(Phenylethynyl)trimethylphosphonium bromide and bromoaurates(I)

Article abstract of DOI:10.1515/znb-2006-0806

(Phenylethynyl)trimethylphosphonium bromide (1) has been reinvestigated by NMR spectroscopy and its crystal structure determined. In the monoclinic crystals, the cations are arranged in layers in the a-c planes, with their P-CsC-Ph axes parallel within one layer, but alternating in consecutive layers. The bromide anions are accommodated in channels between the cations. The spectroscopic and structural results are in agreement with the special reactivity pattern documented for ethynylphosphonium salts, in particular with the sensitivity to nucleophiles which e.g. prevents standard ylide formation. A slurry of polymeric phenylethynylgold [PhC≡CAu]_n in dichloromethane reacts with [Me₃PC=CPh]Br to give a clear solution of [Me₃PC≡CPh]⁺ [PhC≡CAuBr]^- (2). In a similar reaction, with soluble pentafluorophenylgold(tetrahydrothiophene), C₆F₅Au(IhI), the salt [Me₃PC≡CPh] ⁺ [C₆F₅AuBr]^- (3) is produced. All attempts to generate gold(I) complexes of the corresponding phosphonium ylide [Me₂(PhC≡C)P≡CH₂] by treatment of the two phosphonium salts (2,3) with strong base were not successful owing to side reactions induced by base.

Full text of DOI:10.1515/znb-2006-0806

(Phenylethynyl)trimethylphosphonium Bromide and Bromoaurates(I)
Oliver Schuster and Hubert Schmidbaur
Department Chemie, Technische Universita¨t Mu¨nchen, Lichtenbergstraße 4, D-85747 Garching,
Germany
Reprint requests to Prof. H. Schmidbaur. Fax +49 (0)89 2891 3125.
E-mail: H.Schmidbaur@lrz.tum.de
Z. Naturforsch. 61b, 961 – 967 (2006); received May 2, 2006
(Phenylethynyl)trimethylphosphonium bromide (1) has been reinvestigated by NMR spectroscopy
and its crystal structure determined. In the monoclinic crystals, the cations are arranged in layers
in the a-c planes, with their P-C≡C-Ph axes parallel within one layer, but alternating in consec-
utive layers. The bromide anions are accommodated in channels between the cations. The spec-
troscopic and structural results are in agreement with the special reactivity pattern documented for
ethynylphosphonium salts, in particular with the sensitivity to nucleophiles which e. g. prevents stan-
dard ylide formation. A slurry of polymeric phenylethynylgold [PhC≡CAu]n in dichloromethane
reacts with [Me3PC≡CPh]Br to give a clear solution of [Me3PC≡CPh]+ [PhC≡CAuBr]− (2). In
a similar reaction, with soluble pentafluorophenylgold(tetrahydrothiophene), C6F5Au(tht), the salt
[Me3PC≡CPh]+ [C6F5AuBr]− (3) is produced. All attempts to generate gold(I) complexes of the
corresponding phosphonium ylide [Me2(PhC≡C)P=CH2] by treatment of the two phosphonium salts
(2, 3) with strong base were not successful owing to side reactions induced by base.
Key words: Ethynylphosphonium Salts, Phosphonium Salts, Bromoaurates(I), Aurates(I)
Introduction
In recent work the first examples of tri(alkyn-
yl)gold(III) complexes (RC≡C)3Au(L) have been pre-
pared. A strong trialkylphosphine donor L is required
in order to obtain stable compounds which can be iso-
lated and structurally characterized, as shown e. g. for
(PhC≡C)3Au(PMe3) and its dichloromethane solvate.
The donor capacity of triarylphosphines like Ph3P is
not sufficient to lend a comparable stability [1].
However, in the series of exploratory experiments
it was observed by serendipity that phosphonium
ylides may also function as auxiliary ligands L, as
demonstrated for the complex [Me2(PhC≡C)PCH2]
Au(C≡CPh)3 (I). This compound was obtained as
a minor by-product in the reaction of (thf)AuCl3 or
(thf)AuBr3 with PhC≡CLi (molar ratio 1 : 3) followed
by the addition of Me3P and fully characterized by
structural methods [1].
