Organometallic gold(I) and gold(III) complexes containing 1,3,5-triaza-7-phosphaadamantane (TPA): Examples of water-soluble organometallic gold compounds

Article abstract of DOI:10.1021/om050852d

The organometallic gold(I) complexes [Au(C=CCRR′OH)(TPA)J (R = R′ = H, Me, Ph and R = Me, R′ = Et) and [Au(C₆F ₅)(TPA)] as well as the gold(III) complexes trans-[Au(C ₆F₅)₂(TPA)₂]OTf and [A

Full text of DOI:10.1021/om050852d

644
Organometallics 2006, 25, 644-648
Organometallic Gold(I) and Gold(III) Complexes Containing
1,3,5-Triaza-7-phosphaadamantane (TPA): Examples of
Water-Soluble Organometallic Gold Compounds
Fabian Mohr, Elena Cerrada, and Mariano Laguna*
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, UniVersidad de
Zaragoza-CSIC, E-50009 Zaragoza, Spain
ReceiVed October 4, 2005
The organometallic gold(I) complexes [Au(CtCCRR′OH)(TPA)] (R ) R′ ) H, Me, Ph and R ) Me,
R′ ) Et) and [Au(C6F5)(TPA)] as well as the gold(III) complexes trans-[Au(C6F5)2(TPA)2]OTf and
[Au(C6F5)3(TPA)] (TPA ) 1,3,5-triaza-7-phosphaadamantane) were prepared and fully characterized by
spectroscopic methods and, in the case of rac-[Au{CtCC(Et)(Me)OH}(TPA)] and [Au(C6F5)3(TPA)],
by X-ray crystallography. The alkynyl complexes [Au(CtCCRR′OH)(TPA)] (R ) R′ ) H, Me and R
) Me, R′ ) Et) represent rare examples of organometallic gold(I) complexes that are soluble and stable
in water.
scale of more than 600 000 tons per year.7 Among the known
water-soluble phosphines 1,3,5-triaza-7-phosphaadamantane
(TPA) is unique due to its small steric demand (cone angle
similar to PMe3), its resistance to oxidation, and its solubility
in a wide variety of solvents. The synthesis of TPA was first
reported in 1974,8 but the coordination chemistry of this ligand
has been explored only recently.9 Some water-soluble gold(I)
complexes containing TPA have been reported by Fackler Jr.
and co-workers,10-13 but alkynyl complexes containing this
phosphine have never been investigated. Similarly, no gold-
(III) compounds containing TPA have ever been reported. We
have been studying the gold-catalyzed addition of water and
methanol to terminal acetylenes using both organometallic gold-
(III) and gold(I) complexes.14 We found, however, that most
gold complexes we examined were either inactive or very poor
catalysts for this reaction, which may be in part due to their
insolubility and/or instability in the aqueous reaction medium.
In an attempt to improve solubility and stability of organome-
tallic gold(I) and gold(III) complexes in water, we were
interested in synthesizing some gold(I) and gold(III) complexes
that were both water-soluble and stable in water. The results of
this investigation are presented herein.
Introduction
Alkynyl complexes of gold(I) containing phosphine ligands
have been known for many years and have been studied in great
detail.1,2 Recent research efforts in this field have focused on
studying luminescence,3 nonlinear optical properties,4 and the
supramolecular chemistry of gold(I) acetylide complexes.5 The
phosphine ligand in the majority of known alkynylgold(I)
complexes is either an arylphosphine including PPh3, P(4-
MeOC6H4)3, PPh2Me, PPhMe2, or, less frequently, PMe3 or
PCy3 (Cy ) cyclohexyl). To the best of our knowledge, none
of the known alkynyl complexes of gold are soluble in water.
The rapid development of “green chemistry” and the desire to
be able carry out important industrial chemical processes in
water has led to a surge in research in aqueous organometallic
chemistry, in particular the development of water-soluble
catalysts.6 A spectacular example of commercial success in this
field is the Rhurchemie/Rhoˆne-Poulenc hydroformylation pro-
cess carried out using the water-soluble organometallic rhodium
complex [RhH(CO)(TPPTS)3] (TPPTS ) trisulfonated triphen-
ylphosphine sodium salt) in an aqueous biphasic system on a
* To whom correspondence should be addressed. E-mail:
mlaguna@unizar.es.
(1) Grohmann, A.; Schmidbaur, H. In ComprehensiVe Organometallic
Chemistry II; Wardell, J., Eds.; Pergamon: Oxford, 1995.
(2) Schmidbaur, H.; Grohmann, A.; Olmos, M. E. In Gold Progress in
Chemistry, Biochemistry and Technology; Schmidbaur, H., Eds.; John Wiley
& Sons: Chichester, 1999.
