Gold(I) thiolates as metalloligands for the synthesis of the first zirconocene-gold complexes

Article abstract of DOI:10.1002/1099-0682(200207)2002:7<1761::AID-EJIC1761>3.0.CO;2-N

The reactions of the mercaptocarboxylic acids HOOC(CH₂)_nSH (n = 1, 2) with H[AuCl₄] followed by treatment with PMe₂Ph led to the (phosphane)gold f [Au{S(CH₂)_nCOOH}(PMe₂Ph)] [n =

Full text of DOI:10.1002/1099-0682(200207)2002:7<1761::AID-EJIC1761>3.0.CO;2-N

FULL PAPER
Gold(I) Thiolates as Metalloligands for the Synthesis of the First
Zirconocene؊Gold Complexes
Barbara Wenzel,[a] Peter Lönnecke,[a][‡] and Evamarie Hey-Hawkins*[a]
Dedicated to Professor Dr. Peter Welzel on the occasion of his 65th birthday
Keywords: Metallocenes / Zirconium / Gold / O,S ligands / Bridging ligands
1
The
reactions
of
the
mercaptocarboxylic
acids
characterized by H, 13C, 31P NMR and IR spectroscopy. The
crystal structure of 4 shows mono- and bidentate coordina-
tion of two metalloligands to one zirconocene fragment. In
solution at room temperature 3 and 4 are dynamic, and the
carboxylato groups alternate between the mono- and bident-
ate bonding modes. Complex 4 shows catalytic activity in the
oxidation of PPh3 with O2.
HOOC(CH2)nSH (n = 1, 2) with H[AuCl4] followed by treat-
ment with PMe2Ph led to the (phosphane)gold thiolates
[Au{S(CH2)nCOOH}(PMe2Ph)] [n = 1, (1) 2 (2)], which can
act as metalloligands towards complex fragments of a second
metal. Compounds 1 and 2 react with [Cp°2ZrMe2] (Cp° =
C5EtMe4) to give the trinuclear Zr/Au complexes
[Cp°2Zr{κ1O-OOC(CH2)nSAu(PMe2Ph)}{κ2O,OЈ-OOC(CH2)n-
SAu(PMe2Ph)}] [n = 1 (3), n = 2 (4)]. Complexes 1−4 were
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
2002)
Introduction
and the formation of a tetranuclear Zr/Mo complex.[13] In
the present study, we prepared AuI-based metalloligands.
Thus, we describe the synthesis of phosphanylgold thiolates
from mercaptoacetic and mercaptopropionic acid and
their reactions with [Cp°2ZrMe2] to give trinuclear Zr/Au
complexes. The formation of linearly coordinated thiolato
complexes is a well-known property of AuI that is also im-
portant for our purposes, since an attempt to prepare a re-
lated bis(phosphane)nickel thiolate as a metalloligand led
only to formation of the energetically stable chelate com-
plex.[14]
Research in early/late heterobimetallics (ELHBs) has
grown in the last few years and has been the subject of
numerous reports.[1Ϫ4] The reasons for the interest include
their relevance to bioinorganic bimetallic systems and their
potential in homogeneous catalysis. The pairing of two elec-
tronically different metals in a single compound may lead
to cooperative interactions between them, such as those ob-
served in heterogeneous catalysis, and there is also the pos-
sibility for stereo- or regioselective catalysis. Heterogeneous
catalysts in which late transition metals are dispersed on a
Lewis acid (TiO2 or Al2O3) support often show increased
catalytic activity.[5Ϫ9] Such strong metalϪsupport interac-
tions (SMSI) are not well understood but have been attrib-
uted to the electronic communication between the metals
and cooperative activation of substrates by the different
metal centers.[10,11]
For the synthesis of related homogeneous systems we
have used an early transition metal complex of a bifunc-
tional ligand as a so-called metalloligand for a late trans-
ition metal. For example we reported on the synthesis of a
monomeric (mercaptoacetato)zirconocene complex that
acted as metalloligand to form heterobimetallic Zr/Ni and
Zr/Pd complexes.[12] Furthermore, we described the syn-
thesis of macrocyclic, dimeric zirconocene complexes as
metalloligands by using thioglycolates as bridging ligands,
Results and Discussion
Gold(I) Thiolates [Au{S(CH2)nCOOH}] (n ؍ 1, 2)
Gold(I) thiolates are well known.[15] Their preparation
usually starts from gold(III), in the form of sodium tetra-
chloroaurate(III) or the corresponding acid, which then re-
quires a reduction step. Bishop et al.[16] described the syn-
thesis of [Au(SCH2COOH)] using ethyl 2-hydroxyethyl sulf-
ide as reducing agent. We found that HSCH2COOH and
HS(CH2)2COOH also function as reductants to give nearly
quantitative yields of the thiolates [Au(SCH2COOH)] and
[Au(SCH2CH2COOH)].
