The course of oxidative addition reactions of haloalkynes and haloalkenes to dimethyl- and dialkynylaurate(I) anions [RAuR]-

Article abstract of DOI:10.1016/j.ica.2006.01.041

The reactions of halo-alkynes Cl-C{triple bond, long}CH, C-lC{triple bond, long}C-Cl or PhC{triple bond, long}C-I with solutions of Li⁺[MeAuMe]^- in diethylether containing Ph₃P do not give the expected oxidative addition products Me₂(RC{triple bond, long}C)Au(PPh₃) with R = H, Cl, Ph. A mixture of other complexes is obtained instead which are generated in secondary reactions involving reductive elimination of ethane and/or dialkyne. However, addition of the halo-alkene H(Cl)C{double bond, long}CCl₂ to the same substrate solution affords trans-Me₂[trans-H(Cl)C{double bond, long}C(Cl)]Au(PPh₃) in good yield. Its molecular structure with pseudo-C_s symmetry has been determined by the solution NMR spectra and a single-crystal X-ray diffraction study. The reaction of methyl iodide with solutions of Li⁺[RC{triple bond, long}CAuC{triple bond, long}CR]^- in diethylether containing PPh₃ give the quaternary salts Ph₃PMe⁺ [RC{triple bond, long}CAuC{triple bond, long}CR]^- as the main products and only small amounts of cis-Me₂(RC{triple bond, long}C)Au(PPh₃) complexes probably formed in a series of oxidative addition, reductive elimination, and substitution reactions. The structure of Ph₃PMe⁺ [PhC{triple bond, long}CAuC{triple bond, long}CPh]^- has been determined.

Full text of DOI:10.1016/j.ica.2006.01.041

Inorganica Chimica Acta 359 (2006) 3769–3775
www.elsevier.com/locate/ica
The course of oxidative addition reactions of haloalkynes and
haloalkenes to dimethyl- and dialkynylaurate(I) anions [RAuR]ꢀ
*
Oliver Schuster, Hubert Schmidbaur
Department Chemie, Technische Universita¨t Mu¨nchen, Lichtenbergstrasse 4, 85747 Garching, Germany
Received 31 January 2006; accepted 31 January 2006
Available online 10 March 2006
Dedicated to Professor D. Michael R. Mingos.
Abstract
The reactions of halo-alkynes Cl–C„CH, C–lC„C–Cl or PhC„C–I with solutions of Li+[MeAuMe]ꢀ in diethylether containing
Ph3P do not give the expected oxidative addition products Me2(RC„C)Au(PPh3) with R = H, Cl, Ph. A mixture of other complexes
is obtained instead which are generated in secondary reactions involving reductive elimination of ethane and/or dialkyne. However, addi-
tion of the halo-alkene H(Cl)C@CCl2 to the same substrate solution affords trans-Me2[trans-H(Cl)C@C(Cl)]Au(PPh3) in good yield. Its
molecular structure with pseudo-Cs symmetry has been determined by the solution NMR spectra and a single-crystal X-ray diffraction
study. The reaction of methyl iodide with solutions of Li+[RC„CAuC„CR]ꢀ in diethylether containing PPh3 give the quaternary salts
Ph3PMe+ [RC„CAuC„CR]ꢀ as the main products and only small amounts of cis-Me2(RC„C)Au(PPh3) complexes probably formed
in a series of oxidative addition, reductive elimination, and substitution reactions. The structure of Ph3PMe+ [PhC„CAuC„CPh]ꢀ has
been determined.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Gold complexes; Oxidative addition; Reductive elimination; Alkenylgold(III) complex; Alkynylgold(III) complex; cis-Dialkylgold(III) complex
1. Introduction
leptic tetraalkynylgold(III) anions [Au(C„CR)4]ꢀ were
also finally discovered as components of salts with large
quaternary cations [14]. All these alkynylgold(III) species
were shown to undergo facile reductive elimination of alk-
anes R02 or dialkynes RC„CC„CR to leave the corre-
sponding alkynylgold(I) analogues (L)AuC„CR and
[Au(C„CR)2]ꢀ, respectively. For the mixed complexes of
the type ðLÞAuR02ðCBCRÞ only the cis-isomers have been
confirmed.
In the course of complementary attempts to find better
access to alkynyl gold(III) complexes in general, and to
compounds trans-Me2(RC„C)Au(L) in particular, the
oxidative addition of alkynyl halides to lithium dimethyl-
aurates(I), and of alkyl halides to dialkynylaurates(I), were
also probed, but the results were not encouraging. As
described below, all reactions of this type were quickly
followed by substitution, redistribution or reductive elimi-
nation processes. However, from peripheral observations it
became obvious that alkenyl gold(III) complexes can be
In the last two decades, alkynylgold(I) complexes
(L)Au–C„C–R have received growing interest due to their
potential for a range of applications, mainly in non-linear
optical and optoelectronic devices, as well as in mesogenic
and multidimensional arrays [1]. Their rigid-rod structures
with highly polarizable p-systems parallel to the molecular
axis can be tuned by introducing a large variety of donors
L and substituents R. The research activities have led to an
explosive growth of the literature [2–6], for which only a
few key references can be given [7–12].
By contrast, alkynylgold(III) complexes have remained
almost unknown, and it was only recently that the first com-
plexes of the types ðLÞAuR0 ðCBCRÞ and (L)Au(C„CR)3
2
could be isolated and fully characterized [13,14]. The homo-
*
Corresponding author. Tel.: +49 89 28913130.
E-mail address: h.schmidbaur@lrz.tum.de (H. Schmidbaur).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.01.041

