Synthesis and molecular structures of the cationic gold(I)-aziridine complexes [Ph3PAuAz]O3SCF3 (Az = C 2H4NH, CH2CHMeNH, CH2CMe 2NH, CH2CHEtNH, CH2CHPhNH, C2H 4NBz, C2H4NC2H4OH)

Article abstract of DOI:10.1016/j.jorganchem.2004.11.026

The gold(I) complex Ph₃PAuCl (1) reacts in the presence of AgO₃SCF₃ (=AgOTf) with a series of aziridines with various NH-, NR-, CHR- and CR₂-functionalities via halide elimination at ambient temperature, to give the cationic mixed phosphane-aziridine gold(I) complexes [Ph₃PAuAz]OTf (2-8) (Az = aziridine, 2-methylaziridine, 2,2-dimethylaziridine, 2-ethylaziridine 2-phenylaziridine, N-benzylaziridine, N-hydroxyethylaziridine). The X-ray structure analyses show the gold(I) centres are linearly coordinated by the PPh₃ and Az ligands, and the intact three membered aziridine rings coordinate through the distorted tetrahedral N-atoms. Compounds 2-8 are stable with respect to both directed thermal or photolytic alkene elimination, or any ring N-C opening reaction which would result in the corresponding cationic nitrene complexes [Ph₃PAuNH]OTf and [Ph₃PAuNR]OTf, or any oxidative addition products. The phenyl substituent in the 2-position of 6 is obviously bowed with its plane towards the Au centre, indicating some Au-π-ring interaction with the distance Au-C _n ≈ 4.00 A?. The O atom of the hydroxy group in 8 also lies very close to the Au centre, with the distance Au-O = 3.078 A?. The IR, ¹H, ¹³C and ³¹P NMR, and MS spectra are reported and discussed, and the molecular structures of 3, 4, 6 and 8 have been determined by single crystal X-ray diffraction analyses.

Full text of DOI:10.1016/j.jorganchem.2004.11.026

Journal of Organometallic Chemistry 690 (2005) 1986–1993
www.elsevier.com/locate/jorganchem
Synthesis and molecular structures of the cationic
gold(I)–aziridine complexes [Ph3PAuAz]O3SCF3 (Az = C2H4NH,
CH2CHMeNH, CH2CMe2NH, CH2CHEtNH,
CH2CHPhNH, C2H4NBz, C2H4NC2H4OH)
*
Ingo-Peter Lorenz , Christoph Krinninger, Roland Wilberger, Roman Bobka,
Holger Piotrowski, Markus Warchhold, Heinrich Noth
¨
Department of Chemistry and Biochemistry, Ludwig-Maximilian-University Munich, Butenandtstr. 5-13, D-81377 Mu¨nchen, Germany
Received 12 November 2004; accepted 15 November 2004
Available online 29 December 2004
Abstract
The gold(I) complex Ph3PAuCl (1) reacts in the presence of AgO3SCF3 (=AgOTf) with a series of aziridines with various NH-,
NR-, CHR- and CR2-functionalities via halide elimination at ambient temperature, to give the cationic mixed phosphane-aziridine
gold(I) complexes [Ph3PAuAz]OTf (2–8) (Az = aziridine, 2-methylaziridine, 2,2-dimethylaziridine, 2-ethylaziridine 2-phenylaziri-
dine, N-benzylaziridine, N-hydroxyethylaziridine). The X-ray structure analyses show the gold(I) centres are linearly coordinated
by the PPh3 and Az ligands, and the intact three membered aziridine rings coordinate through the distorted tetrahedral N-atoms.
Compounds 2–8 are stable with respect to both directed thermal or photolytic alkene elimination, or any ring N–C opening reaction
which would result in the corresponding cationic nitrene complexes [Ph3PAuNH]OTf and [Ph3PAuNR]OTf, or any oxidative addi-
tion products. The phenyl substituent in the 2-position of 6 is obviously bowed with its plane towards the Au centre, indicating some
˚
Au–p-ring interaction with the distance Au–Cn ꢀ 4.00 A. The O atom of the hydroxy group in 8 also lies very close to the Au centre,
1
with the distance Au–O = 3.078 A. The IR, H, 13C and 31P NMR, and MS spectra are reported and discussed, and the molecular
˚
structures of 3, 4, 6 and 8 have been determined by single crystal X-ray diffraction analyses.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Gold(I) complexes; Aziridine ligands; Au–p-ring interaction; X-ray crystalography
1. Introduction
thesis of oxo (and acylmethyl) and thio complexes by
simple and easy alkene elimination [1,2]. It is interesting
to note, only few examples of C2H4X complexes (X = O,
S) are known. The aziridines, however, generally remain
intact as three-membered rings, and coordinate through
their N atom when reacted with transition metal com-
plexes [3–9]. Hitherto, no nitrene complex has been gen-
erated by the alkene elimination of an aziridine. In two
papers, however, a N–C ring opening reaction of aziri-
dine ligands with hydrido- and chloro complexes
CpMo(CO)3X (X = H, Cl) has been reported to give
the corresponding b-aminoacyl complexes as the final
Although aziridines are isolobal to oxiranes and thi-
iranes (C2H4X; X = NH, O, S), their reactivity as li-
gands in transition metal complexes is quite different.
Oxiranes and thiiranes are suitable oxidation (and oxi-
dative addition) reagents for organic compounds, and
are also useful in organometallic chemistry for the syn-
*
Corresponding author. Tel.: +49 89 2180 77486; fax: +49 89 2181
77867.
E-mail address: ingo-peter.lorenz@cup.uni-muenchen.de (I.-P.
Lorenz).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.11.026

I.-P. Lorenz et al. / Journal of Organometallic Chemistry 690 (2005) 1986–1993
1987
products [7,10] via N-protonation and addition of the
2. Results and discussion
opened ring onto the M–C bond of a carbonyl ligand
(see Scheme 1). The structures of two further b-amino-
acyl complexes have also been reported [11,12].