(Phosphane)gold(I) Thiolates [Au{S(CH2)nCOOH}-
(PMe2Ph)] [n ؍ 1 (1), n ؍ 2 (2)]
Bishop et al.[16] also reported the synthesis of [Au(SCH2-
COOH)(PPh3)], which is only sparingly soluble in ethanol.
[a]
Institut für Anorganische Chemie der Universität Leipzig
Johannisallee 29, 04103 Leipzig, Germany
[‡]
Crystal structure determinations
Eur. J. Inorg. Chem. 2002, 1761Ϫ1764  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 1434Ϫ1948/02/0707Ϫ1761 $ 20.00ϩ.50/0
1761

B. Wenzel, P. Lönnecke, E. Hey-Hawkins
FULL PAPER
To increase the solubility in common solvents, which is im- complexes. Both Au atoms are almost linearly coordinated
portant for the introduction of the second metal in sub- by one P and one S donor [S1ϪAu1ϪP1 174.63(6),
sequent reactions, we used PMe2Ph instead of PPh3. S2ϪAu2ϪP2 176.83(6)°]. The AuϪS and AuϪP bond
[Au(SCH2COOH)(PMe2Ph)] (1) and [Au(SCH2CH2- lengths are similar to those in related AuI complexes, e.g.,
COOH)(PMe2Ph)] (2) were obtained by treating the gold(I) [Au(SCH2COOH)(PPh3)],
[Au(SCMe2COOH)(PPh3)][16]
thiolates [Au(SCH2COOH)] and [Au(SCH2CH2COOH)] and [Au(SPh)(PPh3)].[20] The Au1ϪAu2 distance of
˚
with 1 equiv. of PMe2Ph in ethanol at room temperature; 1 3.2992(4) A suggests intramolecular goldϪgold interaction.
was obtained as a pale yellow solid, but 2 was only obtained Intermolecular AuϪAu contacts are very common and are
as a yellow oil. Both complexes are soluble in THF and also found for other gold(I) complexes with sulfur-con-
1
were characterized by H, 31P, 13C NMR and IR spectra. taining ligands; the distances observed range from 2.9 to 3.5
[21]
In the 1H NMR spectra the protons of the carboxyl groups
A
and are attributed to relativistic effects in the valence
˚
were observed as very broad signals in a range of δ ϭ orbitals of gold atoms,[22] e.g., [Au(SPh)(PPh3)] [AuϪAu
[20]
˚
10Ϫ12 ppm owing to exchange processes. The IR spectrum 3.1355(3) A].
To facilitate this interaction the SϪAuϪP
of 1 shows two strong bands at 1690 and 1303 cmϪ1 for the fragments in 4 have an almost perpendicular arrangement
CϭO and CϪO stretching vibrations of the COOH group. [torsion angles: P1ϪAu1ϪAu2ϪP2 116.5(3),
S1ϪAu1ϪAu2ϪS2 118.9(3)°; see Figure 2]. This arrange-
ment is similar to that in [Au(SPh)(PPh3)], in which torsion
angles of 96.1 and 110.8° were observed.[20] Depending on
the structural properties of the ligands, in other complexes
the ‘‘head-to-head’’ or ‘‘head-to-tail’’ arrangements were
found.
Trinuclear Gold(I)؊Zirconocene Complexes [Cp°2Zr{κ1O-
OOC(CH2)nSAu(PMe2Ph)}{κ2O,OЈ-OOC(CH2)n-SAu-
(PMe2Ph)}] [n ؍ 1 (3), n ؍ 2 (4)]
The trinuclear Zr/Au complexes 3 and 4 were obtained
by reaction of the metalloligands 1 and 2 with [Cp°2ZrMe2]
in a molar ratio of 2:1 (Scheme 1). Both complexes were
obtained as pale yellow solids, and X-ray quality crystals
of 4 were grown from a concentrated solution in THF at
room temperature.