Results and Discussion
Gold(I) Alkynyl Complexes. The strategy we employed to
obtain water-soluble gold(I) alkynyl complexes was to utilize
(3) See for example: (a) Cheung, K. L.; Yip, S. K.; Yam, V. W. W. J.
Organomet. Chem. 2004, 689, 4451-4462. (b) Lu, W.; Xiang, H. F.; Zhu,
N.; Che, C. M. Organometallics 2002, 21, 2343-2346. (c) Che, C. M.;
Chao, H. Y.; Miskowski, V. M.; Li, Y.; Cheung, K. K. J. Am. Chem. Soc.
2001, 123, 4985-4991. (d) Yam, V. W. W.; Choi, S. W. K. J. Chem. Soc.,
Dalton Trans. 1996, 4227-4232.
(7) Cornils, B. Org. Process Res. DeV. 1998, 2, 121-127.
(8) Daigle, D. J.; Pepperman, A. B., Jr.; Vail, S. L. J. Heterocycl. Chem.
1974, 11, 407.
(9) Phillips, A. D.; Gonsalvi, L.; Romerosa, A.; Vizza, F.; Peruzzini,
M. Coord. Chem. ReV. 2004, 248, 955-993.
(10) Assefa, Z.; McBurnett, B. G.; Staples, R. J.; Fackler, J. P., Jr.;
Assmann, B.; Angermaier, K.; Schmidbaur, H. Inorg. Chem. 1995, 34, 75-
83.
(4) Cifuentes, M. P.; Humphrey, M. A. J. Organomet. Chem. 2004, 689,
3968-3981.
(5) See for example: (a) Irwin, M. C.; Vittal, J. J.; Puddephatt, R. J.
Organometallics 1997, 16, 3541-3547. (b) McArdle, C. P.; Irwin, M. C.;
Jennings, M. C.; Puddephatt, R. J. Angew. Chem., Int. Ed. 1999, 38, 3376-
3378. (d) McArdle, C. P.; Irwin, M. C.; Jennings, M. C.; Vittal, J. J.;
Puddephatt, R. J. Chem. Eur. J. 2002, 723-734. (e) Mohr, F.; Jennings,
M. C.; Puddephatt, R. J. Eur. J. Inorg. Chem. 2003, 217-223.
(6) See for example: (a) Aqueous-phase organometallic catalysis
concepts and applications; Cornils, B., Herrmann, W. A., Eds.; Wiley-
VCH: Weinheim, 1998. (b) Joo´, F. Aqueous organometallic catalysis;
Kluwer Academic Publishers: Dordrecht, 2001.
(11) Assefa, Z.; McBurnett, B. G.; Staples, R. J.; Fackler, J. P., Jr. Inorg.
Chem. 1995, 34, 4965-4972.
(12) Forward, J. M.; Fackler, J. P., Jr.; Staples, R. J. Organometallics
1995, 14, 4194-4198.
(13) Assefa, Z.; Forward, J. M.; Grant, T. A.; Staples, R. J.; Hanson, B.
E.; Mohamed, A. A.; Fackler, J. P., Jr. Inorg. Chim. Acta 2003, 352, 31-
45.
(14) Casado, R.; Contel, M.; Laguna, M.; Romero, P.; Sanz, S. J. Am.
Chem. Soc. 2003, 125, 11925-11935.
10.1021/om050852d CCC: $33.50 © 2006 American Chemical Society
Publication on Web 12/21/2005

Gold(I) and Gold(III) Complexes Containing TPA
Organometallics, Vol. 25, No. 3, 2006 645
Scheme 1
a combination of organometallic ligands with solubilizing groups
in combination with the highly water-soluble TPA ligand. The
readily available propargyl alcohols, HCtCRR′OH (R ) R′ )
H, Me, Ph and R ) Me, R′ ) Et), seemed an obvious ligand
choice due to the presence of a hydroxy group. Some gold(I)
complexes containing propargyl groups [Au(CtCCR2OH)(P)]
(R ) H, Me, P ) PPh3; R ) H, P ) PCy3) have previously
been described;15,16 however because of the large phosphine
ligands, these complexes are insoluble in water. The reaction
of [AuCl(TPA)] with the propargyl alcohols HCtCCRR′OH
(R ) R′ ) H, Me, Ph; R ) Me, R′ ) Et) in the presence of
base affords the alkynylgold(I) complexes [Au(CtCCRR′OH)-
(TPA)] (R ) R′ ) H 1, Me 2, Ph 3; R ) Me, R′ ) Et 4) as
colorless or pale yellow solids in good yields (Scheme 1).
Complexes 1-4 show singlet resonances at ca. -50 ppm in
their 31P{1H} NMR spectra, consistent for linear gold(I)
compounds containing TPA acting as a P-donor ligand. The
proton NMR spectra show, in addition to the signals from the
propargyl ligands, a singlet resonance and an AB quartet (ca.