Electrophilic ring opening reactions of aziridines are
well-known in organic chemistry [13] and therefore, azir-
idines should be reacted with more electrophilic organo-
metallic complex fragments than have previously been
used. We chose the easily obtainable chloro complex
Ph3PAuCl (1) which is very electrophilic in the presence
of AgO3SCF3, for reaction with several aziridines. No
alkene elimination and no nitrene formation, however,
was observed, but again simple N-coordination of the
aziridines to give the cationic gold(I) complexes
[Ph3PAuAz]OTf (2–8) (Az = aziridine, 2-methylaziri-
dine, 2,2-dimethylaziridine, 2-ethylaziridine, 2-phenylaz-
iridine, N-benzylaziridine, N-hydroxyethylaziridine) was
observed.
2.1. Synthesis and spectra
The gold(I) complex Ph3PAuCl (1) reacts with stoichi-
ometric amounts (1:1) of the aziridines (Az = C2H4NH,
C2H3MeNH, C2H2Me2NH, C2H3EtNH, C2H3PhNH,
C2H4NBz, C2H4NC2H4OH) after treatment with
CF3SO3Ag (=AgOTf) and separation of the precipitated
AgCl, to give the ionic monoaziridine complexes
[Ph3PAuAz]OTf (2–8) in good yields (60–90%, Scheme
2). Without the addition of AgOTf no reaction is ob-
served. Even the strongly electrophilic intermediate
{Ph3PAuO3SCF3} is unable to induce the desired twofold
N–C opening reaction to give either the ionic gold(I) com-
plexes [Ph3PAuNX]OTf (X = H, R; nitrene stabilisation)
or [Ph3PAu(C2H2X2)]OTf (X = H, R; alkene coordina-
tion), respectively. Not even the simple N–C cleavage
R
N
+LnMCO
-CO
+LnM(CO)H
-CO
+LnMCO
-C2H4
H
R
LnM
R
N
N
LnM
LnM
N
R
O
aziridine
complex
nitrene
complex
β-aminoacyl
complex
Scheme 1. Reaction modes of aziridines with transition metal complexes.
R1
OTf
R1
N
R2
R2
N
+ AgOTf
Ph3P
Au
Cl
Ph3P
Au
R3
R3
- AgCl
1
2-8
7
2
3
4
5
6
8
R1
R2
R3
H
H
H
H
H
H
H
Bz EtOH
Me Me Et Ph
Me
H
H
H
H
H
H
H
Scheme 2. Synthesis of the gold(I)–aziridine complexes 2–8.

1988
I.-P. Lorenz et al. / Journal of Organometallic Chemistry 690 (2005) 1986–1993
reaction of the aziridines, followed by their oxidative
addition reaction to give a-iminomethyl complexes is ob-
served. The aziridine complexes 2–8 are colourless solids,
which melt (P100 ꢁC) without decomposition, and are air
sensitive as well as somewhat light sensitive. They are sol-
uble in polar solvents like acetone or CH2Cl2, but insolu-
ble in non-polar ones.
P–C coupling. The quartet for the CF3-carbon atom of
the OTfꢁ anion of 2–8 is always observed at about
122 ppm (1J(C,F) ꢀ 312 Hz).
In the 31P NMR spectra of 2–8 the signals are always
found at approximately 31 ppm (e.g. 30.0 ppm (8) and
31.3 ppm (6)).
In the FAB+ mass spectra of 2–8 the parent signals
for the intact cations are measured at m/z = 502.1 (2),
516.3 (3), 530.1 (4 and 5), 578.2 (6), 592.0 (7) and
546.1 (8). In all cases, signals for the fragments after
cleavage of the aziridine ligands are detected
The IR, 1H, 13C, 31P NMR and mass spectra of com-
pounds 2–8 were measured. The IR spectra show almost
the same absorptions between 500 and 4000 cmꢁ1, be-
cause the compounds all contain both the phenyl groups
of the PPh3 ligand and the aziridine rings in the cations,
as well as the same OTfꢁ anion. Only the spectrum of 8
shows additional absorptions at 3500 cmꢁ1 for m(OH)
and 1043 cmꢁ1 for m(C–O). The OTfꢁ anion is clearly
observed by its very strong and characteristic bands at
1150 cmꢁ1–1260 cmꢁ1 for m(CF) and m(SO).
([M+ ꢁ Az]). A peak at m/z = 721 for ½AuðPPh3Þþꢂ, often
2
observed for Ph3PAu containing species has not been
detected. The OTfꢁ anion present in 2–8 gives a signal
at m/z = 149.1 in the FABꢁ mass spectra.
2.2. X-ray structure analyses of 3, 4, 6 and 8
1
In the H NMR spectra of the NH-aziridine com-
plexes 2–6, a broad signal is found at 2.83–4.94 ppm
for the NH proton. The protons of the CH2 groups of
2 and 4 appear as singlets at 2.62 ppm, whereas those
of 3, 7 and 8 show two doublets at 2.43 and 2.69 ppm
(3J = 4.89 Hz, 3), 2.92 and 3.14 ppm (3J = 4.10 Hz, 7),
and 2.55 and 3.04 ppm (3J = 4.05 Hz, 8). Compound 5
shows two double doublets at 2.47 and 2.71 ppm
Single Crystals of 3, 4, 6 and 8 suitable for X-ray dif-
fraction analyses were obtained by the isothermic diffu-
sion of pentane into CH2Cl2 solutions. Relevant data
are summarised in Table 1, and the molecular structures
together with the most important bond lengths and
bond angles are given in Figs. 1–4.
