH ) 1.8 Hz, 1 H, H4′), 7.26 (td, 1 H, 3JHH ) 4.8
Hz, 4JHH ) 1.1 Hz, H5′), 1.83 (dq, 2JPH ) 9.6 Hz, 3JHH ) 7.7 Hz,
(ddd, JHH ) 4.7, JHH ) 1.8 Hz, JHH ) 0.8 Hz, 1 H, H6′), 8.42
(53) Owen, G. R.; Stahl, J.; Hampel, F.; Gladysz, J. A. Organometallics
2004, 23, 5889.
3
3
6 H, CH2), 1.22 (dt, JPH ) 18.1 Hz, JHH ) 7.6 Hz, 9 H, Me).

Luminescent Alkynyl Gold Metalaligands
Organometallics, Vol. 27, No. 4, 2008 657
13C{1H} NMR (100.8 MHz, CDCl3): δ 155.8 (C2′), 153.1 (C2),
152.4 (C6), 149.1 (C6′), 141.0 (br s, CtCAu) 139.9 (C4), 136.8
(C4′), 123.4 (C5′), 122.1 (C5), 121.0 (C3′), 120.0 (C3), 100.6 (s,
CtCAu), 17.7 (d, 1JPC ) 33 Hz, CH2), 8.8 (s, Me). 31P{1H} (162.3
MHz, CDCl3): δ 38.0 (s).
131.41 (quaternary, C6H4), 129.7 (d, 1JCP) 55.6 Hz, C1, Ph), 129.2
(d, 3JCP ) 11.4 Hz, C3, Ph), 125.6 (quaternary, C6H4), 123.9 (C5′),
121.4 (C3′), 120.7 (quaternary, C6H4), 120.4 (C3 and C5), 103.8
3
(d, JCP ) 26.1 Hz, CtCAu), 93.8 (bpylCtC), 87.5 (bpylCtC);
the signal of CtCAu was not observed. 31P{1H} NMR (121.5
MHz, CDCl3): δ 42.7 (s).
[Au(CtCphtpyl)(CNXy)] (9). A suspension of 4 (132 mg, 0.25
mmol) was treated with XyNC (33 mg, 0.25 mmol). The mixture
was stirred for 30 min at room temperature and then filtered through
Celite. The filtrate was concentrated to about 1 mL under vacuum.
By addition of Et2O (30 mL), a pale yellow solid precipitated, which
was filtered off, washed with Et2O (3 × 5 mL) and acetone (3 ×
5 mL), and dried under vacuum. Yield: 115 mg, 70%. Mp: 167 °C
(dec). Anal. Calcd for C32H23AuN4: C, 58.19; H, 3.51; N, 8.48.
Found: C, 57.93; H, 3.45; N, 8.56. IR (Nujol, cm-1): ν(CtN) 2202,
ν(CtC) 2124. 1H NMR (400.9 MHz, CDCl3): δ 8.73–8.72
(overlapped s and m, 4 H, H3 and H6′), 8.66 (d, 3JHH ) 7.9 Hz, 2
[{Au(CtCbpyl)}2(µ-dppm)] (12). A suspension of 3 (139 mg,
0.37 mmol) in CH2Cl2 (20 mL) was treated with dppm (71 mg,
0.185 mmol). The mixture was stirred for 30 min and concentrated
under vacuum to about 1 mL. By addition of Et2O (20 mL) a
colorless solid precipitated, which was filtered off, washed with
Et2O (3 × 5 mL), and dried under vacuum. Yield: 180 mg, 85%.