Formula I.
produced in step a) can quaternize the Me3P ligand
present in the reaction mixture to give the phospho-
nium salts [Me3PC≡CPh]+ Cl/Br−. c) After reduc-
tive elimination of alkynes in step a) there is an ex-
cess of PhC≡CLi left in solution which can act on
the phosphonium salts as a base to generate the ylide
Me2(PhC≡C)P=CH2. d) This ylide can trap any sol-
vated Au(C≡CPh)3 or react with its Me3P adduct to
give the ylide complex. (It has been established previ-
ously beyond doubt that non-stabilized phosphonium
ylides like Me3PCH2 are superior ligands for gold(I)
and gold(III) as compared to most other donors includ-
ing in particular tertiary phosphines [2 – 4].)
To rationalize the unexpected result the following
In an attempt to prove this reaction sequence,
steps were assumed for the overall reaction: a) The some of the proposed intermediates have been pre-
partial substitution, PhC≡C for Cl/Br, in (thf)AuCl3 or pared and subsequently subjected to the respec-
(thf)AuBr3 is accompanied by some reductive elimina- tive treatment, but the expected gold(I) complex
tion of PhC≡C-C≡C or PhC≡CCl/Br leaving the cor- [Me2(PhC≡C)PCH2]AuC≡CPh could not be de-
responding gold(I) complexes. b) The alkynyl halides tected. Because of the failure of this crucial step, there
c
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O. Schuster – H. Schmidbaur · (Phenylethynyl)trimethylphosphonium Bromide and Bromoaurates(I)
Fig. 1. Cation and anion of
compound 1 with atomic
numbering (ORTEP, 50%
probability
ellipsoids,
H atoms with arbitrary
radii). Selected bond
˚
lengths [A] and angles
[◦]: P1-C1 1.739(3),
P1-C11
1.778(3),
P1-C12 1.777(2), P1-C13
1.776(3); C1-C2 1.202(4),
C2-C3 1.431(4). P1-C1-
C2 175.6(3), C1-C2-C3
177.5(3),
C1-P1-C11
108.75(12), C1-P1-C12
108.69(12), C1-P1-C13
108.56(13), C11-P1-C12
109.75(13), C11-P1-C13
110.70(12), C12-P1-C13
110.52(12).
was no substrate basis for the oxidative addition using trichloromethane. The solutions in CD2Cl2 show a
1
31
1
[PhC≡C)2TlCl]2, which could finally have afforded { H} P NMR signal at δ = 5.4 ppm. The H NMR
the target gold(III) complex (I). This addition had been spectrum features the doublet of the methyl protons at
carried out successfully with PhC≡CAu(PMe3) [1].
δ = 2.57 with 2J(P,H) = 15.2 Hz (9H) and the phenyl
1
13
The present report is an account of the pertinent in- multiplet at 7.41– 7.67 ppm (5H). The { H} C res-
vestigations.
onance of the methyl groups appears at δ = 12.6
with 1J(P,C) = 15.2 Hz. The ethynyl carbon atoms
give rise to two doublets at δ = 72.9 and 112.5 with
1/2J(P,C) = 163.7/29.2 Hz, respectively. The phenyl
13C resonances include a doublet for C-1 at δ = 117.8
Results
(Phenylethynyl)trimethylphosphonium Bromide (1)
There is only
a
limited number of mixed
1
with J(P,C) = 4.5 Hz and singlets for C-2, C-3 and
ethynylphosphoniumsalts of the type [R3(R’C≡C)P]+
X− (with R/R’ = alkyl and/or aryl) in the literature
[5 – 11]. Their preparation generally followed the most
obvious route, vic. the quaternization of tertiary phos-
phines with alkynyl halides, but other routes have also
been described [5, 6, 11]. For the present case, ori-
ented at the substitution pattern of the target molecule
(I) and the proposed step b) of its formation (v. s.),
trimethylphosphine and phenylethynyl bromide were
chosen as the reactants. In agreement with literature
observations [11], the reaction was found to be fast
and exothermic in a tetrahydrofuran / toluene mixed
solvent at r. t. The product precipitated as a colourless
crystalline solid which could be recrystallized from
dichloromethane/pentane (86% yield).