3770
O. Schuster, H. Schmidbaur / Inorganica Chimica Acta 359 (2006) 3769–3775
obtained via this route as demonstrated in detail for the
addition of trichloroethene.
When the reaction was first carried out with Cl–C„C–
Cl, an unexpected product was identified, which subse-
quently could be traced to an impurity in the
dichloroethyne: Cl–C„C–Cl had been prepared from tri-
chloroethene by dehydrochlorination. With the conditions
applied some Cl2C@C(Cl)H also evaporates and therefore
some starting material is left in the product [17]. Addition
of this alkene to the [MeAuMe]ꢀ anion appears to give the
trans-(alkenyl)(chloro)dimethylaurate anion, of which the
chlorine atom is finally substituted by the PPh3 ligand
(Eq. (4)). Further purified Cl–C„C–Cl gave only traces
of this product together with (Ph3P)AuMe and
(Ph3P)AuCl. It should be noted, that in neither case any
evidence for the formation of isomeric cis-H(Cl)C@C(Cl)-
or Cl2C@CH-complexes could be found. The above
observations suggest that alkynyl halide addition to [MeA-
uMe]ꢀ is very slow whilst alkenyl halide addition takes
place easily
2. Preparative results
2.1. Oxidative addition of alkynyl halides to Li[MeAuMe]/
PPh3
Following the pioneering work of Tobias and co-worker
[15,16], lithium dimethylaurates(I) are readily obtained by
treatment of Ph3PAuCl with two equivalents of MeLi in
diethylether. The solutions of the reagent thus obtained
contain one equivalent of the Ph3P ligand liberated in the
process (Eq. (1)). In the present context, this is to be taken
as an advantage, since the phosphine can function as a sta-
bilizing ligand for the products of subsequent reactions
þ2MeLi
Ph P–Au–Cl
Liþ½Me–Au–Meꢁꢀ þ PPh þ LiCl ð1Þ
ꢀꢀꢀ!
3
3
Cl
Me
Ph3P
Me
Me
Cl
H
+ PPh3
- LiCl
Au
Cl
Cl
H
Au
Cl
Cl
H
Li
Au Me
Li
Me
+
Me
ð4Þ
Cl
Cl
1
Treatment of the solutions of Li[MeAuMe]/PPh3 with
Compound 1 in Eq. (4) is a colourless crystalline solid
which decomposes above 125 ꢁC. It is readily soluble in
di- and trichloromethane, but almost insoluble in pentane.
The 1H and {1H}13C NMR spectra of solutions in CD2Cl2
show single doublets for the methyl hydrogen and carbon
atoms at dH 0.14 and dC 9.7 ppm, respectively. Together
with the small coupling constants (3JP,H = 6.2 Hz and
2JP,C = 4.7 Hz) this is proof for the trans-position of the
methyl groups. The alkenyl proton appears at dH
an excess of HC„C–Cl in diethylether gave a mixture of
products, in which Ph3PAuMe, Ph3PAuMe3, Ph3PAuCl,
and traces of cis-Me2(HC„C)AuPPh3 were positively
identified by their NMR spectra (Eq. (2))
Cl
H
H
Cl
NaOH
4
6.74 ppm as a doublet with JP,H = 15.6 Hz. Of the two
Me
Ph3P Au Me
Me
Ph3P
Me
Me
alkenyl carbon atoms, only Cb could be located by its sig-
nal at dC 113.8 ppm (3JP,C = 3.1 Hz). In the {1H}31P NMR
spectrum there is only a single resonance at dP 26.2 ppm, in
a chemical shift range typical for R3AuPPh3 complexes.
Crystals of compound 1 are monoclinic, space group
P21/n, with Z = 4 molecules in the unit cell. The molecules
have no crystallographically imposed symmetry (Fig. 1).
The metal atom is in a square planar coordination environ-
ment and has the two methyl groups in trans positions with
ClC CH
(Ph3P)
+
Li
Au Me
Me
Au
C
HC
+
+
Ph3P Au Cl
Ph3P Au Me
ð2Þ
The same reaction with phenylethynyl iodide PhC„C–I
afforded Ph3PAuMe, Ph3PAuMe3, Ph3PAuI, cis-
Me2IAuPPh3, and cis-Me2(PhC„C)AuPPh3, and thus
followed a similar pattern (Eq. (3)). According to the
NMR data, the reaction mixture also contained a methyl-
triphenylphosphonium salt with an unknown anion, indi-
cating quaternization of the tertiary phosphine.
˚
Au1–C3 and Au1–C4 distances of 2.112(3) and 2.123(3) A,
respectively. These distances are in very good agreement
˚
with those of (Ph3P)AuMe3 (average 2.111 A for its mutu-
ally trans methyl groups) [18].
Li
Au Me
Me
IC
CPh
(Ph3P)
ð3Þ
Me
Me
PPh3
Me
Me
Ph
Ph
Ph
Au
+ Ph3P Au Me + Ph3P Au Me + Ph3P Au Me + Ph3P Au I +
Me
P
Me
I
PhC