13 Hz geminal H-H coupling) due to the NCH2P and NCH2N
methylene groups, respectively. The presence of only a singlet
for the NCH2P methylene protons is unusual since two-bond
P-H coupling would be expected. However, by use of 2D
(HETCOR) and 1H{31P} NMR spectra we could unambiguously
confirm the assignment of the TPA ligand protons. It is
interesting to note that the solvent also affects the NMR signal
of the NCH2P methylene groups; in free TPA they resonate as
a doublet with 2JP-H ) 9 Hz in D2O, whereas in CDCl3 a singlet
is observed. In the 13C NMR spectra of complexes 2 and 4 the
resonances of only the Au-CtC carbon atoms, in addition to
the TPA and alkyne signals, were observed at 111 and 110 ppm,
respectively; very similar chemical shifts have been reported
for other alkynylgold(I) complexes.17 Due to the large quadru-
pole moment of gold, the Au-C carbon signals are very rarely
observed in 13C NMR spectra. The poor solubility of complexes
1 and 3 did not allow us to measure the 13C NMR spectra of
these compounds. The IR spectra of complexes 1-4 show a
Figure 1. ORTEP21 view of one tetranuclear unit of complex 4.
Ellipsoids show 30% probability; hydrogen atoms omitted for
clarity.
Figure 2. Polymeric structure of complex 4. For clarity only the
P atoms of the TPA ligands and the CtC of the propargyl groups
are shown.
in a head-to-tail arrangement, with a torsion angle of ca. 105°,
through short intramolecular gold-gold contacts [3.1178(1) and
3.1164(9) Å] into a trinuclear chain. In addition, a further single
molecule of 4 is attached, again via a short gold-gold contact
of 3.1388(11) Å, to the last gold atom in the chain (Figure 1).
These tetranuclear units are then connected via slightly longer
gold-gold contacts of 3.3294(9) Å to form an infinite chain
polymer with gold “side chains” as shown in Figure 2. In
addition to the aurophilic interactions present in the polymer,
the tetranuclear units are held together by hydrogen-bonding
interactions between hydroxyl groups (O-O ca. 2.75 Å) as well
as between hydroxy groups and one of the TPA nitrogen atoms
(O-N ca. 2.87 Å) as shown in Figure 1. Curiously, the
distribution of the two enantiomers in the polymer does not
follow any particular pattern such as R R, S S, or S R, instead
it seems to be completely random; however, in each tetranuclear
unit the number of R and S enantiomers is exactly equal. The
gold-gold distances present in the structure [3.1178(10),
3.1164(9), 3.1388(11), and 3.3294(9) Å] fall in the range
typically observed for aurophilic bonds between two gold(I)
centers.18 Although similar chain polymers are observed in the
gold(I) cyano complexes [Au(TPA)2][Au(CN)2] [d(Au‚‚‚Au) )
3.45 Å]19 and [Au(CN)(PMe3)] [d(Au‚‚‚Au) ) 3.32 Å],20 the
polymeric structure of complex 4 containing gold “side chains”
finds no precedence in the literature.
weak band due to the CtC stretch at ca. 2100 cm-1
,
characteristic for alkynyls σ-bonded to a gold(I) center, as well
as a very broad band at ca. 3400 cm-1 due to the O-H stretch.
The FAB+ mass spectra of complexes 1-4 do not show
molecular ion peaks; in all cases the base peak corresponds to
loss of the hydroxyl group. This spectral datum is consistent
with the proposed structure (Scheme 1), consisting of linear
alkynyl gold(I) complexes containing P-coordinated TPA ligands.
This was confirmed by an X-ray diffraction study of rac-[Au-
{CtCC(Et)(Me)OH}(TPA)], 4. The basic structure of complex
4 consists of a TPA ligand and the chiral alkyne linearly
coordinated to a gold atom. Three of such units self-assemble
The average Au-P distance in complex 4 [2.269(5) Å] is
slightly longer than that in [AuCl(TPA)] [2.226(2) Å]10 and
slightly shorter than that in [AuPh(TPA)] [2.289(5) Å]12 but
similar to that found in [Au(CtCtBu)(PPh3)] [2.271(2) Å].15
(15) Vicente, J.; Chicote, M. T.; Abrisqueta, M. D.; Jones, P. G.
Organometallics 1997, 16, 5628-5636.
(18) Schmidbaur, H. Chem. Soc. ReV. 1995, 24 (11), 391-400.
(19) Assefa, Z.; Omary, M. A.; McBurnett, B. G.; Mohamed, A. A.;
Patterson, H. H.; Staples, R. J.; Fackler, J. P., Jr. Inorg. Chem. 2002, 41,
6274-6280.