C-4 at δ = 129.0, 132.9 and 132.4. The data follow
trends already demonstrated in previous studies for
homologous ethynylphosphonium salts [7, 8]. The IR
spectrum of the solid in KBr has a band of the ν(C≡C)
vibration at 2186 cm−1 [11]. These spectroscopic data
are important benchmarks for the bromoaurate(I) com-
plexes (below) which have the same cation.
Crystals of compound 1 are monoclinic, space
group P21/c, with Z = 4 formula units in the unit
cell (Figs 1 – 3). In the cation, the phosphorus atom
has an only slightly distorted tetrahedral environ-
ment. All C-P-C angles are in the narrow range
from 108.55(12)– 110.75(13)◦. The three P-C(Me)
˚
distances are equal (1.777 0.001 A) within the stan-
˚
dard deviations (0.003) A), and significantly longer
˚
Me3P+Ph-C ≡ C-Br → [Me3P-C ≡ C-Ph]+Br− 1 (1)
than the P-C1(ethynyl) distance of 1.739(3) A clearly
reflecting the different hydridization of the carbon
The compound is readily soluble in dichloro- and atoms and a resonance effect. The ethynyl group is
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O. Schuster – H. Schmidbaur · (Phenylethynyl)trimethylphosphonium Bromide and Bromoaurates(I)
963
Fig. 2. Projection of
the crystal structure
of compound 1 along
the a axis (arbitrary
radii). Br–H-C con-
tacts are indicated
by thin broken lines.
[(Ph)C6-H–Br 2.971,
(Me)C-H–Br 2.865,
˚
2.897, 2.986 A. Only
two layers of bromine
atoms are shown.]
Formula III.
P-C(Me) bond along the main axis of the cation (For-
mula III and Fig. 3).
Formula II.
In the crystal, the cations form layers in the a-c
planes. The orientation of the main axes of the cationic
units is opposite in consecutive layers, but unidirec-
tional and parallel to the c-axis in each individual
layer (Figs 2, 3). The bromide anions are accommo-
dated in channels between the cations and have long
C-H- - -Br contacts with three methyl groups and one
phenyl group (in its p-position) which are indicated by
thin dotted lines in Fig. 2.
quasi- linear with angles P1-C1-C2 and C1-C2-C3 at
175.6(3) and 177.5(3)◦, respectively. The bond lengths
˚
C1-C2 = 1.202(4) and C2-C3 = 1.431(4) A are also as
expected for a triple bond in conjugation with a phenyl
substituent. Finally, there is a concomitant significant
shortening of the bonds C3-C4 and C3-C8 (average
˚
1.402 A), which are longer than the remainder four
˚
bonds of the phenyl ring (average 1.379 A) indicat-
ing resonance involving electron redistribution as in-
dicated by Formula II.
The orientation of the plane of the phenyl group with
respect to the threefold rotor of the Me3P group corre-
(Phenylethynyl)trimethylphosphonium bromo(phenyl-
ethynyl)aurate(I) (2)
A suspension of polymeric phenylethynylgold(I),
sponds to the most strain-free (minimal eclipse) con- [(PhC≡C)Au]n, in dichloromethane reacts with an
formation, vic. perpendicular to the projection of one equivalent quantity of compound 1 to give a clear so-
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964
O. Schuster – H. Schmidbaur · (Phenylethynyl)trimethylphosphonium Bromide and Bromoaurates(I)
Fig. 3. Projection of the crystal
structure of compound 1 along
the c axis (arbitrary radii).