Figure 1. ORTEP plot of 4 (50% probability thermal ellipsoids are
shown; hydrogen atoms are omitted for clarity); selected bond
˚
lengths [A] and angles [°]: Zr1ϪO1 2.352(4), Zr1ϪO2 2.213(4),
Zr1ϪO3 2.067(4), Au1ϪS1 2.302(2), Au1ϪP1 2.265(2), Au2ϪS2
2.306(2), Au2ϪP2 2.268(2), O1ϪC23 1.260(7), O2ϪC23 1.279(6),
O3ϪC26 1.291(7), O4ϪC26 1.226(7); O1ϪZr1ϪO2 56.5(1),
O2ϪZr1ϪO3 78.9(1), S1ϪAu1ϪP1 174.63(6), S2ϪAu2ϪP2
176.83(6), O1ϪC23ϪO2 117.0(5), O3ϪC26ϪO4 123.2(6)
Scheme 1
Structural Studies on 4
An ORTEP plot of 4 is shown in Figure 1. The trinuclear
¯
complex crystallizes in the triclinic space group P1 with two
molecules of the complex and three THF molecules in the
unit cell. One of the THF molecules is disordered and lies
on the inversion center. The zirconium atom is coordinated
by two η5-cyclopentadienyl rings, as well as one monodent-
ate and one bidentate carboxylato group, so that the Zr
atom has 18 valence electrons. This bonding mode was also
observed in related zirconocene bis(carboxylates)[17Ϫ19] and
in a zirconocene mercaptoacetate[12] and the ZrϪO bond
lengths and OϪZrϪO bond angles are similar to these Figure 2. Front and top view of the SϪAuϪP fragments in 4
1762 Eur. J. Inorg. Chem. 2002, 1761Ϫ1764

Gold(I) Thiolates as Metalloligands
FULL PAPER
oil, which was dissolved in 10 mL of THF. At Ϫ20 °C, 1 was ob-
tained as a nearly colorless precipitate. Yield: 0.70 g (73%); m.p.
134Ϫ136 °C. 1H NMR (CDCl3, 25 °C, 400 MHz): δ ϭ 1.81 [d,
2JH,P ϭ 9.7 Hz, 6 H, P(CH3)2Ph], 3.68 (s, 2 H, SCH2COOH), 7.49
(br. m, 3 H, PMe2C6H5), 7.51 (m, 2 H, PMe2C6H5) ppm, OH signal
not observed. 13C{1H} NMR (CDCl3, 25 °C, 100.6 MHz): δ ϭ 16.3
Spectroscopic Studies on 3 and 4
The IR spectra of 3 and 4 exhibit two strong bands for
the CϭO and CϪO stretching vibrations of the monodent-
ate ligand, and two strong bands for the asymmetric and
symmetric vibrations of the bidentate ligand. Compared to
the free carboxyl group in 1, the CϭO and CϪO vibration
bands in the heterobimetallic complexes are shifted to lower
wavenumbers owing to coordination to the Lewis acidic zir-
conium atoms.
In the NMR spectra of 3 and 4 the CH2 groups of the
two metalloligands next to the carboxylate groups were ob-
served as one signal for both complexes. On the basis of the
molecular structure of 4 in the solid state, we would expect
at least two signals for these CH2 groups owing to the dif-
ferent bonding mode of the ligands. Therefore the NMR
spectroscopic data suggest a rapid dynamic process in
which the carboxylato groups alternate between mono- and
bidentate bonding. Such dynamics are well known and were
observed for most zirconocene bis(carboxylates)[17Ϫ19] and
in a zirconocene mercaptoacetate[12] and dimeric zir-
conocene thioglycolates.[13] Low-temperature NMR experi-
ments on 3 and 4 down to Ϫ70 °C failed to freeze out this
dynamic process, and we only observed slight broadening
of the signals.