(20) Ahrland, S.; Aurivillius, B.; Dreisch, K.; Noren, B.; Oskarsson, A.
Acta Chem. Scand. 1992, 46, 262-265.
(16) Bruce, M. I.; Horn, E.; Matisons, J. G.; Snow, M. R. Aust. J. Chem.
1984, 37, 1163-1167.
(17) Schuster, O.; Liau, R. Y.; Shier, A.; Schmidbaur, H. Inorg. Chim.
Acta 2005, 358, 1429-1441.

646 Organometallics, Vol. 25, No. 3, 2006
Mohr et al.
Table 1. Selected Bond Lengths (Å) and Angles (deg) for
Complex 4
Au(1)-P(1)
Au(1)-C(7)
Au(2)-P(2)
Au(2)-C(19)
Au(1)-Au(2)
Au(1)-Au(4)
2.258(4)
1.992(15)
2.266(4)
2.020(18)
3.1388(11)
3.3294(9)
Au(3)-P(3)
2.276(5)
2.027(16)
2.277(5)
2.077(5)
3.1178(10)
3.1164(9)
Au(3)-C(31)
Au(4)-P(4)
Au(4)-C(43)
Au(1)-Au(3)
Au(3)-Au(4)*
C(7)-Au(1)-P(1)
C(31)-Au(3)-P(3)
172.2(4)
173.7(5)
C(19)-Au(2)-P(2)
C(43)-Au(4)-P(4)
166.1(4)
178.5(3)
Scheme 2
Figure 3. ORTEP21 view of complex 7 showing one of the two
molecules in the unit cell. Ellipsoids show 50% probability levels.
Table 2. Selected Bond Lengths (Å) and Angles (deg) for
Complex 7
Au(1)-P(1)
Au(1)-C(7)
Au(2)-P(2)
Au(2)-C(31)
2.3285(10)
2.066(2)
2.3228(10)
2.069(2)
Au(1)-C(13)
Au(1)-C(19)
Au(2)-C(37)
Au(2)-C(43)
2.079(2)
2.068(2)
2.066(2)
2.074(2)
C(7)-Au(1)-C(19)
C(7)-Au(1)-C(13)
90.02(8) C(37)-Au(2)-C(31)
90.88(8)
87.67(8) C(37)-Au(2)-C(43) 176.25(8)
C(19)-Au(1)-C(13) 177.31(8) C(31)-Au(2)-P(2)
179.09(6)
87.67(8)
89.15(6)
92.36(6)
C(7)-Au(1)-P(1)
C(19)-Au(1)-P(1)
C(13)-Au(1)-P(1)
174.51(6) C(31)-Au(2)-C(43)
94.14(6) C(37)-Au(2)-P(2)
88.07(6) C(43)-Au(2)-P(2)
coupling constants similar to those of complexes 1-4. However,
the 19F{1H} NMR spectra provide some further information in
order to confirm the structures of these compounds. The C6F5
group gives rise to three resonances for the ortho-, meta-, and
para-fluorine atoms. For complexes 5 and 6 just one set of C6F5
signals is observed in addition to a singlet resonance due to the
triflate anion of complex 6. In contrast, the 19F{1H} NMR
spectrum of compound 7 shows two sets of C6F5 signals in a
1:2 ratio, corresponding to the C6F5 groups trans and cis to the
TPA ligand. The FAB mass spectra of 5-7 show intense
molecular ion peaks and, in the case of complex 7, additional
peaks corresponding to the loss of one, two, and three C6F5
groups. The trans stereochemistry of complex 6 was deduced
from the IR spectrum. A single band at 801 cm-1 is character-
istic of two mutually trans C6F5 groups;23 in the starting material
also one single band at 797 cm-1 is observed. The structure of
complex 7 was confirmed by an X-ray diffraction study. A view
of one of the two independent molecules in the unit cell is shown
in Figure 3, and selected bond lengths and angles are listed in
Table 2. The complex consists of one TPA molecule and three
C5F6 groups coordinated to the gold atom in a slightly distorted
square-planar arrangement with CAuC and CAuP angles ranging
from 87.67(8)° to 94.14(6)° (molecule A) and 87.67(8)° to
92.36(6)° (molecule B). The Au-P distances [2.3285(10) and
2.3228(10) Å] are considerably shorter than those found in other
gold(III) phosphine complexes such as [Au(C6F5)3{PPh2CH2-
CH(OMe2)}] 2.3692(8) Å,24 [Au(C6F5)3{PPh2(2-HSC6H4)}]
2.3884(16) Å,25 and [AuMe3(PPh2)] 2.350(6) Å.26 This Au-P
The Au-C bond lengths in complex 4 show much greater
variation (Table 1) than the Au-P distances; however the
average Au-C bond distance in 4 [2.019(14) Å] is shorter than
those in [AuPh(TPA)] [2.040(2) Å]12 and [Au(CtCCH2Br)-
(PCy3)] [2.080(12) Å]15 but longer than that observed in [Au-
(CtCtBu)(PPh3)] [1.997(8) Å].15
The aim of producing water-soluble organometallic gold(I)
complexes was indeed achieved: the TPA alkynyl gold(I)
complexes 2 and 4 are soluble (ca. 8 mg/mL) and also stable in
water. Surprisingly, complex 1, with the least bulky R groups,
is only very poorly soluble in water (ca. 0.7 mg/mL) and dmso
and completely insoluble in other common organic solvents.