lution. Upon addition of pentane the product 2 precipi- (Phenylethynyl)trimethylphosphonium Bromo(penta-
tates as a colourless solid (90% yield, m. p. 91 – 93 ◦C). fluorophenyl)aurate(I) (3)
Compound 1 reacts with (tetrahydrothiophene)
n[Me3PC ≡ CPh]+ Br− +[(PhC ≡ C)Au]n
pentafluorophenylgold(I), C6F5Au(tht), in homoge-
neous dichloromethane solution to give compound 3
and tht. The phosphonium salt is isolated as colourless
(2)
→ n[Me3PC ≡ CPh]+[PhC ≡ CAuBr]− 2
◦
The NMR spectra of solutions of compound 2 in
dichloromethane show the 31P signal at δ = 5.9 ppm,
virtually unchanged as compared to the value for 1, and
the same is true for the 13C and 1H cation resonances
(Exp. Section). The anion has separate resonances for
its PhC≡C group which are readily assigned referring
to literature data of other salts with the [PhC≡CAuX]−
anions (X = Cl, Br, I) [12 – 15].
plates (80% yield, m. p. 81 – 82 C).
[Me3PC ≡ CPh]+Br− +C6F5Au(tht)
(3)
→ tht+[Me3PC ≡ CPh]+[C6F5AuBr]− (3)
In the NMR spectra of compound 3 in dichloromethane
solution the signals of the cation show the same chem-
ical shifts and multiplicities as those of 1 and 2 (Exp.
These reference salts have been prepared in anal- Section). For the anion, the usual multiplet 13C res-
ogous reactions employing tetraalkylammonium bro- onances of the pentafluorophenyl group are detected.
mides [R4N]+Br− with R = Et, Bu as the reagents Salts with anions [C6F5AuX]− with X = Cl, Br, I
n
for [(PhC≡C)Au]n [12]. Related compound were ob- were prepared in the course of several previous stud-
tained with [(Ph3P)2N]+ as the cation and simple ies [16– 20]. The bromo complex anion in particular
HC≡C [14] or substituted phenylethynyl groups [15] was also observed in the phosphonium salts with the
n
in the anion. In all cases their spectroscopic data cations MePh3P+, EtPh3P+ and PrPh3P+ [16] and
n
are different from those of the related homolep- in the ammonium salt with the cation Bu4N+ [20].
tic [(RC≡C)2Au]− anions which were identified un- The chloro complex has been isolated with the “PPN”
equivocally [13]. For product 2, therefore, an iso- cation, [(Ph3P)2N]+ [C6F5AuCl]− [16] and the crystal
meric constitution with two different homoleptic an- structure of [BzPh3P]+ [C6F5AuCl]− has been deter-
ions [AuBr2]− and [PhC≡C)2Au]− in the ratio 1 : 1 mined [18]. Closely related compounds were obtained
can be excluded.
with the 2,4,6-trifluorophenylligand [19]. Based on the
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O. Schuster – H. Schmidbaur · (Phenylethynyl)trimethylphosphonium Bromide and Bromoaurates(I)
965
data of 3 and of these reference compounds a structure of the atoms of the P-C≡C-Ph unit of compound 1 and
with homoleptically coordinated anions can again be of reference compounds [7, 8] leads to the same con-
excluded.
clusions.
In previous work, most reactions were carried out
Attempted conversion of 2 and 3 into ylide complexes
with triaryl(ethynyl)phosphoniumsalts for which stan-
dard ylide formation is excluded. Reactions with base
in all cases took a different course including either P-C
bond breaking or even an increase of the coordination
number of the phosphorus atom to give hypercoordi-
nated species such as Ph3P(C≡CP)2 [10].
In attempts to convert compounds 2 and 3 into the
corresponding gold(I) ylide complexes (4, 5) the com-
pounds were reacted with strong base (nBuLi) in di-
ethylether or tetrahydrofuran solution under mild con-
ditions (0◦ and −78 ◦C). The expected products [eq. (4)
and (5)] could not be isolated or detected in the reac-
tion mixtures (by NMR spectroscopy).
However, among the reactions and transformations
of the few trialkyl(ethynyl)phosphonium salts reported
in the literature, which are homologues of compound 1,
there is also no example for the formation of the cor-
responding ylides. It is therefore very likely that at-
tack of a strong base on the [Me3PC≡CPh]+ cation
of compounds 2 and 3 is not taking the course formu-
lated in equations (4, 5) but leads to either P-C bond
cleavage or to a reversible or irreversible addition of
the nucleophile to C-β, possibly followed by polymer-
ization [11]. Deprotonation at a methyl group by base
is therefore overruled and no ylide can be generated.