Mp: 152–159 °C. Anal. Calcd for C49H36Au2N4P2: 51.77; H, 3.19;
N, 4.93. Found: C, 51.63; H, 3.35; N, 4.87. IR (Nujol, cm-1):
ν(CtC) 2101. 1H NMR (400.9 MHz, CDCl3, 25 °C): δ 8.73 (br s,
2 H, H6), 8.56 (br s, 2 H, H6′), 8.23 (d, 3JHH ) 7.7 Hz, 2 H, H3′),
8.12 (d, 3JHH ) 8.0 Hz, 2 H, H3), 7.80 (br d, 3JHH ) 7.6 Hz, 2 H,
3
4
H, H3′), 7.87 (td, JHH ) 8.1 Hz, JHH ) 1.9 Hz, 2 H, H4′), 7.83
(vd, J ) 8.6 Hz, 2 H, C6H4), 7.62 (vd, J ) 8.6 Hz, 2 H, C6H4),
7.35 (ddd, 3JHH ) 7.6 and 4.8 Hz, 4JHH ) 1.2 Hz, 2 H, H5′), 7.33
3
H4), 7.67–7.36 (m, 22 H, Ph and H4′), 7.19 (br t, JHH ) 4.9 Hz,
2
2 H, H5′), 3.62 (t, JPH ) 10.7 Hz, 2 H, CH2). 13C{1H} NMR
3
3
(t, JHH ) 8.0 Hz, 1 H, H4 of Xy), 7.17 (d, JHH ) 8.0 Hz, 2 H,
H3 of Xy), 2.45 (s, 6 H, Me). 13C{1H} NMR (100.8 MHz, CDCl3):
δ 156.2, 155.9 (C2 and C2′), 149.7 (C4), 149.1 (C6′), 136.8 (C4′),
136.7 (CtCAu), 136.2 (C4, C6H4), 133.0 (CH, C6H4), 130.9 (C4,
Xy), 128.4 (C3, Xy), 126.9 (CH, C6H4), 125.4 (C-CtCAu), 124.1
(C2, Xy), 123.8 (C5′), 121.3 (C3′), 118.6 (C3), 103.8 (CtCAu),
18.7 (s, Me). The signals of the CtN-C carbons were not
observed.
(100.8 MHz, CDCl3, 25 °C): δ 156.1, 152.9 (C2 and C2′), 152.5
(C6), 149.1 (C6′), 139.9 (C4), 136.7 (C4′), 133.6 (vt, N ) 14.7
Hz, C2, Ph), 132.2 (C4, Ph), 129.5 (vt, N ) 11.1 Hz, C3, Ph),
129.2 (br m, C1, Ph), 123.2 (C5′), 122.6 (C5), 121.2 (C3′), 120.1
(C3), 101.9 (br vt, N ) 24 Hz, CtCAu), 29.5 (t, 1JPC ) 25.0 Hz,
CH2). The signal of CtCAu was not observed. 31P{1H} NMR
(162.3 MHz, CDCl3, 25 °C): δ 32.1 (s).
Solution Data of 12 + 17 Mixture. 1H NMR (400.9 MHz,
CD3COCD3, -60 °C): δ 8.78–7.09 (several m, bpyl and Ph), 5.54
and 5.30 (both m, CH2 of [Au3(CtCbpyl)2(dppm)2]+), 4.64 (t, 2JPH
) 12.3 Hz, CH2 of 12). 13C{1H} NMR (150.9 MHz, CD3COCD3/
CDCl3 4:1, 25 °C): δ 155.0, 154.7, 154.5, 152.4, 151.5, 151.0,
150.9, 150.8, 150.5, 148.3, 148.1, 148.0 (all s, C2, C2′, C6 and
C6′ of 12 and 17), 141.8–140.4 (s and two m, CtCAu of 12 and
17), 138.2, 138.0, 137.8 (C4 of 12 and 17), 136.0, 135.64, 135.55
(C4′ of 12 and 17), 132.7–128.2 (Ph), 124.0, 122.9, 122.4, 122.2,
120.7, 119.8, 119.6, 119.4, 118.9, 118.6 (all s, C5, C5′, C3, and
[Au(CtCphtpyl)(PPh3)] (10). A solution of 2 (119 mg, 0.36
mmol) in CH2Cl2 (15 mL) was treated with [Au(acac)(PPh3)] (200
mg, 0.36 mmol). The solution was stirred for 3 h, filtered through
Celite, and concentrated to about 1 mL under vacuum. By addition
of Et2O (20 mL), a colorless solid precipitated, which was filtered
off, washed with Et2O (3 × 5 mL) and acetone (3 × 5 mL), and
dried under vacuum. Yield: 231 mg, 83%. Mp: 254–253 °C. Anal.
Calcd for C41H29AuN3P: C, 62.20; H, 3.69; N, 5.31. Found: C,
62.31; H, 3.80; N, 5.29. IR (Nujol, cm-1): ν(CtC) not observed.