Preliminary catalytic investigations in oxidation reactions
were performed with 4. We used the model system O2/PPh3,
and the ratio PPh3/PPh3O was determined by 31P NMR
spectroscopy. Complex 4 catalyzes the oxidation of PPh3 in
a molar ratio of 1:10 without apparent decomposition (only
the PMe2Ph ligands are partly oxidized) over 1.5 h at 50
°C. On the basis of earlier investigations on the catalytic
properties of a similar zirconocene mercaptoacetato com-
plex,[12] we assume that the catalytic activity of 4 is due to
the Lewis acidic Zr atom, which is coordinatively unsatur-
ated in solution. Investigations on possible interactions be-
tween the two metals in these complexes are in progress.
1
[d, JC,P ϭ 35.9 Hz, P(CH3)2Ph], 32.1 (s, SCH2COOH), 130.0 (d,
3JC,P ϭ 11.3 Hz, m-C of PC6H5), 132.3 (br. s, p-C of PC6H5), 132.5
1
(s, o-C of PC6H5), 132.6 (d, JC,P ϭ 57.3 Hz, ipso-C of PC6H5),
176.5 (s, SCH2COOH) ppm. Signals for THF are observed in the
1H and 13C NMR spectrum. 31P{1H} NMR (CDCl3, 25 °C,
162 MHz): δ ϭ 11.2 (s, PMe2Ph). IR (KBr pellet): ν˜ ϭ 1690 (Cϭ
O), 1303 (CϪO) cmϪ1. C10H14AuO2PS·1/4THF (444.25): calcd. C
29.7, H 3.6, S 7.2; found C 29.1, H 4.3, S 6.9.
[Au(SCH2CH2COOH)(PMe2Ph)] (2): 0.21 mL (1.4 mmol) of
PMe2Ph was added to a suspension of 0.44 g (1.4 mmol) of
[Au(SCH2CH2COOH)] in 20 mL of ethanol. After about 30 min,
the yellow solution became clear. Complete removal of the solvent
gave a yellow oil which was dissolved in 20 mL of THF. However,
in contrast to 1, complex 2 could only be isolated as an oil. Yield:
0.45 g (85%). 1H NMR (CDCl3, 25 °C, 400 MHz): δ ϭ 1.75 [d,
3
2JH,P ϭ 8.8 Hz, 6 H, P(CH3)2Ph], 2.70 (t, JH,H ϭ 7.2 Hz, 2 H,
SCH2CH2COOH), 3.07 (t, 3JH,H ϭ 7.2 Hz, 2 H, SCH2CH2COOH),
7.44 (br. s, 3 H, PMe2C6H5), 7.62 (m, 2 H, PMe2C6H5) ppm, OH
signal not observed. 13C{1H} NMR (CDCl3, 25 °C, 100.6 MHz):
1
δ
ϭ
16.4 [d, JC,P
ϭ
32.8 Hz, P(CH3)2Ph], 23.4 (s,
3
SCH2CH2COOH), 42.0 (s, SCH2CH2COOH), 129.7 (d, JC,P
ϭ
4
10.8 Hz, m-C of PC6H5), 131.9 (d, JC,P ϭ 1.8 Hz, p-C of PC6H5),
132.2 (d, 2JC,P ϭ 13.5 Hz, o-C of PC6H5), 133.8 (d, 1JC,P ϭ 51.3 Hz,
ipso-C of PC6H5), 177.2 (s, SCH2COOH) ppm. 31P{1H} NMR
(CDCl3, 25 °C, 162 MHz): δ ϭ 7.2 (s, PMe2Ph) ppm.
[Cp°2Zr{κ1O-OOCCH2SAu(PMe2Ph)}{κ2O,OЈ-OOCCH2SAu-
(PMe2Ph)}] (3): A solution of 0.08 g (0.2 mmol) of [Cp°2ZrMe2] in
5 mL of THF was added to a solution of 0.17 g (0.4 mmol) of 1 in
5 mL of THF. The reaction mixture was stirred overnight at room
temperature. Concentration of the solution to about half of its vol-
ume and addition of 10 mL of petroleum ether gave a pale yellow
precipitate of 3 at Ϫ20 °C. Yield: 0.21 g (85%); m.p. 163Ϫ169 °C.