Similarly, the phenyl derivative (3) is poorly soluble in dmso
and, as was expected, insoluble in water.
Gold(I) and Gold(III) C6F5 Complexes. Since we have
extensively studied gold(I) and gold(III) containing one, two,
and three C6F5 groups in the past,22 we wished to prepare some
TPA analogues in the hope to obtain water-soluble C6F5
derivatives. The neutral gold(I) complex [Au(C6F5)(TPA)] (5)
as well as the cationic and neutral gold(III) complexes trans-
[Au(C6F5)2(TPA)2]OTf (6) and [Au(C6F5)3(TPA)] (7) were
prepared by displacement of the weakly coordinated tetrahy-
drothiophene (tht) ligand from [Au(C6F5)(tht)], trans-[Au(C6F5)2-
(tht)2]OTf, and [Au(C6F5)3(tht)], respectively (Scheme 2).
The 31P{1H} and 1H NMR spectra of complexes 5-7 display
resonances due to the TPA ligand, with chemical shifts and
(21) Farrugia, J. L. J. Appl. Crystallogr. 1997, 30, 565.
(23) Uso´n, R.; Laguna, A.; Laguna, M.; Abad, M. J. Organomet. Chem.
1983, 249, 437-443.
(22) See for example: (a) Uso´n, R.; Laguna, A.; Laguna, M.; Fernandez,
E.; Jones, P. G.; Sheldrick, G. M. J. Chem. Soc., Dalton Trans. 1982, 1971-
1976. (b) Uso´n, R.; Laguna, A.; Laguna, M.; Abad, M. J. Organomet. Chem.
1983, 249, 437-443. (c) Uso´n, A.; Laguna, A.; Laguna, M.; Jime´nez, J.;
M. E., D. Inorg. Chim. Acta 1990, 168, 89-92.
(24) Bardaj´ı, M.; Laguna, A.; Jones, P. G. Organometallics 2001, 20,
3906-3912.
(25) Jones, P. G.; Terroba, R.; Fernandez, E.; Laguna, M. Acta
Crystallogr. 2002, E58, m90-m92.

Gold(I) and Gold(III) Complexes Containing TPA
Organometallics, Vol. 25, No. 3, 2006 647
4 the resulting solutions were taken to dryness and the solid residue
was extracted with CH2Cl2. After filtration through Celite and
concentration in a vacuum the complexes were isolated by addition
of pentane. In the case of complex 3, the precipitated product was
isolated by filtration and washed well with water, EtOH, and
pentane.
[Au(CtCCH2OH)(TPA)], 1: pale yellow solid (93% yield);
31P{1H} NMR (DMSO-d6) δ -48.78; 1H NMR (DMSO-d6) δ 3.97
(s, 2 H, CH2O), 4.24 (s, 6 H, CH2P), 4.41 (AB q, J ) 12.6 Hz, 6
H, CH2N), 4.74 (br s, 1 H, OH); FAB-MS m/z 392 [M - OH]+;
IR (KBr disk) 3400 ν(-OH), 2118 cm-1 ν(CtC). Anal. Calcd for
C9H15AuN3OP (409.2): C 26.42, H 3.70, N 10.27. Found: C 26.35,
H 3.61, N 9.96.
bond shortening is likely due to the low steric bulk of the TPA
ligand, as evident by the similarity of the Au-P distances in
complex 7 with those in [AuI3(PMe3)] 2.334(2) Å; the analogous
complex containing the more bulky PPhMe2 ligand has slightly
longer Au-P distances of 2.342(2) and 2.345(2) Å.27 The Au-C
bond lengths for the C6F5 groups trans and cis to the phosphine
[molecule A: 2.066(2), 2.079(2), and 2.068(2) Å, molecule B:
2.069(2), 2.074(2), and 2.066(2) Å, respectively] are almost
equal, with one of the trans Au-C distances being slightly
longer. The same observations, and almost identical Au-C bond
lengths, have been reported for other tris(pentaflurophenyl)gold-
(III) compounds.24,25 To the best of our knowledge complex 7
represents the first structurally characterized gold(III) derivative
of TPA.