All four compounds have the same linear arrange-
ment at the Au(I) centre with P–Au–N angles between
177.2(11)ꢁ (8) and 179.5(2)ꢁ (3), average Au–P distances
2
(3J ꢀ 6 Hz, J = 1.04 Hz, 5), whereas 6 shows a broad
signal at 3.25 ppm as well as a doublet at 3.07 ppm
(3J = 7.27 Hz). The proton in the 2-position of the rings
in 3, 5 and 6 gives either a broad multiplet at 3.04–3.13
ppm (3) and 3.07–3.25 ppm (6) or a resolved one at 2.99
ppm (ddt, 3J = 6.90 and 5.57 Hz, 5). The exo-NCH2 pro-
tons of 7 and 8 are observed as a singlet at 4.27 ppm (7)
or triplets at 3.13 ppm (t, 3J = 4.90 Hz) and 3.99 ppm (t,
3J = 4.75 Hz, CH2OH, 8). The proton of the hyrdoxy-
ethyl group in 8 gives a broad signal at 4.71 ppm. The
methyl protons in 2-position of 3–5 are found at 1.60
ppm (d, 3J = 5.89 Hz, 3), 1.51 and 1.61 ppm (s, 4) as well
˚
˚
of about 2.233 A, and Au–N distances of about 2.08 A,
with the exception of 4 where both distances are some-
˚
what longer (2.278(2) and 2.118(6) A). This may be
due to the steric effect of both Me groups in the 2-posi-
tion. The N atoms of the aziridines coordinate with their
distorted tetrahedral configuration towards the gold(I)
centres. Both N–C bond lengths in 4, 6 and 8 are nearly
˚
equal and are about 1.50 A, whereas those in 3 differ sig-
˚
nificantly (1.603(13) and 1.381(7) A), possibly because of
the presence of the non-equivalent CH2 and CHMe moi-
eties. The C–C ring distances of complexes 6 and 8 are
3
as 1.19 ppm (t, J = 7.35 Hz, 5). The phenyl protons of
˚
very similar (1.478(8) and 1.467(7) A), whereas those
˚
in 3 and 4 differ significantly (1.408(2) and 1.542(2) A).
the PPh3 ligands of 2–8 and those in the 2-position
(6), or N-bound (7) give multiplets in the same region
(7.37–7.76 ppm), whereby assignments were made
when possible based on the P–C coupling modes
(see Section 4).
Again, both the methyl substituted aziridine complexes
3 and 4 show this characteristic. Moreover, although 3
shows the longest N–C and shortest C–C bonds, it
was not possible to induce the desired alkene elimination
to form the nitrene complex [Ph3PAu@NH]OTf. Per-
haps the introduction of a bulky substituent on N for ki-
netic stabilisation reasons is necessary. The planes of the
aziridine ligands are bent against the Au–N axis with an-
gles of 66.91ꢁ (3), 67.98ꢁ (4), 69.46ꢁ (6) and 71.24ꢁ (8).
A look at the molecular structure of 6 (Fig. 3) shows
that the phenyl group in the 2-position is very close to
the central Au atom, and its ring plane is bent towards
the metal. The resulting average distance between Au
In the 13C NMR spectra of 2, 7 and 8 only one signal
is found at 24.6 ppm (2), 35.2 (7) and 34.5 ppm (8) for
both ring CH2 groups, and also one for the CH2 group
in 3 (32.0 ppm), 4 (39.9 ppm), 5 (31.8 ppm), and 6 (30.7
ppm). The C-atom in the 2-position of 3–6 gives signals
at 34.2 ppm (3), 40.9 ppm (4), 38.7 ppm (5) and 37.6
ppm (6). For the N-bound CH2 groups of 7 and 8, sig-
nals are found at 66.7 ppm (7) and 61.1 ppm (8), and the
O-bound CH2 group gives a signal at 66.3 ppm (8). The
phenyl C-atoms in the 2-position of 6 and of the benzyl
ligand of 7 show multiplets at 128–137 ppm, and those
of the PPh3 ligands of 2–8 in the same region also as
multiplets, but with doublet character because of the
˚
and the six phenyl C-atoms is about 4.00 A, which
means there is obviously some Au–p-ring interaction
due to either electronic reasons or packing effects.

I.-P. Lorenz et al. / Journal of Organometallic Chemistry 690 (2005) 1986–1993
1989
Table 1
Summary of crystallographic data for 3, 4, 6 and 8 [14]
Compound
3
4
6
8
Empiric formula
Formula weight (g molꢁ1
Crystal size (mm)
Crystal colour, habit
Crystal system
C22H22AuF3NO3S
665.40
C23H24AuF3NO3PS
679.43
C27H24AuF3NO3PS
727.47
C23H24AuF3NO4PS
695.43
)
0.18 · 0.11 · 0.04
Colourless, plate
Monoclinic
0.20 · 0.20 · 0.05
Colourless, plate
Triclinic
0.25 · 0.10 · 0.06
Colourless, stick
Monoclinic
P21/n
0.55 · 0.44 · 0.40
Colourless, prismatic
Monoclinic
P21/n
ꢀ
ꢀ
Space group
˚
P1
P1
9.667(7)
a (A)
˚
15.003(3)
8.9403(18)
18.710(4)
90
8.9911(18)
11.599(2)
26.464(5)
90
10.06790(10)
9.48250(10)
25.9465(2)
90
b (A)
9.949(7)
15.245(11)
99.807
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
107.44(3)
90
106.514(9)
103.370(11)
1323.1(16)
2
97.16
90
1.765