O. Schuster, H. Schmidbaur / Inorganica Chimica Acta 359 (2006) 3769–3775
3771
Fig. 1. Molecular structure of compound 1 (ORTEP, 50% probability
ellipsoids; phenyl and methyl hydrogen atoms omitted, vinyl hydrogen
˚
atom with arbitrary radius.) Selected bond lengths (A) and angles (ꢁ),
standard deviations in parentheses: Au1–C1 2.038(3), Au1–C3 2.112(3),
Au1–C4 2.123(3), Au1–P1 2.3241(8), C1–C2 1.307(5), C1–Cl1 1.758(4),
C2–Cl2 1.741(4), C2–H2 1.01(4); C1–Au1–C3 88.37(14), C1–Au1–C4
88.19(13), C3–Au1–P1 94.46(11), C4–Au1–P1 89.22(10), Au1–C1–C2
126.5(3), Au1–C1–Cl1 118.59(18), C1–C2–Cl2 120.8(3), C2–C1–Cl1
114.9(3).
Fig. 2. Unit cell of crystals of compound 1 projected down the c-axis
(arbitrary radii).
Ph
Ph
Ph
MeI
(Ph3P)
The Au–C distance involving the alkenyl carbon atom is
RC
C
Au C CR
P
RC C
Au C CR
Li
˚
Me
distinctly shorter at Au1–C1 2.038(3) A. This shortening
may not only be due to the sp2-hybridization of C1, but
also to the trans-influence of the tertiary phosphine which
is known to stabilize Au–C bonds. This is also reflected
by the data for (Ph3P)AuMe3 with the Au–C bond trans
2a = H
2b = Me
2c = Ph
Ph3P
Me
Me
+
Au
˚
to the phosphine at only 1.968 A, and thus shorter than
C
RC
for the two mutually trans methyl groups (average
2.111 A) [18].
˚
ð6Þ
Maybe not unexpectedly, this result demonstrates that
The chlorine atoms of the alkenyl group are in trans
positions and the plane of the olefin is roughly perpendic-
ular to the coordination plane of the metal atom. The chlo-
rine atom Cl1 is located in a plane bisecting the angle
C121–P1–C131, and this staggered conformation places
the more distant chlorine atom Cl2 in an eclipsed position
relative to the phenyl group C111–C116.
In the crystal, the molecular units (1) are arranged in
double-stacks along the c-axis without any specific inter-
molecular contacts discernible (Fig. 2).
the quaternization of the tertiary phosphine with MeI is fas-
ter than the oxidative addition of MeI to the dialkynylau-
rate anion. The structures of the by-products suggest that
the slow MeI addition to the anion is followed by fast ligand
redistribution (probably involving reductive eliminations)
to give the stable cis-dimethyl(alkynyl)gold complexes. It
seems, that the formation of the gold(III) species does not
take place at all, when the acetylene C„C–R is substituted
with an electron withdrawing group (R = Ph), but this
observation has to be proven in further experiments.
2.2. Attempted oxidative addition of alkyl halides to
Li[RC„CAuC„CR]/PR3
Compounds 2a–c are colourless, crystalline solids with
melting points at 145–146, 109–110 and 137–139 ꢁC,
respectively. The complexes are readily soluble in di- and
trichloromethane, but sparingly soluble in hydrocarbons.
The NMR spectra of the solutions in CD2Cl2 show the
same resonances for the Ph3PMe+ cation in each case.
For the anions the signals of the hydrogen and carbon
atoms are all in the expected shift ranges. As in previous
cases, the Au–C„ resonances were not detected. In the
IR spectra of 2a–c (in KBr) the m(C„C) stretching frequen-
cies are found at 2219, 2119 and 2099 cmꢀ1, respectively.
Solutions containing salts Li[RC„CAuC„CR]/PPh3
(R = H, Me, Ph) are obtained from Ph3PAuCl and two
equivalents of RC„CLi in diethylether (Eq. (5))
+2 LiC CR
+ PPh3 + LiCl
Ph3P Au Cl
RC C
Au C CR
Li
ð5Þ
Treatment of these solutions with methyl iodide gives
mainly the quaternary salts Ph3PMe+ [RC„CAuC„CR]ꢀ
with minor amounts of cis-Me2(RC„C)AuPPh3 as the by-
products (Eq. (6)). The latter have been identified previ-
ously [13]
For 2a, m(„C–H) was located at 3273 cmꢀ1
Crystals of compound 2c are monoclinic, space group
P21/c, with Z = 4 formula units in the unit cell. The cations
.