Unfortunately, none of the C6F5 complexes described here
are soluble in water. However, perhaps surprisingly, [Au(C6F5)3-
(TPA)] (7) is soluble in MeOH, whereas the cationic complex
6 containing two TPA ligands, which could be expected to be
more water soluble, is soluble in acetone but poorly soluble in
CH2Cl2 and CHCl3.
The findings presented here illustrate that water solubility of
a given complex is difficult to predict, and thus the tailored
design of water-soluble gold compounds is currently still based
on trial and error studies. However, as our results of the
propargylgold(I) complexes show, the combination of a water-
soluble ligand with a ligand possessing solubilizing groups (here
-OH) can give water-soluble complexes. The presence of a
water-soluble ligand alone seems not enough to make a complex
water soluble, as evidenced by the water-insoluble complex [Au-
(C6F5)(TPA)]. Further work is currently in progress to attempt
to design more water-soluble gold derivatives by ligand
modification and to examine the catalytic properties of some
of these compounds in aqueous medium.
[Au(CtCC{Me}2OH)(TPA)], 2: pale yellow solid (86% yield);
1
31P{1H} NMR (CDCl3) δ -50.72; H NMR (CDCl3) δ 1.50 (s, 6
H, Me), 3.24 (br s, 1 H, OH), 4.37 (s, 6 H, CH2P), 4.54 (AB q, J
) 13.1 Hz, 6 H, CH2N); 13C NMR (CDCl3) δ 32.79 (Me), 52.42
(d, J ) 20.2 Hz, NCH2P), 65.10 (COH), 73.22 (d, J ) 7.4 Hz,
NCH2N), 111.24 (Au-CtC), Au-CtC not observed; FAB-MS
m/z 420 [M - OH]+; IR (KBr disk) 3407 ν(-OH), 2100 cm-1
ν(CtC). Anal. Calcd for C11H19AuN3OP (437.2): C 30.22, H 4.38,
N 9.61. Found: C 30.34, H 4.22, N 9.52.
[Au(CtCC{Ph}2OH)(TPA)], 3: colorless solid (96% yield);
31P{1H} NMR (DMSO-d6) δ -48.43; 1H NMR (DMSO-d6) δ 4.25
(s, 6 H, CH2P), 4.42 (AB q, J ) 12.6 Hz, 6 H, CH2N), 6.23 (br s,
1 H, OH), 7.14 (tt, J ) 7.3/1.3 Hz, 2 H, Ph p-H), 7.24 (t, J ) 7.8
Hz, 4 H, Ph m-H), 7.53 (dd, J ) 7.0/1.3 Hz, 4 H, Ph o-H); FAB
MS m/z 545 [M - OH]+; IR (KBr disk) 3430 ν(-OH), 2112 cm-1
ν(CtC). Anal. Calcd for C21H23AuN3OP (561.4): C 44.93, H 4.13,
N 7.49. Found: C 44.94, H 4.01, N 7.12.
rac-[Au(CtCCMe{Et}OH)(TPA)], 4: pale yellow solid (86%
yield); 31P{1H} NMR (CDCl3) δ -50.49; 1H NMR (CDCl3) δ 1.04
(t, J ) 7.6 Hz, 3 H, CH3), 1.44 (s, 3 H, Me), 1.65 (q, J ) 7.3 Hz,
2 H, CH2), 3.11 (br s, 1 H, OH), 4.34 (s, 6 H, CH2P), 4.53 (AB q,
J ) 13.1 Hz, 6 H, CH2N); 13C NMR (CDCl3) δ 9.40 (CH3), 30.27
(Me), 37.26 (CH2), 52.16 (d, J ) 20.5 Hz, NCH2P), 68.44 (COH),
72.96 (d, J ) 7.3 Hz, NCH2N), 109.72 (Au-CtC), Au-CtC
not observed; FAB-MS m/z 434 [M - OH]+; IR (KBr disk) 3413
ν(-OH), 2105 cm-1 ν(CtC). Anal. Calcd for C12H21AuN3OP
(451.2): C 31.94, H 4.69, N 9.31. Found: C 32.06, H 4.24, N
9.11. Crystals suitable for X-ray diffraction were grown by slow
diffusion of hexane into a CH2Cl2 solution of the complex.
In conclusion we have prepared and characterized a series
of organometallic gold(I) and gold(III) complexes including the
first gold(III) complexes containing TPA as well as examples
of organometallic gold compounds that are soluble and stable
in water.
Experimental Section
General Procedures. 1H, 13C, 31P{1H}, and 19F{1H} NMR
spectra were recorded on a 400 MHz Bruker Avance spectrometer.