91.1160 (5)
90
3
˚
V (A )
2394.3(8)
4
1.846
2476.61(4)
4
1.865
Z
4
1.765
Dcalc (g cmꢁ3
)
1.705
5.743
660
Absorption coefficient (mmꢁ1
F(000)
Index ranges
)
6.345
1288
5.556
1416
6.142
1352
ꢁ17 6 h 6 17,
ꢁ10 6 k 6 10,
ꢁ22 6 l 6 22
3.23–25.08
26421
ꢁ11 6 h 6 11,
ꢁ7 6 k 6 7,
ꢁ19 6 l 6 19
1.44–27.15
6980
ꢁ11 6 h 6 11,
ꢁ15 6 k 6 14,
ꢁ34 6 l 6 34
3.13–27.47
46429
ꢁ11 6 h 6 11,
ꢁ10 6 k 6 10,
ꢁ29 6 l 6 29
1.57–24.00
24884
h Range (ꢁ)
Reflections collected
Independent reflections
Observed reflections
Parameter/restrains
R1/wR2 (all data)
R1/wR2 (final)
4237
2932
3545
3084
6240
4939
3895
3168
285/0
304/0
334/0
311/0
0.0772/0.1082
0.0443/0.0962
1.035
0.0480/0.0976
0.0405/0.0943
1.050
0.0602/0.0963
0.0407/0.0893
1.039
0.0380/0.1105
0.0280/0.0960
1.147
Goodness-of-fit
ꢁ3
˚
Minimum/maximum qe (e A
T (K)
)
ꢁ1.764/1.131
200(2)
ꢁ2.515/1.066
200(2)
ꢁ1.645/3.731
200(2)
ꢁ2.325/0.933
200(2)
Diffractometer used
Scan type
Solution
Nonius Kappa CCD
Area detection
SHELXS-97
SHELXS-97
255032
Siemens SMART Area-detector
Area detection
SHELXS-97
SHELXS-97
254788
Nonius Kappa CCD
Area detection
SHELXS-97
SHELXS-97
255033
Nonius Kappa CCD
Area detection
SHELXS-97
SHELXS-97
255030
Refinement
Deposit number
A very similar effect is observed in compound 8 (Fig. 4)
with the N-bound hydroxyethyl group. The O-atom of
the hydroxy group lies very close to the Au centre, with
for the cationic induced polymerisation reaction of aziri-
dines ((–N(R)–CH2–CH2–)n). Compound 1 is also unsuit-
able to undergo an oxidative addition reaction leading to
a-iminomethyl complexes of gold(III) (H–Au+–CH2–
CH@NR). With respect to the cleavage of both N–C
bonds, 1 cannot be used for the synthesis of nitrene com-
plexes (Au@N–R). This is surprising because the use of
gold(I) complexes in catalysis is steadily increasing. Be-
cause in special cases [7,10–12] one N–C bond has been
opened to give b-aminoacyl complexes, further investiga-
tions should be focussed on influencing the reactivity of
aziridine ligands by using suitable substituents at N- or
C-atoms.
˚
the short Au–O distance of 3.078 A, which is signifi-
cantly shorter than the sum of the van der Waal radii.
The short Au–O distance observed in
8 arises
even although there is no deviation from linearity of
the P–Au–N moiety and no peculiar Au–Au interaction.
Interestingly, despite these observations no significant
1
shifts of the corresponding signals in the IR or H and
13C NMR spectra of 6 and 8 were observed.
3. Conclusions
The synthesis of the new complexes 2–8 indicates that
even the strong electrophilic complex {Ph3PAuO3SCF3},
which is the resulting intermediate in the reaction of
Ph3PAuCl (1) with CF3SO3Ag, cannot cleave one or both
N–C bonds of the aziridines. Therefore, with respect to
the first case, 1 does not appear to be active as a catalyst
4. Experimental
4.1. General procedures
All operations were carried out under Ar in dry
solvents. Ph3PAuCl (1) was prepared according to the

1990
I.-P. Lorenz et al. / Journal of Organometallic Chemistry 690 (2005) 1986–1993
˚
Fig. 1. Molecular structure of 3: selected bond lengths (A) and angles (ꢁ): Au(1)–N(1) 2.073(6), Au–P(1) 2.231(2), N(1)–C(19) 1.603(13), N(1)–C(20)
1.381(7), C(19)–C(20) 1.408(19), C(20)–C(21) 1.307(17); N(1)–Au(1)–P(1) 179.5(2), C(19)–N(1)–C(20) 55.7(8), C(19)–N(1)–Au(1) 125.1(6), C(20)–
N(1)–Au(1) 128.1(7), N(1)–C(20)–C(19) 54.1(6), N(1)–C(20)–C(21) 113.6(11).
˚
Fig. 3. Molecular structure of 6: selected bond lengths (A) and angles
˚
Fig. 2. Molecular structure of 4: selected bond lengths (A) and angles
(ꢁ): Au(1)–N(1) 2.082(4), Au(1)–P(4) 2.2368(15), N(1)–C(2) 1.504(7),
N(1)–C(1) 1.467(7), C(1)–C(2) 1.478(8), C(2)–C(3) 1.494(8), C(3)–C(4)
(ꢁ): Au(1)–N(1) 2.118(6), Au(1)–P(1) 2.278(2), N(1)–C(2) 1.513(10),
N(1)–C(1) 1.540(12), C(1)–C(2) 1.542(14), C(2)–C(4) 1.517(12), C(2)–
C(3) 1.531(12); N(1)–Au(1)–P(1) 178.4(2), C(2)–N(1)–C(1) 60.7(6),
C(2)–N(1)–Au(1) 122.6(5), C(1)–N(1)–Au(1) 122.7(5), N(1)–C(1)–C(2)
58.8(6), N(1)–C(2)–C(4) 115.3(6), N(1)–C(2)–C(3) 114.0(7), C(4)–C(2)–
C(3) 117.9(10), N(1)–C(2)–C(1) 60.5(6), C(4)–C(2)–C(1) 117.7(8),
C(3)–C(2)–C(1) 118.3(8).
1.387(8); N(1)–Au(1)–P(4) 178.04(13), C(1)–N(1)–C(2) 59.4(4), C(2)–
N(1)–Au(1) 119.3(3), C(1)–N(1)–Au(1) 124.0(4), N(1)–C(1)–C(2)
61.5(4), N(1)–C(2)–C(3) 116.1(4), C(1)–C(2)–N(1) 61.5(4).