1H NMR (400.9 MHz, CDCl3): δ 8.73 (s, 2 H, H3), 8.72 (ddd,
3JHH ) 4.8 Hz, 4JHH ) 1.7 Hz, 5JHH ) 0.8 Hz, 2 H, H6′), 8.66 (d,
3JHH ) 7.9 Hz, 2 H, H3′), 7.86 (td, 3JHH ) 7.7 Hz, 4JHH ) 1.5 Hz,
2 H, H4′), 7.83 (vd, J ) 8.3 Hz, 2 H, C6H4), 7.65 (vd, J ) 8.3 Hz,
3
C3′ of 12 and 17), 102.2 (d, JPC ) 26.6 Hz, [Au3(Ct
Cbpyl)2(dppm)2]+), 99.6 (vt, N ) 27.2 Hz, AuCtC of 12), 98.2
1
(s, [Au(CtCbpyl)2]-), 26.0 (t, JPC ) 28.0 Hz, CH2 of 12), 24.7
(m, CH2 of 17). 31P{1H} NMR (162.3 MHz, CDCl3, 25 °C): δ
32.1 (s); (CD3COCD3, -60 °C): δ 37.6–37.1 (A part of an AA′XX′
system, P-Au-P of 17), 32.8 (s, P-Au-CtC of 12), 32.3–31.9
(X part of an AA′XX′ system, P-Au-CtC of 17). MS (+ESI,
MeCOMe): m/z 1716 ([M – H]+, M ) [Au3(CtCbpyl)2-
(dppm)2]), 1537 ([M - HCtCbpyl]+), 1357 ([M – 2 HCt
Cbpyl]+), 1333 ([M – dppm]+), 1189, 957 ([Au2(CtCbpyl)-
(dppm)]+); (-ESI, MeCOMe): m/z 555 ([Au(CtCbpyl)2]-).
[{Au(CtCbpyl)}2(µ-dppe)] (13). This was prepared in the same
way as 12 from 3 (132 mg, 0.35 mmol) and dppe (70 mg, 0.18
mmol). Colorless solid. Yield: 180 mg, 89%. Mp: 217–220 °C.
Anal. Calcd for C50H38Au2N4P2: C, 52.18; H, 3.33; N, 4.87. Found:
3
2 H, C6H4), 7.60–7.44 (m, 15 H, Ph), 7.34 (ddd, JHH ) 7.6 and
4
4.0 Hz, JHH ) 1.0 Hz, 2 H, H5′). 13C{1H} NMR (100.8 MHz,
CDCl3): δ 156.2, 155.9 (C2 and C2′), 149.7 (C4), 149.1 (C6′), 136.8
2
(C4′), 136.5 (C4, C6H4), 134.3 (d, JCP) 14.0 Hz, C2, Ph), 134.0
(d, 2JCP) 141.1 Hz, CtCAu), 132.9 (CH, C6H4), 131.6 (d, 4JCP
)
2.1 Hz, C4, Ph), 129.7 (d, 1JCP ) 56.0 Hz, C1, Ph), 129.1 (d, 3JCP
4
) 11.1 Hz, C3, Ph), 126.9 (CH, C6H4), 125.7 (d, JCP ) 3.0 Hz,
3
C-CtCAu), 123.8 (C5′), 121.3 (C3′), 118.6 (C3), 103.9 (d, JCP
) 26.7 Hz, CtCAu). 31P{1H} NMR (81.0 MHz, CDCl3): δ 42.8
(s).