3
1H NMR (CDCl3, 25 °C, 400 MHz): δ ϭ 0.84 (t, JH,H ϭ 7.6 Hz,
2
6 H, C5Me4CH2CH3), 1.82 [d, JH,P ϭ 10.0 Hz, 12 H, P(CH3)2Ph],
1.88 [s, 12 H, C5Et(CH3)4], 1.90 [s, 12 H, C5Et(CH3)4], 2.38 (q,
3JH,H ϭ 7.6 Hz, 4 H, C5Me4CH2CH3), 3.74 (s, 4 H, SCH2COO),
7.46 (br. m, 6 H, PMe2C6H5), 7.77 (m, 4 H, PMe2C6H5) ppm.
13C{1H} NMR (CDCl3, 25 °C, 100.6 MHz): δ ϭ 11.7, 11.9 [s,
Experimental Section
General Details: All operations except the synthesis of the gold thi-
olates were carried out under dry nitrogen using standard Schlenk
techniques. The reagents and solvents were purified by standard
procedures. The 1 H, 13C and 31P NMR spectra were recorded with
an AVANCE DRX 400 spectrometer. The IR spectra were recorded
with an FT-IR spectrometer PerkinϪElmer System 2000 in the
range 400Ϫ4000 cmϪ1. [Cp°2ZrMe2][23] was prepared by a literature
procedure. Mercaptoacetic and mercaptopropionic acid were pur-
chased from Fluka. H[AuCl4] was donated by Degussa.
1
C5Et(CH3)4], 15.0 (s, C5Me4CH2CH3), 16.6 [d, JC,P ϭ 35.1 Hz,
P(CH3)2Ph], 19.7 (s, C5Me4CH2CH3), 32.9 (s, SCH2COO), 121.4,
3
122.2, 127.1 (s, C5EtMe4), 129.7 (d, JC,P ϭ 11.1 Hz, m-C of
2
PC6H5), 132.0 (s, p-C of PC6H5), 132.5 (d, JC,P ϭ 13.1 Hz, o-C
1
of PC6H5), 133.6 (d, JC,P ϭ 55.3 Hz, ipso-C of PC6H5), 183.1 (s,
SCH2COO) ppm. 31P{1H} NMR (CDCl3, 25 °C, 162 MHz): δ ϭ
10.7 (s, PMe2Ph) ppm. IR (KBr pellet): ν˜ ϭ 1635 (CϭO), 1523,
1323 (OϪCϪO), 1191 (CϪO) cmϪ1
.
C42H60Au2O4P2S2Zr
(1240.15): calcd. C 40.6, H 4.8, S 5.1; found C 38.2, H 4.9, S 4.2.
[Au{S(CH2)nCOOH}] (n ؍ 1, 2): An aqueous solution of H[AuCl4]
was treated with an aqueous solution of a mercaptocarboxylic acid
(HOOCCH2SH, HOOCCH2CH2SH) in a molar ratio of 1:3. Both
gold thiolates were obtained as pale yellow solids in nearly quantit-
ative yields and were characterized by elemental analyses.
[Cp°2Zr{κ1O-OOC(CH2)2SAu(PMe2Ph)}{κ2O,OЈ-OOC(CH2)2-
SAu(PMe2Ph)}] (4):
A solution of 0.16 g (0.39 mmol) of
[Cp°2ZrMe2] in 10 mL of THF was added to a solution of 0.35 g
(0.79 mmol) of 2 in 10 mL of THF. The reaction mixture was
stirred overnight at room temperature. Concentration of the solu-
tion to about half of its volume gave a pale yellow precipitate of 4
at Ϫ20 °C. Suitable crystals for a structure analysis were obtained
[Au(SCH2COOH)(PMe2Ph)] (1): 0.31 mL (2.2 mmol) of PMe2Ph
was added to a suspension of 0.64 g (2.2 mmol) of [Au(SCH2-
COOH)] in 20 mL of ethanol. After about 30 min, the yellow solu- from a saturated THF solution at room temperature. Yield: 0.38 g
1
tion became clear. Complete removal of the solvent gave a yellow
(77%); m.p. 95Ϫ98 °C. H NMR (CDCl3, 25 °C, 400 MHz): δ ϭ
Eur. J. Inorg. Chem. 2002, 1761Ϫ1764
1763

B. Wenzel, P. Lönnecke, E. Hey-Hawkins
FULL PAPER
CB2 1EZ, UK [Fax: (internat.)
deposit@ccdc.cam.ac.uk].