N-benzylaziridine were prepared according to the litera-
ture procedure [17–21]. NMR spectra were recorded on
a Jeol 270 spectrometer (1H: 270.17 MHz, 13C: 67.94
MHz and 31P: 109.37 MHz) in [D6]-acetone. Mass
spectra were obtained on a Jeol Mstation JMS 700. IR
literature procedure [15,16]. N-Hydroxyethylaziridine
was purchased from Acros. 2-Methylaziridine, 2,2-dime-
thylaziridine, 2-ethylaziridine, 2-phenylaziridine and

I.-P. Lorenz et al. / Journal of Organometallic Chemistry 690 (2005) 1986–1993
1991
˚
Fig. 4. Molecular structure of 8: selected bond lengths (A) and angles (ꢁ): Au–N 2.090(6), Au(1)–P(1) 2.2327(17), N(1)–C(3) 1.475(6), N(1)–C(1)
1.485(7), N(1)–C(2) 1.494(7), C(1)–C(2) 1.467(7), C(3)–C(4) 1.489(7), C(4)–O(4) 1.420(6); N(1)–Au(1)–P(1) 177.25(14), C(3)–N(1)–C(1) 113.8(5),
C(3)–N(1)–C(2) 114.4(5), C(1)–N(1)–C(2) 59.0(3), C(3)–N(1)–Au(1) 117.3(3), C(1)–N(1)–Au(1) 121.5(3), C(2)–N(1)–Au(1) 117.8(3), C(2)–C(1)–N(1)
60.8(4), C(1)–C(2)–N(1) 60.2(3), N(1)–C(3)–C(4) 112.8(5), O(4)–C(4)–C(3) 111.6(4).
spectra were measured on a Perkin–Elmer Spectrum
One FT-IR-spectrometer. Elemental analyses were per-
formed on a Heraeus Elementar Vario EL.
(m, 15 H, CHarom.). 13C NMR ([D6]-acetone, 67.94
MHz): d 24.6 (Az–CH2), 122.1 (q, 1J(C,F) = 321.65
Hz, CF3), 128.2 (d, 1J(C,P) = 64.37 Hz, CHarom.),
130.0 (d, 3J(C,P) = 12.66 Hz, m-CHarom.), 132.9 (d,
4J(C,P) = 3.12 Hz, p-CHarom.), 134.6 (d, 2J(C,P) =
14.54 Hz, o-CHarom.). 31P NMR ([D6]-acetone, 109.37
MHz): d 30.8 (PPh3). IR (KBr) [cmꢁ1]: 3260 (w), 3085
(w), 3048 (w), 2960 (w), 2923 (w), 2857 (w), 1622 (w),
1591 (w), 1576 (w), 1482 (m), 1437 (s), 1333 (w), 1259
(vs), 1228 (m), 1161 (s), 1103 (s), 1120 (w), 1103 (s),
1073 (w), 1031 (vs), 998 (w), 931 (w), 856 (w), 750 (m),
712 (m), 694 (s), 654 (m), 638 (s), 574 (w), 544 (s), 510
(m), 452 (w). Elemental analysis (%) C21H20AuF3-
NO3PS (651.39): calc. C, 38.73; H, 3.09; N, 2.15; found:
C, 39.23; H, 3.43; N, 2.50%. MS (FAB+): m/z
(%) = 502.1 (79) [M+], 459.1 (100) [M+ ꢁ Az].
4.1.1. General procedure
Ph3PAuCl (1) was dissolved in 20 ml of dichlorome-
thane, AgOTf was added and the solution was stirred
for 15 min until all the AgCl had precipitated. After cen-
trifugation and separation of the solution by decanta-
tion, a small excess of the aziridine was added. After
stirring the solution for about 1 h, the solvent was evap-
orated, and the colourless residue was purified by stir-
ring in n-hexane, followed by filtration and drying the
colourless solid in vacuo.
4.2. [Aziridine-triphenylphosphanegold(I)]-
trifluormethylsulfonate (2)
4.3. [2-Methylaziridine-triphenylphosphanegold(I)]-
trifluomethylsulfonate (3)
113.0 mg (0.235 mmol) Ph3PAuCl (1), 66.0 mg (0.258
mmol) AgOTf, 10.0 ll (0.258 mmol) aziridine. Yield:
99.5 mg (0.153 mmol, 65%), colourless powder; m.p.
115–117 ꢁC. H NMR ([D6]-acetone, 270.17 MHz): d
2.62 (s, 4 H, Az–CH2), 2.83 (br, 1 H, NH), 7.61–7.65
85.0 mg (0.172 mmol) Ph3PAuCl (1), 49.0 mg (0.189
mmol) AgOTf, 61.3 ll (0.189 mmol) 2-methylaziridine.
Yield: 97.0 mg (0.146 mmol, 85%), colourless crystals;
1

1992
I.-P. Lorenz et al. / Journal of Organometallic Chemistry 690 (2005) 1986–1993
1
m.p. 110 ꢁC. H NMR ([D6]-acetone, 270.17 MHz): d
2J = 1.04 Hz, 1 H, Az–CH2), 2.71 (dd, 3J = 6.75 Hz,
3
3
3
1.60 (d, J = 5.81 Hz, 3 H, CH3), 2.43 (d, J = 4.89, 1
H, Az–CH2), 2.69 (d, 3J = 4.89 Hz, 1 H, Az–CH2),
3.04–3.13 (m, 1 H, Az–CH), 7.57–7.76 (m, 15 H, CHarom.).