[Au(CtCphccbpyl)(PPh3)] (11). A solution of 5 (90 mg, 0.33
mmol) in CH2Cl2 (10 mL) was treated with [Au(acac)(PPh3)] (184
mg, 0.33 mmol). The solution was stirred for 3 h, filtered through
Celite, and concentrated to about 1 mL under vacuum. By addition
of Et2O (20 mL), a colorless solid precipitated, which was filtered
off, washed with Et2O (3 × 5 mL), and dried under vacuum. Yield:
181 mg, 74%. Mp: 167 °C (dec). Anal. Calcd for C38H26AuN2P:
C, 61.79; H, 3.55; N, 3.79. Found: C, 61.73; H, 3.59; N, 3.56. IR
(KBr, cm-1): ν(C6H4CtC) 2210, ν(CtCAu) 2110. 1H NMR
(600.1 MHz, CDCl3): δ 8.79 (d, 4JHH ) 1.1 Hz, 1 H, H6), 8.68 (d,
3JHH ) 4.5 Hz, 1 H, H6′), 8.41 (d, 3JHH ) 8.7 Hz, 1 H, H3′), 8.40
(d, 3JHH ) 8.3 Hz, 1 H, H3), 7.91 (dd, 3JHH ) 8.2 Hz, 4JHH ) 2.0
1
C, 51.97; H, 3.28; N, 4.55. IR (Nujol, cm-1): ν(CtC) 2099. H
4
NMR (400.9 MHz, CDCl3): δ 8.81 (d, JHH ) 1.2 Hz, 2 H, H6),
3
3
8.66 (d, JHH ) 4.0 Hz, 2 H, H6′), 8.37 (d, JHH ) 8.0 Hz, 2 H,
3
3
H3′), 8.32 (d, JHH ) 8.3 Hz, 2 H, H3), 7.90 (dd, JHH ) 8.4 Hz,
4JHH ) 2.0 Hz, 2 H, H4), 7.80 (td, 3JHH ) 8.0 Hz, 4JHH ) 1.6 Hz,
2 H, H4′), 7.68–7.48 (m, 20 H, Ph), 7.28 (ddd, 3JHH ) 4.8 and 7.5
Hz, JHH ) 1.0 Hz, 2 H, H5′), 2.68 (br s, 4 H, CH2). 13C{1H}
4
NMR (100.8 MHz, CDCl3): δ 155.9, 153.6 (C2 and C2′), 152.6
(C6), 149.3 (C6′), 140.0 (C4), 140.5 (br s, CtCAu), 136.9 (C4′),
133.5 (vt, N ) 13.6 Hz, C2, Ph), 132.4 (s, C4, Ph), 129.7 (vt, N )
11.1 Hz, C3, Ph), 128.6 (m, C1, Ph), 123.6 (C5′), 121.9 (C5), 121.2
(C3′), 120.3 (C3), 101.1 (s, CtCAu), 24.1 (vt, N ) 38.4 Hz, CH2).
31P{1H} NMR (162.3 MHz, CDCl3): δ 39.8 (s). MS (+ESI,
CH2Cl2): m/z 1745 ([Au3(CtCbpyl)2(dppe)2]+), 1601 ([Au3(Ct
Cbpyl)Cl(dppe)2]+), 1369 ([Au2(CtCbpyl)(dppe)2]+), 1347 ([Au3-
3
4
Hz, 1 H, H4), 7.81 (td, JHH ) 7.9 Hz, JHH ) 1.7 Hz, 1 H, H4′),
3
7.57–7.45 (m, 19 H, Ph and C6H4), 7.31 (dd, JHH ) 7.4 and 4.8
Hz, 1 H, H5′). 13C{1H} NMR (50.3 MHz, CDCl3): δ 155.5 (C2′),
154.7 (C2), 151.6 (C6), 149.3 (C6′), 139.3 (C4), 137.0 (C4′), 134.3
2
(d, JCP ) 13.8 Hz, C2, Ph), 132.4 (CH, C6H4), 131.7 (C4, Ph),

658 Organometallics, Vol. 27, No. 4, 2008
Vicente et al.
(CtCbpyl)2(dppe)]+), 1225 ([Au2(dppe)2Cl]+), 993 ([Au(dppe)2]+),
595 ([Au(dppe)]+); (-ESI, CH2Cl2): m/z 555 ([Au(CtCbpyl)2]-).
[{Au(CtCbpyl)}2(µ-dppb)] (14). This was prepared in the same
way as 12 from 3 (150 mg, 0.40 mmol) and dppb (85 mg, 0.20
mmol). Colorless solid. Yield: 222 mg, 94%. Recrystallization from
CH2Cl2/Et2O and drying under vacuum (<1 mbar, 120 °C) gave
analytically pure 14. Mp: 156–159 °C. Anal. Calcd for
C52H42Au2N4P2: C, 52.98; H, 3.59; N, 4.75. Found: C, 52.74; H,
C3, Ph), 126.9 (CH, C6H4), 125.8 (C-CtCAu), 123.8 (C5′), 121.3
(C3′), 118.6 (C3), 103.8 (br s, CtCAu), 30.9 (d, 3JCP ) 15.9 Hz,
1
CH2), 29.2, 28.9 (both s, CH2), 28.0 (d, JCP ) 33.8 Hz, CH2P),
25.5 (s, CH2). The signal of CtCAu was not observed. 31P{1H}
NMR (81.0 MHz, CDCl3): δ 37.8 (s).