ϩ 44-1223/336-033; E-mail:
Table 1. Crystal data and data collection parameters for 4
Empirical formula
C44H64Au2O4P2S2Zr·1.5THF
Mr
1376.32
223(2)
Acknowledgments
We gratefully acknowledge support from the Deutsche Forschungs-
gemeinschaft (Graduiertenkolleg 378) and we thank the Degussa
AG for a generous donation of H[AuCl4].
T [K]
˚
λ [A]
0.71073
triclinic
Crystal system
Space group
¯
P1 (no. 2)
˚
a [A]
11.2310(14)
15.5919(19)
15.895(2)
89.650(2)
73.971(2)
86.307(2)
2669.5(6)
2
1.712
5.855
1360
1.31Ϫ28.71
27960
12413
full-matrix least squares on F2
12413/8/562
0.976
R1 ϭ 0.0411, wR2 ϭ 0.1026
R1 ϭ 0.0636, wR2 ϭ 0.1213
1.989/Ϫ1.876
˚
[1]
b [A]
D. W. Stephan, Coord. Chem. Rev. 1989, 95, 42.
˚
[2]
c [A]
T. A. Wark, D. W. Stephan, Organometallics 1989, 8, 2836.
[3]
α [°]
β [°]
γ [°]
V [A ]
Z
P. Kalck, C. Serra, C. Machet, R. Broussier, B. Gautheron, G.
Delmas, G. Trouve, M. Kubicki, Organometallics 1993, 12,
1021.
3
˚
[4]
A. Schneider, L. H. Gade, M. Breuning, G. Bringmann, I. J.
Scowen, M. McPartlin, Organometallics 1998, 17, 1643.
Density (calcd.) [Mg/m3]
Absorption coefficient [mmϪ1
F(000)
Θ range [°]
Reflections collected
Independent reflections [R(int) ϭ 0.0597]
Refinement method
Data/restraints/parameters
GOF on F2
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
Largest difference peak/hole [e·A
[5]
S. Naito, J. Chem. Soc., Chem. Commun. 1985, 1212.
[6]
]
J. H. Sinfelt, Sci. Am. 1985, 235, 90.
[7]
T. E. Whyte, R. A. Dalla Betta, Catal. Rev.-Sci. Eng. 1982,
24, 567.
[8]
A. T. Bell, Catal. Rev.-Sci. Eng. 1981, 23, 203.
I. E. Maxwell, Adv. Catal. 1981, 30, 1.
Metal Support Interactions in Catalysis, Sintering and Redisper-
[9]
[10]
sion (Eds.: S. A. Stephenson, J. A. Dumesic, R. T. K. Baker, E.
Ruckenstein), Van Nostrand Reinhold Co., New York, 1987.
Strong Metal Support Interactions (Eds.: R. T. K. Baker, S. J.
[11]
Tauster, J. A. Dumesic), American Chemical Society, Wash-
Ϫ3
˚
]
ington, DC, 1986.
B. Wenzel, P. Lönnecke, M. Stender, E. Hey-Hawkins, J. Chem.
[12]
Soc., Dalton Trans. 2002, 478.
[13]
B. Wenzel, P. Lönnecke, E. Hey-Hawkins, Organometallics, in
3
0.82 (t, JH,H ϭ 7.6 Hz, 6 H, C5Me4CH2CH3), 1.82Ϫ1.79 [overlap-
press.
3
ping signals, 36 H, P(CH3)2Ph and C5Et(CH3)4], 2.26 (q, JH,H
7.6 Hz, 4 H, C5Me4CH2CH3), 2.71 (t, JH,H ϭ 8.8 Hz, 4 H,
SCH2CH2COO), 3.29 (t, JH,H ϭ 8.8 Hz, 4 H, SCH2CH2COO),
ϭ
[14]
B. Wenzel, P. Lönnecke, M. Stender, E. Hey-Hawkins, Z.
Anorg. Allg. Chem., accepted.