13C NMR ([D6]-acetone, 67.94 MHz) d 19.4 (CH3), 32.0
(Az–CH2), 34.2 (Az–CH2), 122.3 (q, 1J(C,F) = 321.64
Hz, CF3), 127.9 (d, J(C,P) = 64.37 Hz, CHarom.), 129.8
(d, 3J(C, P) = 12.46 Hz, m-CHarom.), 132.9 (d,
4J(C,P) = 3.11 Hz, p-CHarom.), 134.3 (d, J(C,P) = 13.50
Hz, o-CHarom.). 31P NMR ([D6]-acetone, 109.37 MHz) d
31.2 (PPh3). IR (KBr) [cmꢁ1]: 3172 (m), 3056 (w), 3016
(w), 2990 (w), 2928 (w), 2864 (w), 1627 (m), 1586 (w),
1574 (w), 1480 (m), 1437 (vs), 1408 (w), 1372 (w), 1330
(w), 1275 (vs), 1256 (vs), 1226 (s), 1165 (vs), 1102 (s),
1046 (s), 1028 (vs), 998 (m), 927 (w), 845 (w), 748 (s),
713 (s), 693 (vs), 656 (s), 637 (s), 545 (s), 501 (s). Elemental
analysis (%) C22H22AuF3NO3PS (679.45): calc. C, 39.71;
H, 3.33; N, 2.10; S, 4.82; found: C, 40.35; H, 3.35; N,
2.21; S, 4.81%. MS (FAB+): m/z (%) = 516.3 [M+] (100),
459.2 [M+ ꢁ Az] (95).
2J = 1.04 Hz, 1 H, Az–CH2), 2.99 (ddt, J = 6.90 Hz,
3J = 5.57 Hz, 1 H, Az–CH), 4.62 (br, 1 H, NH), 7.58–
7.72 (m, 15 H, CHarom.). 13C NMR ([D6]-acetone,
67.94 MHz): d 11.4 (CH3), 28.1 (CH2), 31.8 (Az–CH2),
38.7 (Az–CH), 122.2 (q, 1J(C,F) = 321.53 Hz, CF3),
128.6 (d, 1J(C,P) = 64.10 Hz, CHarom.), 130.5 (d,
3J(C,P) = 11.94 Hz, m-CHarom.), 133.4 (d, 4J(C,P) =
2.60 Hz, p-CHarom.), 135.0 (d, 2J(C,P) = 13.49 Hz,
o-CHarom.). 31P NMR ([D6]-acetone, 109.37 MHz): d
31.2 (PPh3). IR (KBr) [cmꢁ1]: 3180 (m), 3055 (w), 311
(w), 2960 (w), 2931 (w), 2872 (w), 1618 (w), 1588 (w),
1574 (w), 1480 (w), 1438 (w), 1380 (w), 1336 (w), 1288
(vs), 1252 (vs), 1226 (s), 1164 (s), 1102 (vs), 1048 (s),
1029 (vs), 998 (m), 923 (w), 843 (w), 749 (vs), 713 (s),
694 (vs), 657 (s), 637 (vs), 574 (m), 545 (vs), 500 (s). Ele-
mental analysis (%) C23H24AuF3NO3PS (679.45): calc.
C, 40.66; H, 3.56; N, 2.06; found: C, 40.85; H, 3.72;
N, 2.06%. MS (FAB+): m/z (%) = 530.1 (100) [M+],
459.1 (33) [M+ ꢁ Az].
1
2
4.4. [2,2-Dimethylaziridine-triphenylphosphanegold(I)]-
trifluormethylsulfonate (4)
4.6. [2-Phenylaziridine-triphenylphosphanegold(I)]-
trifluormethylsulfonate (6)
167.0 mg (0.336 mmol) Ph3PAuCl (1), 98.3 mg (0.381
mmol) AgOTf, 30.7 ll (0.258 mmol) 2,2-dimethylaziri-
dine. Yield: 211.0 mg (0.311 mmol, 92%), colourless
136.2 mg (0.283 mmol) Ph3PAuCl (1), 80.0 mg (0.311
mmol) AgOTf, 36.0 ll (0.311 mmol) 2-phenylaziridine.
Yield: 125.3 mg (0.173 mmol, 61%), colourless powder;
m.p. 120–123 ꢁC. 1H NMR ([D6]-acetone, 270.17 MHz):
1
crystals; m.p. 129 ꢁC. H NMR ([D6]-acetone, 270.17
3
MHz): d 1.54 (s, 3 H, CH3), 1.61 (s, 3 H, CH3), 2.61
(s, 2 H, Az–CH2), 4.43 (br, 1 H, NH), 7.59–7.69 (m,
15 H, CHarom.). 13C NMR ([D6]-acetone, 67.94 MHz):
d 23.5 (CH3), 26.3 (CH3), 39.9 (Az–CH2), 40.9 (Cq),
122.2 (q, 1J(C,F) = 321.63 Hz, CF3), 128.7 (d,
1J(C,P) = 63.84 Hz, Cq), 130.5 (d, 3J(C,P) = 12.0 Hz,
m-CHarom.), 133.4 (d, 4J(C,P) = 2.24 Hz, p-CHarom.),
135.0 (d, 2J(C,P) = 13.72 Hz, o-CHarom.). 31P NMR
([D6]-acetone, 109.37 MHz): d 31.2 (PPh3). IR (KBr)
[cmꢁ1]: 3172 (w), 3055 (w), 2975 (w), 2923 (w), 2850
(w), 1629 (m), 1588 (s), 1482 (w), 1437 (vs), 1390 (m),
1333 (m), 1282 (vs), 1252 (vs), 1226 (s), 1167 (vs), 1103
(s), 1047 (vs), 1028 (vs), 998 (m), 912 (w), 806 (w), 751
(s), 713 (s), 694 (vs), 656 (vs), 638 (vs), 544 (vs), 510
(s). Elemental analysis (%) C23H24AuF3NO3PS (679.45):
calc. C, 40.66; H, 3.56; N, 2.06; found: C, 40.02; H,
3.42; N, 2.07%. MS (FAB+): m/z (%) = 530.1 (100)
[M+], 459.1 (28) [M+ ꢁ Az].