Chemical shifts are quoted relative to external TMS (1H), 85% H3-
PO4 (31P), CFCl3 (19F); coupling constants are reported in Hz. FAB
mass spectra were measured on a VG Autospec spectrometer in
positive ion mode using NBA as matrix. IR spectra were recorded
as KBr disks on a Perkin-Elmer SpectrumOne instrument. Elemental
analyses were obtained in-house using a Perkin-Elmer 240B
microanalyzer. TPA,28 [AuCl(TPA)],10 [Au(C6F5)(tht)],29 and [Au-
(C6F5)3(tht)]29 were prepared by published procedures; all other
reagents were obtained commercially and used as received. trans-
[Au(C6F5)2(tht)2]OTf was prepared from trans-[nBu4N][AuBr2-
(C6F5)2] and 2 equiv of [Ag(OTf)(tht)].
Synthesis of [Au(CtCCRR′OH)(TPA)] Complexes. To a
solution of NaOEt (0.033 g, 0.485 mmol) in EtOH (10 mL) was
added [AuCl(TPA)] (0.100 g, 0.257 mmol) and the appropriate
alkyne (0.385 mmol). The mixture was allowed to stir at room
temperature overnight. Depending on the solubility of the product,
different workup procedures were used: For complexes 1, 2, and
[Au(C6F5)(TPA)], 5. A solution of [Au(C6F5)(tht)] (110 mg,
0.243 mmol) in CH2Cl2 (10 mL) was treated with solid TPA (38
mg, 0.242 mmol) and stirred for 2 h. The solution was filtered
through Celite and concentrated in a vacuum. Addition of pentane
afforded the complex as a colorless solid in 66% yield: 31P{1H}
NMR (CDCl3) δ -48.40; 1H NMR (CDCl3) δ 4.26 (s, 6 H, CH2P),
4.50 (AB q, J ) 13.1 Hz, 6 H, CH2N); 19F{1H} NMR (CDCl3) δ
-161.93 (m, m-F), -157.66 (t, J ) 20.7 Hz, p-F), -116.27 (m,
o-F); FAB MS m/z 522 [M]+, 354 [M - C6F5]+. Anal. Calcd for
C12H12AuF5N3P (521.2): C 27.65, H 2.32, N 8.06. Found: C 27.70,
H 2.17, N 8.20.
trans-[Au(C6F5)2(TPA)2]OTf, 6. To a solution of TPA (25 mg,
0.159 mmol) in acetone (10 mL) was added solid cis-[Au(C6F5)2-
(tht)2]OTf (61 mg, 0.071 mmol). After stirring for 2 h the solution
was evaporated to dryness and the resulting solid washed with Et2O
and dried. The complex was obtained as a pale yellow solid in
69% yield: 31P{1H} NMR (acetone-d6) δ -20.75; 1H NMR
(acetone-d6) δ 4.55 (s, 6 H, CH2P), 4.59 (AB q, J ) 13.1 Hz, 6 H,
CH2N); 19F{1H} NMR (acetone-d6) δ -156.27 (m, m-F), -151.88
(t, J ) 20.7 Hz, p-F), -119.34 (m, o-F), -75.58 (s, OTf); FAB-
MS m/z 845 [M]+. Anal. Calcd for C25H24AuF13N6OP (994.5): C
30.19, H 2.43, N 8.45. Found: C 30.34, H 2.34, N 8.29.
(26) Stein, J.; Fackler, J. P., Jr.; Paparizos, C.; Chen, H. W. J. Am. Chem.
Soc. 1981, 103, 2192-2198.
(27) Schneider, D.; Schier, A.; Schmidbaur, H. J. Chem. Soc., Dalton
Trans. 2004, 1995-2005.
[Au(C6F5)3(TPA)], 7. To a solution of [Au(C6F5)3(tht)] (100 mg,
0.127 mmol) in CH2Cl2 (5 mL) was added TPA (20 mg, 0.127
mmol). After stirring for ca. 2 h the solution was concentrated in
(28) Daigle, D. J. Inorg. Synth. 1998, 32, 40-45.
(29) Uso´n, R.; Laguna, A.; Laguna, M. Inorg. Synth. 1989, 26, 85-91.

648 Organometallics, Vol. 25, No. 3, 2006
Table 3. Details of Crystal Data and Structure Refinement for Complexes 4 and 7
Mohr et al.