3
3
[15]
J. Vicente, M. T. Chicote, C. Rubio, Chem. Ber. 1996, 129, 327;
7.46 (m, 6 H, PMe2C6H5), 7.75Ϫ7.69 (m, 4 H, PMe2C6H5) ppm.
P. J. Bonasia, D. E. Gindelberger, J. Arnold, Inorg. Chem. 1993,
13C{1H} NMR (CDCl3, 25 °C, 100.6 MHz): δ ϭ 11.5, 11.7 (s,
´
32, 5126; R. M. Davila, A. Elduque, T. Grant, R. J. Staples,
1
C5Et(CH3)4], 14.9 (s, C5Me4CH2CH3), 16.4 (d, JC,P ϭ 34.8 Hz,
J. P. Fackler, Jr., Inorg. Chem. 1993, 32, 1749; and references
cited therein.
P. Bishop, P. Marsh, A. K. Brisdon, B. J. Brisdon, M. F. Ma-
hon, J. Chem. Soc., Dalton Trans. 1998, 675; and references
cited therein.
W. A. Howard, T. M. Trnka, M. Waters, G. Parkin, J. Or-
ganomet. Chem. 1997, 528, 95.
U. Thewalt, T. Güthner, J. Organomet. Chem. 1989, 361, 309.
H.-M. Gau, C.-T. Chen, T.-T. Jong, M.-Y. Chien, J. Organomet.
Chem. 1993, 448, 99.
M. Nakamoto, W. Hiller, H. Schmidbaur, Chem. Ber. 1993,
126, 605; and references cited therein.
P(CH3)2Ph), 19.6 (s, C5Me4CH2CH3), 25.0 (s, SCH2CH2COO),
46.7 (s, SCH2CH2COO), 121.3, 122.0, 127.1 (s, C5EtMe4), 129.8 (d,
[16]
[17]
3JC,P ϭ 11.0 Hz, m-C of PC6H5), 132.1 (d, JC,P ϭ 2.3 Hz, p-C of
4
PC6H5), 132.4 (d, 2JC,P ϭ 13.2 Hz, o-C of PC6H5), 133.5 (d, 1JC,P ϭ
54.4 Hz, ipso-C of PC6H5), 181.4 (s, SCH2CH2COO) ppm. 31P{1H}
NMR (CDCl3, 25 °C, 162 MHz): δ ϭ 11.6 (s, PMe2Ph) ppm. IR
(KBr pellet): ν˜ ϭ 1644 (CϭO), 1538, 1353 (OϪCϪO), 1186 (CϪO)
cmϪ1. C44H64Au2O4P2S2Zr·1.5THF (1376.32): calcd. C 43.6, H 5.6,
S 4.6; found C 44.1, H 5.1, S 4.2.
[18]
[19]
[20]
[21]
Data Collection and Structural Refinement of 4: The X-ray diffrac-
P. G. Jones, Gold Bull. 1981, 14, 102; 1983, 16, 114; 1986, 19,
46; and references cited therein.
tion data[24] were measured with a Siemens diffractometer of the
[22]
[23]
[24]
˚
type SMART CCD (Mo-Kα ϭ 0.71073 A). All observed reflections
P. Pyykkö, J. P. Desclaux, Acc. Chem. Res. 1979, 12, 276.
R. S. Threlkel, J. E. Bercaw, J. Organomet. Chem. 1977, 136, 1.
Absorption correction with SADABS (G. M. Sheldrick, SAD-
ABS, Program for Scaling and Correction of Area-detector
Data). Structure solution with SHELXS-97 (G. M. Sheldrick,
SHELXS-97, Program for Crystal Structure Solution, Univer-
sität Göttingen, 1997) and refinement with SHELXL-97 (G.
M. Sheldrick, SHELXL-97, Program for the Refinement of
Crystal Structures, Universität Göttingen, 1997).
Received January 16, 2002
were used for refinement (SAINT) of the unit cell parameters. Em-
pirical absorption correction with SADABS.[24] The structures was
solved by direct methods (SHELXTL PLUS).[24] Zr, Au, P, S, O,
and C atoms were refined anisotropically; H atoms were refined
isotropically in calculated positions. Table 1 lists crystallographic
details. CCDC-177457 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge
[I02030]
1764
Eur. J. Inorg. Chem. 2002, 1761Ϫ1764