d 3.07 (d, J = 7.27 Hz, 1 H, Az–CH2), 3.25 (br, 1 H,
Az–CH2), 4.10 (t, 3J = 6.38 Hz, 1 H, Az–CH), 4.94
(br, 1 H, NH), 7.37–7.45 (m, 5 H, CHarom.), 7.46–7.65
(m, 15 H, CHarom.). 13C NMR ([D6]-acetone, 67.94
MHz) d 30.7 (Az–CH2), 37.6 (Az–CH2), 128.1 (d,
1J(C,P) = 65.39 Hz, CHarom.), 128.5 (CHarom.), 128.7
(CHarom.), 129.4 (CHarom.), 129.5 (CHarom.), 129.9 (d,
3J(C,P) = 12.46 Hz, m-CHarom.), 132.3 (CHarom.), 132.8
(d, J(C,P) = 3.11 Hz, p-CHarom.), 134.4 (d, J(C,P) =
13.49 Hz, o-CHarom.). 31P NMR ([D6]-acetone, 109.37
MHz) d 31.3 (PPh3). IR (KBr) [cmꢁ1]: 3261 (w), 3057
(w), 1635 (m), 1606 (m), 1496 (w), 1481 (w), 1437 (s),
1396 (w), 1333 (w), 1257 (vs), 1167 (s), 1102 (m), 1071
(w), 1031 (s), 998 (w), 889 (w), 862 (w), 754 (m), 712
(m), 694 (s), 638 (s), 575 (w), 544 (s), 509 (m). Elemental
analysis (%) C27H24AuF3NO3PS (727.47): calc. C, 44.58;
H, 3.30; N, 1.93; found: C, 45.51; H, 3.41; N, 2.24%.
MS (FAB+): m/z (%) = 578.2 (100) [M+], 469.2 (60)
[M+ ꢁ Az].
4
2
4.5. [2-Ethylaziridine-triphenylphosphanegold(I)]-
trifluormethylsulfonate (5)
4.7. [N-Benzylaziridine-triphenylphosphanegold(I)]-
trifluormethylsulfonate (7)
88.9 mg (0.185 mmol) Ph3PAuCl (1), 49.2 mg (0.192
mmol) AgOTf, 16.6 ll (0.190 mmol) 2-ethylaziridine.
Yield: 105.0 mg (0.155 mmol, 82%), colourless powder;
105.3 mg (0.219 mmol) Ph3PAuCl (1), 56.7 (0.221
mmol) AgOTf, 30.2 ll (0.220 mmol) N-benzylaziridine.
Yield: 142.0 mg (0.191 mmol, 86%), colourless powder;
m.p. 96 ꢁC. H NMR ([D6]-acetone, 270.17 MHz): d
2.92 (d, J = 4.08 Hz, 2 H, Az–CH2), 3.14 (d, J = 4.15
1
m.p. 97 ꢁC. H NMR ([D6]-acetone, 270.17 MHz): d
1.19 (t, 3J = 7.35 Hz,
3
H, CH3), 1.82 (dq,
3
1
3J = 3J = 7.27 Hz, 2 H, CH2), 2.47 (dd, J = 5.27 Hz,

I.-P. Lorenz et al. / Journal of Organometallic Chemistry 690 (2005) 1986–1993
1993
Hz, 2 H, Az–CH2), 4.22 (s, 2 H, Ph-CH2), 7.36–7.45 (m,
5 H, Bz–H), 7.54–7.75 (m, 15 H, CHarom.). 13C NMR
([D6]-acetone, 67.94 MHz): d 35.2 (Az–CH2), 66.7 (Ph-
tions were then worked up as described above, and the
original complexes 2–8 were obtained.
Solutions of 2–8 in THF were irradiated with a UV
lamp (Hg, 125 W) for about 2 h. The same work-up
of the solutions yielded the original compounds 2–8.
In both cases, no alkene elimination and no formation
of the desired nitrene complexes was observed.
1
CH2-N), 122.4 (q, J(C,F) = 322.34 Hz, CF3), 128.4 (d,
1J(C,P) = 66.05 Hz, Cq, arom.), 129.9 (p-Bz–C), 129.9
(o-Bz–C), 130.4 (d, 3J(C,P) = 11.94 Hz, m-CHarom.),
130.6 (m-Bz–C), 133.3 (d, 4J(C,P) = 2.34 Hz, p-CHarom.),
134.9 (d, 2J(C,P) = 13.49 Hz, o-CHarom.), 137.7 (Bz–Cq).
31P NMR ([D6]-acetone, 109.37 MHz) d 30.2 (PPh3). IR
(KBr) [cmꢁ1]: 3063 (w), 3026 (w), 2989 (w), 2923 (w),
2814 (w), 1605 (w), 1586 (w), 1495 (m), 1481 (m), 1438
(s), 1331 (w), 1260 (vs), 1224 (s), 1155 (s), 1102 (vs),
1047 (s), 1031 (vs), 998 (m), 923 (w), 869 (w), 823 (w),
748 (vs), 713 (s), 693 (vs), 656 (s), 637 (vs), 572 (m),
545 (vs), 501 (s). Elemental analysis (%) C28H26AuF3-
NO3PS (741.52): calc. C, 45.35; H, 3.53; N, 1.89; found:
C, 46.59; H, 3.78; N, 2.14%. MS (FAB+): m/z
(%) = 592.0 (28) [M+], 459 (21) [M+ ꢁ Az].
References
[1] D. Milstein, J.C. Calabrese, J. Am. Chem. Soc. 104 (1982) 3773–
3774, and references cited therein.
[2] I.-P. Lorenz, S. Drobnik, G. Beuter, A. Lubik, Chem. Ber. 125
(1992) 2363–2366.
[3] R. Lussier, J.O. Edwards, R. Eisenberg, Inorg. Chim. Acta 3
(1969) 468–470.
[4] R. Ho¨fer, A. Engelmann, W. Beck, Chem. Ber. 106 (1973) 2590;
W. Beck, W. Danzer, R. Ho¨fer, Angew. Chem., Int. Ed. Engl. 12
(1973) 77.