PPN[Au(CtCbpyl)2] (18). A solution of 1 (61 mg, 0.34 mmol)
in CH2Cl2 (10 mL) was treated with PPN[Au(acac)2] (156 mg, 0.17
mmol). The solution was stirred at room temperature for 3 h, filtered
through Celite, and concentrated under vacuum to about 4 mL. By
addition of Et2O (15 mL) a pale beige solid precipitated, which
was filtered off, washed with Et2O (3 × 5 mL), and dried under
vacuum. Yield: 165 mg, 90%. Recrystallization from CH2Cl2/Et2O
and drying under vacuum (<1 mbar, 55 °C) gave analytically pure
18. Mp: 73–76 °C. Anal. Calcd for C60H44AuN5P2: C, 65.87; H,
4.05; N, 6.40. Found: C, 66.20; H, 3.98; N, 6.44. IR (Nujol, cm-1):
1
3.59; N, 4.63. IR (Nujol, cm-1): ν(CtC) 2113. H NMR (400.9
4
5
MHz, CDCl3): δ 8.79 (dd, JHH ) 2.1 Hz, JHH ) 0.9 Hz, 2 H,
3
4
5
H6), 8.66 (ddd, JHH ) 4.8 Hz, JHH ) 1.7 Hz, JHH ) 0.9 Hz, 2
3
4
H, H6′), 8.37 (dt, JHH ) 8.1 Hz, JHH
)
5JHH ) 0.9 Hz, 2 H,
H3′), 8.30 (dd, 3JHH ) 7.3 Hz, 5JHH ) 0.7 Hz, 2 H, H3), 7.88 (dd,
3JHH ) 8.3 Hz, 4JHH ) 2.0 Hz, Hz, 2 H, H4), 7.79 (dt, 3JHH ) 7.9
Hz, 4JHH ) 1.7 Hz, 2 H, H4′), 7.68–7.44 (m, 20 H, Ph), 7.27 (ddd,
3JHH ) 4.8 and 7.4 Hz, 4JHH ) 1.0 Hz, 2 H, H5′), 2.42 (br m, 4 H,
CH2), 1.80 (br m, 4 H, CH2). 13C{1H} NMR (75.5 MHz, CDCl3):
δ 155.8, 153.4 (C2 and C2′), 152.5 (C6), 149.2 (C6′), 140.0 (C4),
1
ν(CtC) 2114. H NMR (400.9 MHz, CDCl3): δ 8.66 (br s, 2 H,
H6), 8.63 (d, 3JHH ) 3.6 Hz, 2 H, H6′), 8.31 (d, 3JHH ) 7.9 Hz, 2
3
H, H3′), 8.16 (d, JHH ) 7.9 Hz, 2 H, H3), 7.75 (m, 4 H, H4 and
2
136.8 (C4′), 133.3 (d, JCP) 13.2 Hz, C2, Ph), 131.8 (s, C4, Ph),
H4′), 7.68–7.43 (m, 30 H, Ph), 7.24 (dd, 3JHH ) 6.3 and 5.0 Hz, 2
H, H5′). 13C{1H} NMR (50.3 MHz, CDCl3): δ 156.4 (C2 or C2′),
152.6 (C6), 151.6 (C2′ or C2), 149.1 (C6′), 140.6 (CtCAu), 139.8
(C4), 136.8 (C4′), 134.0 (C4, PPN), 132.1, 129.7 (both m, C2 and
C3, PPN), 127.0 (d, 1JPC ) 118.1 Hz, C1, PPN), 124.7 (C5), 123.1
(C5′), 120.9 (C3′), 119.9 (C3), 99.8 (CtCAu). 31P{1H} NMR
(162.3 MHz, CDCl3): δ 21.2 (s).