The original concept of the present work was based on
the hope that in the presence of the metal center of the
anions in compounds 2 and 3 any “hot” ylide interme-
diate would be trapped and stabilized, but the experi-
ments proved that this is not the case. It remains even
more surprising then that compound I was formed in
the reaction mentioned in the introduction [1].
[Me3PC≡CPh]+[PhC≡CAuBr]−+n BuLi-//→
(4)
nBuH+LiBr+(PhC≡C)Me2PCH2AuC≡CPh (4)
[Me3PC≡CPh]+ [C6F5AuBr]−+nBuLi-//→
(5)
nBuH+LiBr+(PhC ≡ C)Me2PCH2AuC6F5 (5)
Therefore, no further experiments could be car-
ried out aiming at the preparation of the orig-
inal target complex, vic. the gold(III) complex
[(PhC≡C)3AuCH2PMe2(C≡CPh)], I.
Discussion
Although quite a number of trialkyl- and triaryl-
(ethynyl)phosphonium salts have been prepared and
used in a variety of transformations [5 – 11], to the
best of our knowledge no compound has been struc-
turally characterized. The structure of compound 1, a
very simple, representative example has now been de-
termined. Its structural details nicely reflect the reso-
nance situation proposed on the basis of the reactiv-
ity pattern observed in previous experiments. Thus,
the hydrolysis of [Ph3PC≡CPh]+ Br− was found to
lead either to Ph3PO, PhC≡CH and HBr, or to
Experimental Section
General
All experiments were routinely carried out under an at-
mosphere of pure and dry nitrogen. Solvents were thor-
oughly dried using conventional methods and saturated with
nitrogen, glassware was oven-dried and filled with nitro-
[Ph3PCH2C(O)Ph]+ Br−, depending on the reaction gen. Standard equipment was used throughout. Me3P [21],
PhC≡CBr and [Me3PC≡CPh]Br [11], [(PhC≡C)Au]n [22]
conditions [5, 6], indicating a primary nucleophilic at-
and [C6F5Au(tht)] [12] were prepared according to literature
tack of H2O at the β carbon atom P-C≡C-Ph. Similar
procedures. NMR: Jeol JNM-GX-270/400 and Jeol JNM-
results were obtained with amines R2NH, phosphines
LA-400; residual resonances of the deuterated solvent, con-
R2PH and thiols RSH [6]. Compound 1 was shown to
undergo base-catalyzed polymerization at only slightly
elevated temperatures. The mechanism proposed for
this polymerization involves a primary nucleophilic at-
1
verted to TMS, as standards for H and 13C signals; conc.
aqueous H3PO4 as an external standard for 31P; δ values in
[ppm], J values in [Hz].
tack of pyridine or picoline at C-β [11].
Compound 1
The bond lengths in the P-C≡C-Ph unit of com-
pound 1 are in agreement with a delocalization of the
The solution of PhC≡CBr (0.5 g, 2.8 mmol) in 25 ml of
positive charge over P, C-β and the periphery of the
tetrahydrofuran was combined with 3 ml of a 1.0 M solution
phenyl ring (II). The evaluation of the chemical shifts of Me3P in toluene at r. t. with efficient stirring. A colourless
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966
O. Schuster – H. Schmidbaur · (Phenylethynyl)trimethylphosphonium Bromide and Bromoaurates(I)
Ph; 115.3, d, 2JP,C 31.7, P-C≡C; Au-C not observed. 117.1,
Table 1. Crystal and structure solution data of compound 1.
[Me3PC≡CPh]Br
127.4, 129.4, and 133.4, all s, for i, o, p, and m of PhC2Au,
3
respectively. 118.3, d, JP,C 4.2, i-PhC2P; 130.3, 134.0,
Empirical formula
Mr
C11H14BrP
257.10
1
134.5, all s, for o, p, m of PhC2P, respectively. H: 2.44, d,
2JP,H 14.8, 9H, Me; 7.11 – 7.42, m, 5H, Ph(C2Au); 7.42 –
7.76, m, 5H, Ph(C2P).