[5] W. Danzer, R. Ho¨fer, H. Menzel, B. Olgemo¨ller, W. Beck, Z.
Naturforsch. B 39 (1984) 167;
T. Hauck, K. Sunkel, W. Beck, Inorg. Chim. Acta 235 (1995) 391.
¨
4.8. [N-Hydroxyethylaziridine-triphenylphosphane-
gold(I)]trifluormethylsulfonate (8)
[6] D.C. Ware, B.G. Siim, K.G. Robinson, W.A. Denny, P.J.
Brothers, G.R. Clark, Inorg. Chem. 30 (1991) 3750–3757.
[7] R. Ben Cheikh, M.C. Bonnet, R. Chaabonni, F. Dahan, J.
Organomet. Chem. 438 (1992) 217–228.
87.1 mg (0.235 mmol) Ph3PAuCl (1), 66.5 mg (0.259
mmol) AgOTf, 20.1 ll (0.259mmol) N-hydroxyethylazir-
idine. Yield: 112.0 mg (0.161 mmol, 88%), colourless
[8] S.v. Beckerath, I.-P. Lorenz, R. Fawzi, M. Steinmann, Z.
Naturforsch. B 51 (1996) 959;
1
crystals; m.p. 118 ꢁC. H NMR ([D6]-acetone, 270.17
3
I.-P. Lorenz, S.v. Beckerath, H. No¨th, Eur. J. Inorg. Chem.
(1998) 645.
MHz): d 2.55 (d, J = 4.01 Hz, 2 H, Az–CH2), 3.04 (d,
3
3J = 4.08 Hz, 2 H, Az–CH2), 3.13 (t, J = 4.90 Hz, 3
[9] R. Wilberger, H. Piotrowkski, M. Warchhold, I.-P. Lorenz, Z.
Anorg. Allg. Chem. 629 (2003) 2485;
3
H, N–CH2), 3.99 (t, J = 4.75 Hz, 3 H, CH2OH), 4.71
(br, 1 H, OH), 7.50–7.72 (m, 15 H, CHarom.). 13C
NMR ([D6]-acetone, 67.94 MHz): d 34.5 (Az–CH2),
61.1 (N–CH2), 66.3 (CH2OH), 122.3 (q, 1J(C,F) =
321.09 Hz, CF3), 128.8 (d, 1J(C,P) = 67.99 Hz, Cq, arom.),
130.4 (d, 3J(C,P) = 11.94 Hz, m-CHarom.), 133.3 (d,
R. Wilberger, C. Krinninger, H. Piotrowski, P. Mayer, M.
Ossberger, I.-P. Lorenz, Z. Anorg. Allg. Chem. 630 (2004)
1495–1500.
[10] W. Beck, W. Danzer, A.T. Liu, G. Huttner, H. Lorenz, Angew.
Chem., Int. Ed. Engl. 15 (1976) 495.
[11] G.A. Jones, L.G. Guggenberger, Acta Crystallogr., Sect. B 31
(1975) 900.
4J(C,P) = 2.34
Hz,
p-CHarom.),
135.1
(d,
2J(C,P) = 13.75 Hz, o-CHarom.). 31P NMR ([D6]-ace-
tone, 109.37 MHz): d 30.0 (PPh3). IR (KBr) [cmꢁ1]:
3502 (s), 3072 (w), 3050 (w), 2989 (w), 2953 (w), 2828
(w), 1630 (w), 1588 (w), 1574 (w), 1480 (s), 1436 (s),
1364 (w), 1330 (w), 1261 (vs), 1231 (s), 1176 (s), 1103
(vs), 1043 (vs), 999 (m), 936 (w), 882 (w), 748 (vs), 713
(s), 693 (vs), 652 (s), 579 (w), 545 (vs), 501 (s), 449 (w).
Elemental analysis (%) C23H24AuF3NO4PS (695.45):
calc. C, 39.72; H, 3.48; N, 2.01; found: C, 40.33; H,
3.50; N, 2.05%. MS (FAB+): m/z (%) = 546.1 (35)
[M+], 459 (88) [M+ ꢁ Az].
[12] J. Protas, P. Controt, A. El Gadi, Acta Crystallogr., Sect. C 45
(1989) 1189.
[13] D. Tanner, Angew. Chem., Int. Ed. Engl. 33 (1994) 599–619, and
references cited therein.
[14] Crystallographic data for the structural analysis has been depos-
ited with the Cambridge Crystallographic Data Centre, CCDC
No. 255032 for compound 3, CCDC No. 254788 for compound 4,
CCDC No. 255033 for compound 6, CCDC No. 255030 for
compound 8. Copies of this information may be obtained free of
charge from the Director, CCDC, 12, Union Road, Cambridge
CB2 1EZ, UK [fax: +44 1223 336 033 or e-mail deposit@ccdc.ca-
m.ac.uk or www.ccdc.cam.ac.uk].
[15] C.A. McAuliffe, R.V. Parish, P.D. Randall, J. Chem. Soc., Dalton
Trans. (1979) 1730–1735.
[16] F.G. Mann, A.F. Wells, D. Purdie, J. Chem. Soc. (1937) 1828–
1836.
4.9. Thermal and photolytic experiments for alkene
elimination of 2–8
[17] H. Wenker, J. Am. Chem. Soc. 57 (1935) 2328.
[18] S. Gabriel, H. Ohle, Chem. Ber. 50 (1917) 804–818.
[19] T.L. Cairns, J. Am. Chem. Soc. 63 (1941) 871–872.
[20] S. Brois, J. Org. Chem. 27 (1962) 3532–3534.
All compounds were dissolved in CH2Cl2 and kept
under reflux conditions for about 1 h. The clear solu-
[21] R. Appel, R. Kleinstuck, Chem. Ber. 107 (1974) 5–12.
¨