1
3
129.8 (d, JCP) 55.5 Hz, C1, Ph), 129.4 (d, JCP) 11.3 Hz, C3,
Ph), 123.5 (C5′), 121.9 (C5), 121.1 (C3′), 120.2 (C3), 100.9 (br s,
CtCAu), 27.8 (d, 1JCP ) 13.2 Hz, CH2), 27.1 (d, 2JCP ) 18.0 Hz,
CH2). The signal of CtCAu was not observed. 31P{1H} NMR
(121.5 MHz, CDCl3): δ 37.5 (s). MS (+ESI, CH2Cl2/MeCOMe):
m/z 1801 (M+ ) [Au3(CtCbpyl)2(dppb)2]+), 1375 ([M - dppb
- H]+), 1281 ([Au2(dppb)2Cl]+), 999 ([Au2(CtCbpyl)(dppb)]+),
623 ([Au(dppb)]+); (-ESI, CH2Cl2/MeCOMe): m/z 555
([Au(CtCbpyl)2]-).
PPN[Au(CtCphtpyl)2] (19). This was prepared in the same
way as 18 from 2 (18 mg, 0.054 mmol) and PPN[Au(acac)2] (25
mg, 0.027 mmol). 19 was obtained as a colorless solid by
precipitation with Et2O. Yield: 31 mg, 82%. Mp: 241–243 °C. Anal.
Calcd for C82H58AuN7P2: C, 70.33; H, 4.17; N, 7.00. Found: C,
70.32; H, 4.15; N, 7.19. IR (nujol, cm-1): ν(CtC) 2100. 1H NMR
(300.1 MHz, CDCl3): δ 8.69–8.67 (overlapped m and s, 8 H, H6′
[{Au(CtCbpyl)}2(µ-dppd)] (15). This was prepared in the same
way as 12 from 3 (200 mg, 0.53 mmol) and dppd (136 mg, 0.26
mmol). The mixture was stirred at room temperature for 45 min
and concentrated up to about 1 mL. A pale yellow solid precipitated
by addition of n-pentane (20 mL). It was filtered off, washed with
n-pentane (3 × 5 mL), and dried under vacuum. Yield: 210 mg,
62%. Mp: 91–95 °C. Anal. Calcd for C58H54Au2N4P2: C, 55.16;
H, 4.31; N, 4.44. Found: C, 54.83; H, 4.39; N, 4.44. IR (KBr,
cm-1): ν(CtC) 2104. 1H NMR (400.9 MHz, CDCl3): δ 8.80 (s, 2
H, H6), 8.66 (d, 3JHH ) 4.3 Hz, 2 H, H6′), 8.36 (d, 3JHH ) 7.9 Hz,
2 H, H3′), 8.30 (d, 3JHH ) 8.3 Hz, 2 H, H3), 7.89 (dd, 3JHH ) 8.1
Hz, 4JHH ) 2.4 Hz, 2 H, H4), 7.79 (td, 3JHH ) 7.7 Hz, 4JHH ) 1.4
Hz, 2 H, H4′), 7.70–7.65 (m, 8 H, Ph), 7.47–7.44 (m, 12 H, Ph),
7.27 (dd, 3JHH ) 7.5 Hz, 4JHH ) 2.4 Hz, 2 H, H5′), 2.40 (m, 4 H,
CH2P), 1.65 (m, 4 H, CH2), 1.43 (m, 4 H, CH2), 1.21 (m, 8 H,
CH2). 13C{1H} NMR (100.8 MHz, CDCl3): δ 155.8, 153.2 (C2
and C2′), 152.4 (C6), 149.1 (C6′), 139.9 (C4), 136.8 (C4′), 133.2
3
3
and H3), 8.63 (d, JHH ) 7.9 Hz, 4 H, H3′), 7.84 (td, JHH ) 8.0
Hz, 4JHH ) 1.8 Hz, 4 H, H4′), 7.68–7.39 (m, 38 H, PPN and C6H4),
3
4
7.32 (ddd, JHH ) 7.6 and 4.7 Hz, JHH ) 0.9 Hz, 4 H, H5′).
13C{1H} NMR (75.5 MHz, CDCl3): δ 156.3, 155.7 (C2 and C2′),
150.0 (C4), 149.0 (C6′), 137.4 (CtCAu), 136.8 (C4′), 134.3 (C4,
C6H4), 133.9 (m, C4, PPN), 132.7 (CH, C6H4), 132.0, 129.6 (both
m, C2 and C3, PPN), 128.8 (C-CtCAu), 126.9 (vdd, 1JCP + 1JCP
) 109.4 Hz, C1, PPN), 126.3 (CH, C6H4), 123.7 (C5′), 121.3 (C3′),
118.3 (C3), 102.6 (s, CtCAu). 31P{1H} NMR (81.0 MHz, CDCl3):
δ 21.2 (s).