4
7
empirical formula
fw
temp/K
C
12.50H22AuClN3O1.75
P
C24H12AuF15N3P
855.30
150
505.72
100
wavelength/Å
cryst syst
space group
a/Å
b/Å
c/Å
0.71073
monoclinic
P2(1)/c
18.489(4)
21.169(4)
18.701(4)
90
112.47(3)
90
6764(2)
16
0.71073
triclinic
P-1
10.256(2)
13.206(3)
20.794(4)
79.12(3)
76.88(3)
71.28(3)
2577.1(9)
4
R/deg
â/deg
γ/deg
V/Å3
Z
density (calcd)/(Mg/m3)
abs coeff/mm-1
F(000)
1.986
8.956
3888
2.204
5.902
1624
cryst habit
pale yellow needle
colorless block
0.25 × 0.21 × 0.18
3.73-32.02
cryst size/mm
θ range for data collecn/deg
index ranges
no. of reflns collected
no. of indep reflns
no. of data/restraints/params
R1 (I > 2σ(I))a
wR2 (all data)b
S (all data)c
largest diff peak, hole/(e Å-3
0.26 × 0.038 × 0.033
3.70-25.03
-22 e h e 21, -25 e k e 25, -10 e l e 22
-12 e h e 15, -18 e k e 18, -30 e l e 29
23 026
24 589
6899 (R(int) ) 0.0360)
6899/22/740
0.0512
0.1448
1.034
15 308 (R(int) ) 0.0108)
15 308/0/793
0.0180
0.0403
1.007
)
1.819, -0.754
1.514, -1.082
2
2
2
2
2
2
a R1(F) ) ∑|Fo| - |Fc|/∑|Fo|. b wR2(F2) ) [∑[w(Fo - Fc )2]/∑[w(Fo )2]1/2, w-1 ) [σ2(Fo ) + (aP)2 + bP], where P ) [max(Fo , 0) + 2Fc )]/3. c S )
2
2
[∑[w(Fo - Fc )2]/(n - p)]1/2, where n is the number of reflections and p the number of refined parameters.
a vacuum and pentane was added. The resulting colorless solid was
isolated by filtration, washed with pentane, and dried. The product
was obtained in 65% yield: 31P{1H} NMR (CDCl3) δ -55.83; 1H
NMR (CDCl3) δ 4.18 (s, 6 H, CH2P), 4.49 (AB q, J ) 13.1 Hz, 6
H, CH2N); 19F{1H} NMR (CDCl3) δ -160.77 (m, cis-m-F),
-158.87 (m, trans-m-F), -156.47 (t, J ) 19.5 Hz, cis-p-F),
-154.12 (t, J ) 19.5 Hz, trans-p-F), -121.93 (m, cis-o-F), -120.88
(m, trans-o-F); FAB-MS m/z 856 [M]+, 688 [M - C6F5]+, 521 [M
- 2C6F5]+, 354 [M - 3C6F5]+. Anal. Calcd for C24H12AuF15N3P
(855.3): C 33.70, H 1.41, N 4.91. Found: C 33.73, H 1.32, N
5.03. Crystals suitable for X-ray diffraction were grown by slow
diffusion of hexane into a CH2Cl2 solution of the complex.
X-ray Crystallography. Crystals of complex 4 and 7 were
mounted in oil on a glass fiber, and data were collected on an
Oxford Diffraction Xcalibur 2 CCD diffractometer at 100 and 150
K, respectively. Data were reduced and absorption corrections
applied using CrysalisRED30 and SADABS.31 The structures were
solved using SIR-9232 (4) and direct methods33 (7). Both structures
were refined to Fo2 using full-matrix least squares.33 All hydrogen
atoms were placed on calculated positions and refined as riding on
their respective carbon atoms. Complex 4 contained a disordered
CH2Cl2 molecule in which one of the chlorine atoms was refined
with a 60:40 site occupancy and fixed C-Cl distances of 1.75 Å.
Furthermore, the crystal contained three waters of crystallization,
the hydrogen atoms of which could not be located. One of the water
molecules was disordered and was refined with a 55:45 site
occupancy. Crystallographic and refinement details for complexes
4 and 7 are summarized in Table 3.
Acknowledgment. We thank the Ministerio de Ciencia y
Tecnolog´ıa Spain for financial support (CTQ2005-08099-C03-
01) and for a research grant to F.M. (Grant No. SB2003-0235).
We are grateful to Prof. Larry Falvello for crystallographic
advice.
Supporting Information Available: Crystallographic details
for complexes 4 and 7 in CIF format. This material is available
free of charge via the Internet at http://pubs.acs.org.
OM050852D
(32) Altomare, A.; Cascarano, M.; Giacovazzo, C.; Guagliardi, A.; Burla,
M. C.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 1045-
1050.
(30) CrysAlis CCD and CrysAlis RED, V 1.171.27p8; Oxford Diffraction,
Ltd., 1995-2005.
(31) Sheldrick, G. M. SADABS Version 2.03; Universia¨t Go¨ttingen, 2002.
(33) Sheldrick, G. M. SHELXTL-NT 6.1; Universita¨t Go¨ttingen, 1998.