Crystal system
Space group
monoclinic
P21/c
˚
a [A]
5.7525 (1)
7.6158 (2)
27.3932(6)
91.308(1)
1199.78(5)
1.423
˚
b [A]
Compound 3
˚
c [A]
β [◦]
(C6F5)Au(tht) (91 mg, 0.2 mmol) was treated with com-
pound 1 (51 mg, 0.2 mmol) in 25 ml of dichloromethane at
20 ◦C. A clear solution was obtained. The product was pre-
cipitated by adding pentane, filtered off and dried in a vac-
uum; yield 99 mg (80%), m. p. 81 – 82 ◦C. C17H14AuBrF5P
(621.13): calcd. C 3◦2.87, H 2.27; found C 32.77, H 2.01.
3
˚
V [A]
ρcalc [g cm−3
Z
]
4
F(000)
520
35.16
143
µ (Mo-Kα ) [cm−1
T [K]
]
1
1
NMR (CD2Cl2, 25 C), 31P{ H}: 5.7, s. 13C{ H}: 13.0,
Reflections measured
Reflections unique
Refined parameters
R1 [I ≥ 2σ(I)]
27506
2204 [Rint = 0.034]
122
0.0299
0.0809
1
1
s, JP,C 62.3, Me; 71.1, d, JP,C 173.0, P-C≡C; 114.6, d,
4
2JP,C 32.7, P-C≡C; 117.2, d, JP,C 4.7, i-Ph; 129.0, 132.8
wR2a
and 133.1, all s, for o, p and m of Ph, respectively; 135.2,
138.8, 146.7, and 150.0, all br m., for i, o, p, and m of C6F5,
respectively. 1H: 2.38, d, 2JP,H 14.6, 9H, Me; 7.41 – 7.69, m,
5H, Ph.
Weighting scheme
a = 0.0420
b = 0.9455
0.528 / −0.517
−3
˚
σfin (max/min)/eA
wR2 = {Σ[w(Fo − Fc2)2]/Σ[w(Fo2)2]}1/2; w = 1/[σ2(Fo2) +
a
2
(ap)2 +bp]; p = (F 2 +2F 2)/3.
o
c
Crystal structure determination
The single crystal of 1 was placed in inert oil on the
top of a glass pin and transferred to the cold gas stream of
the diffractometer. Crystal data was collected using a No-
nius DIP2020 system with monochromated Mo-Kα (λ =
precipitate was formed in an exothermic reaction. The sus-
pension was stirred for 12 h at 40 ◦C and filtered. The prod-
uct was recrystallized from dichloromethane/pentane; yield
◦
◦
0.61 g (86%), m. p. 217 – 220 C (lit. 218 – 221 C [11]).
C11H14BrP (257.10): calcd. C 51.39, H 5.49; found C 50.76,
H 5.50. IR (KBr): ν(C≡C) 2186 cm−1. NMR (CD2Cl2,
◦
˚
0.71073 A) radiation at −130 C. The structure was solved
by direct methods (SHELXS-97) and refined by full matrix
least-squares calculations on F2 (SHELXL-97) [23]. Non-
hydrogen atoms were refined with anisotropic displacement
parameters. Hydrogen atoms were placed in idealized posi-
tions and refined using a riding model with fixed isotropic
contributions. Further information on crystal data, data col-
lection and structure refinement are summarized in Table 1.
Important interatomic distances and angles are given in the
caption of Fig. 1. Complete lists of displacement parameters
and tables of interatomic distances and angles have been de-
posited with the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK. The data are avail-
able on request on quoting CCDS-606390.
◦
1
1
1
25 C), 31P{ H}: 5.4, s. 13C{ H}: 12.6, d, JP,C 62.3, Me;
72.9, d, 1JP,C 163.7, P-C≡C; 112.5, d, 2JP,C 29.2, C≡C-Ph;
117.8, d, 4JP,C 4.5, i-Ph; 129.0, s, o-Ph; 132.4, s, p-Ph; 132.9,
s, m-Ph. 1H: 2.57, d, JP,H 15.2, 9H, Me; 7.41 – 7.67, m,
2
5H, Ph.