PPN[Au(CtCphccbpyl)2] (20). This was prepared in the same
way as 18 from 5 (41 mg, 0.146 mmol) and PPN[Au(acac)2] (68
mg, 0.073 mmol). 20 was precipitated with Et2O as a beige solid.
Yield: 91 mg, 96%. Mp: 190–196 °C (dec). Anal. Calcd for
C76H52AuN5P2: C, 70.53; H, 4.05; N, 5.41. Found: C, 70.24; H,
3.98; N, 5.52. IR (KBr, cm-1): ν(C6H4CtC) 2210, ν(CtCAu)
2096. 1H NMR (600.1 MHz, CDCl3): δ 8.76 (d, 3JHH ) 1.3 Hz, 2
H, H6), 8.68 (d, 3JHH ) 3.9 Hz, 2 H, H6′), 8.39 (d, 3JHH ) 7.9 Hz,
2 H, H3′), 8.37 (d, 3JHH ) 8.2 Hz, 2 H, H3), 7.88 (dd, 3JHH ) 8.2
2
1
(d, JPC ) 13.0 Hz, C2, Ph), 131.5 (s, C4, Ph), 130.3 (d, JPC
)
3
53.2 Hz, C1, Ph), 129.1 (d, JPC) 11 Hz, C3, Ph), 123.4 (C5′),
121.98 (C5), 121.0 (C3′), 120.1 (C3), 100.7 (s, CtCAu), 30.9 (d,
3JPC ) 16.0 Hz, CH2), 29.1, 28.9 (both s, CH2), 27.9 (d, 1JPC ) 34
2
Hz, CH2P), 25.4 (d, JPC ) 3.4 Hz, CH2). The signal of CtCAu
was not observed. 31P{1H} NMR (162.3 MHz, CDCl3): δ 36.8 (s).
MS (+ESI, MeCOMe): m/z 1083 ([Au2(CtCbpyl)(dppd)]+), 707
([Au(dppd)]+); (-ESI, MeCOMe): m/z 555 ([Au(CtCbpyl)2]-).
[{Au(CtCphtpyl)}2(µ-dppd)] (16). This was prepared in the
same way as 12 from 4 (130 mg, 0.25 mmol) and dppd (64 mg,
0.13 mmol). Yield: 117 mg, 59%. Mp: 139–145 °C. Anal. Calcd
for C80H68Au2N6P2: C, 61.22; H, 4.37; N, 5.35. Found: C, 60.93;
H, 4.56; N, 5.35. IR (nujol, cm-1): ν(CtC) 2102. 1H NMR (300.1
MHz, CDCl3): δ 8.73–8.72 (overlapped s and m, 8 H, H3 and H6′),
Hz, 4JHH ) 2.1 Hz, 2 H, H4), 7.82 (td, 3JHH ) 7.6 Hz and 4JHH
)
1.7 Hz, 2 H, H4′), 7.66 (m, 6 H, PPN), 7.50–7.43 (m, 24 H, PPN),
7.36 (m, 4 H, H2, C6H4), 7.32–7.29 (m, 6 H, H3 of C6H4 and H5′).
13C{1H} NMR (150.9 MHz, CDCl3): δ 155.6 (C2′), 154.6 (C2),
151.5 (C6), 149.3 (C6′), 139.2 (C4), 138.8 (CtCAu), 137.0 (C4′),
134.0 (s, C4, PPN), 132.3 (C2, C6H4), 132.1 (m, C2 or C3, PPN),
131.0 (C3, C6H4), 129.7 (m, C3 or C2, PPN), 128.7 (C4, C6H4),
1
127.0 (d, JCP ) 109.1 Hz, C1, PPN), 123.9 (C5′), 121.4 (C3′),
3
3
4
8.63 (d, JHH ) 8.4 Hz, 4 H, H3′), 7.86 (td, JHH ) 7.8 Hz, JHH
) 1.5 Hz, 4 H, H4′), 7.83 (vd, J ) 8.4 Hz, 4 H, C6H4), 7.72–7.43
(several m, 24 H, Ph and C6H4), 7.34 (ddd, 3JHH ) 7.6 and 4.0 Hz,
4JHH ) 1.0 Hz, 4 H, H5′), 2.41 (m, 4 H, CH2P), 1.69–1.22 (m, 16
H, CH2). 13C{1H} NMR (75.5 MHz, CDCl3): δ 156.2, 155.9 (C2
and C2′), 149.7 (C4), 149.1 (C6′), 136.8 (C4′), 136.5 (C4 of C6H4),
120.7 (C5), 120.4 (C3), 118.5 (C1, C6H4), 102.8 (CtCAu), 94.6
(bpylCtC), 86.7 (bpylCtC). 31P{1H} NMR (162.3 MHz, CDCl3):
δ 21.2 (s).
Crystallography. Compounds 6, 10, and 18 were measured on
a Bruker Smart APEX diffractometer; 13, 14, and 17 on a Bruker
Smart 1000 diffractometer. Data were collected using monochro-
mated Mo KR radiation by ω and ꢁ scans. Crystals of 13
disintegrated at –140 °C and were therefore measured at the slightly
2
133.3 (d, JCP ) 13.0 Hz, C2, Ph), 132.9 (CH, C6H4), 131.5 (C4,
Ph), 130.6 (d, 1JCP ) 53.5 Hz, C1, Ph), 129.2 (d, 3JCP ) 10.9 Hz,

Luminescent Alkynyl Gold Metalaligands
Organometallics, Vol. 27, No. 4, 2008 659
higher temperature of –100 °C. The structures of 10, 17, and 18
were solved by direct methods; others by the heavy atom method.
All were refined anisotropically on F2. Restraints to local aromatic
ring symmetry or light atom displacement factor components were
applied in some cases. The hydrogens were refined using a riding
model. Special features/exceptions: Compound 14 displayed an ill-
resolved region of residual electron density associated with an
inversion center. Because no appropriate refinement model for this
(assumed) half-molecule of diethyl ether could be found, the effect
of the electron density was subtracted mathematically from the
intensity data using the program SQUEEZE (A. L. Spek, Univ. of
Utrecht, Netherlands). For compound 17, C and N atoms were
refined isotropically to avoid the need for blocked refinement.
In general, there may be a problem in distinguishing the C and
N atoms in the pyridinic ring systems in the presence of heavy
atoms, especially when the N atoms are not involved in further
interactions such as metal coordination or H bonds. This problem
is exacerbated in terminal rings of bipyridyl moieties, where the
displacement factors may be appreciably larger. The following
diagnostic factors may be useful: (i) U values. With the correct
assignment, the U values should be approximately equal; if C is
assigned as N and Vice Versa, the U values of the “C” atom will be
too low and that of the “N” atom too high. (ii) Direct localization
of H atoms in difference syntheses. This may be difficult in the
presence of heavy atoms, especially if the crystal quality is not
ideal. (iii) Analysis of C-H contacts. If an H atom is geometrically
positioned (falsely) at a C atom that is really N, then it may make
impossibly short contacts to other atoms. (iv) Bond lengths. C-N
should be shorter than C-C. (v) Usually the N atoms are trans
across the ring-connecting C-C bond. Finally, it should be
remembered that the C/N sites may indeed be disordered. On the
basis of the above-mentioned criteria, the following assignments
were made Compounds 6, 10, 18: All pyridinic ring H were found
directly except for H12 of compound 6. Compound 13: N73 and
N86 are probably reliable, N53 and N66 are highly tentative.
Compounds 14 and 17: N atoms assigned with reasonable confi-
dence. However, the assignment of these atoms cannot be com-
pletely unambiguous using X-ray methods alone, and the results
should be interpreted with caution.
Acknowledgment. We thank the Dirección General de
Investigación/FEDER for financial support (Grant CTQ2004-
05396, a “Ramón y Cajal” contract to J.G.-R. and a FPI grant
to N.B.). We also thank Dr. A. Sironi and Dr. N. Masciocchi
for XRPD measurements.
Supporting Information Available: ORTEP diagram of com-
pound 18, crystallographic data in CIF format for 6, 10, 13, 14,
17, and 18, hydrogen bond distances and angles, simulated 31P{1H}
NMR spectrum of 17. These materials are available free of charge
via the Internet at http://pubs. acs.org.
OM7009123