Compound 2
Compound 1 (77 mg, 0.3 mmol) was added to a sus-
pension of [(PhC≡C)Au]n (90 mg, 0.3 mmol) in 25 ml of
◦
dichloromethane at 20 C. After 1 h a clear colourless so-
lution was obtained. Pentane was added to precipitate the
product, which was filtered off◦and dried in a vacuum; yield
150 mg (90%), m. p. 91 – 93 C. C19H19AuBrP (555.20):
calcd. C 41.10, H 3.45; found C 40.90, H 3.21%. NMR
Acknowledgements
◦
1
1
(CD2Cl2, 25 C), 31P { H}: 5.9, s. 13C{ H}: 14.2, d, 1JP,C
This work was supported by Deutsche Forschungsge-
meinschaft and Fonds der Chemischen Industrie.
1
61.8, Me; 73.0, d, JP,C 170.4, P-C≡C; 99.7, s, Au-C≡C-
[1] O. Schuster, H. Schmidbaur, Organometallics 24, 2289
[4] H. Schmidbaur, Angew. Chem. Int. Ed. Engl. 22, 907
(2005).
(1983).
[2] H. Schmidbaur, R. Franke, Chem. Ber. 108, 1321
(1975).
[5] H. G. Viehe, E. Franchimont, Chem. Ber. 95, 319
(1962).
[3] H. Schmidbaur, Acc. Chem. Res. 8, 62 (1975).
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O. Schuster – H. Schmidbaur · (Phenylethynyl)trimethylphosphonium Bromide and Bromoaurates(I)
967
[6] H. Hofmann, H. Fo¨rster, Tetrahedron Letters 17, 983
(1964).
[7] H. Bestmann, L. Kisielowski, Chem. Ber. 116, 1320
(1983).
[8] T. A. Albright, W. J. Freeman, E. E. Schweizer, J. Am.
Chem. Soc. 97, 2946 (1975).
[9] K. Yasufuku, K. Aoki, H. Yamazaki, J. Organomet.
Chem. 84, C28 (1975).
[15] J. Vicente, M. T. Chicote, M. D. Abrisqueta,
M. Alvarez-Falcon, J. Organomet. Chem. 663,
40 (2002).
[16] R. Uso´n, A. Laguna, J. Vicente, J. Organomet. Chem.
131, 471 (1977).
[17] R. Uso´n, A. Laguna, Coord. Chem. Rev. 70, 1 (1986).
[18] D. A. Briggs, R. G. Raptis, J. P. Fackler (Jr.), Acta Crys-
tallogr. C44, 1313 (1988).
[10] S. Ogawa, Y. Tajiri, N. Furikawa, Tetrahedron Letters
34, 839 (1993).
[19] A. Laguna, M. Laguna, J. Jimenez, A. J. Fumanal,
J. Organomet. Chem. 396, 121 (1990).
[11] P. Zhou, A. Blumstein, Polymer 38, 595 (1997).
[12] O. M. Abu-Salah, A. R. Al-Ohaly, Inorg. Chim. Acta
77, L 159 (1983).
[13] O. M. Abu-Salah, A. R. Al-Ohaly, S. S. Al-Showiman,
I. M. Al-Najjar, Trans. Met. Chem. 10, 207 (1985).
[14] J. Vicente, M. T. Chicote, M. D. Abrisqueta, J. Chem.
Soc., Dalton Trans. 1995, 497.
[20] J. Vicente, M. T. Chicote, M. D. Abrisqueta, P. G.
Jones, Organometallics 19, 2629 (2000).
[21] H. Schmidbaur, W. Wolfsberger, Synth. React. Inorg.
Metalorg. Chem. 4, 149 (1974).
[22] C. Glaser, Liebigs Ann. Chem. 154, 137 (1870).
[23] G. M. Sheldrick, SHELXL-97: Programs for Crystal
Structure Analysis, University of Go¨ttingen (1997).
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