3772
O. Schuster, H. Schmidbaur / Inorganica Chimica Acta 359 (2006) 3769–3775
complexes. Although some of the expected products are
formed in low yield, the major reactions take a different
course to give mainly gold(I) complexes.
By contrast, the oxidative addition of an alkenyl halide –
trichloroethene – was successful and led to an alkenyl-
(dimethyl)gold(III) complex of which NMR and single-
crystal X-ray diffraction studies have shown that it has
the two methyl groups in trans positions. This rare configu-
ration has previously been encountered only in isolated
cases such as Li[AuMe4] and (L)AuMe3 with L = PMe3
[19], PPh3 [18], R3PCH2 [18] or Me2S(O)CH2 [20], where
there is no choice of an isomeric ligand distribution, or in
some cyclic ylide complexes where the trans orientation is
required by the constraints of the metallacycle [21,22].
Mixed trialkylgold(III) complexes RnR03ꢀnAuðLÞ (R = Me,
R0 = Et, n-Pro, i-Pro, etc.) show no distinct configurational
preference and both isomers are available [2,23].
Fig. 3. Structure of the [Ph3PMe]+ cation and the [PhC„CAuC„CPh]ꢀ
anion in crystals of compound 2c (ORTEP, 50% probability ellipsoids,
hydrogen atoms omitted). Selected bond lengths (A) and angles (ꢁ): Au1–
C1 2.042(4), Au1–C3 2.003(4), C1–C2 1.144(6), C3–C4 1.186(6), C1–C11
1.461(6), C4–C21 1.454(6); C1–Au1–C3 179.22(15), Au1–C1–C2 170.1(4),
Au1–C3–C4 176.9(4), C1–C2–C11 177.1(5), C3–C4–C21 176.6(4).
˚
All previously described complexes of the type
Me2R0Au(L), with R0 = g1-CH2C(Me)@CH2, trans-
MeCH@CH [24,25], g1-C5H5 [26], C„CH, C„CMe,
C„CPh [13], and Ph [27], have the methyl groups in cis
positions, arguably due to a kinetic effect, because the com-
monly employed substitution of a precursor molecule with
a cis-configuration proceeds with retention of the cis-
arrangement. In the absence of thermodynamic data on
cis- and trans-isomers it therefore must be assumed that
compound 1 is also the kinetically controlled product of
the oxidative addition of Cl2C@CHCl to [MeAuMe]ꢀ fol-
lowed by substitution of the Au-bound chlorine atom by
the PPh3 ligand (Eq. (1)). To date this is only the second
reaction which gives access to trans-Me2R0Au(L) com-
plexes: Addition of two equivalents of MeAuPMe3 to
CF3C„CCF3
yielded
(Me3P)AuC(CF3)@C(CF3)Au-
Me2(PMe3) with the olefin-bound CF3 groups in cis-, but
the Au-bound methyl groups in trans-position [28].
It should be noted that the assignment of the cis-config-
uration to the two methyl groups in the reference com-
pounds is unambiguous even in cases where it has not
been confirmed by crystallographic data, because the
NMR-equivalence of the two methyl groups leaves no
alternative.
Fig. 4. Unit cell of crystals of compound 2c projected along the a-axis
(arbitrary radii).
Attempts of oxidative addition of methyl iodide to dial-
kynylaurate anions, [RC„CAuC„CR]ꢀ in diethylether
(containing PPh3) led predominantly to the quaternization
of the tertiary phosphine to give salts Ph3PMe+[RC„
CAuC„CR]ꢀ. There are only small amounts of by-prod-
ucts including the type cis-Me2(RC„C)Au(PPh3), which
indicate that any oxidative addition of MeI to the anion is
followed by ligand scrambling probably including reductive
elimination steps. The observation that two methyl groups
are finally ending up mutually cis can be taken as evidence
for a thermodynamic preference of this configuration over
the corresponding trans form. This idea is supported by
the observation that compounds cis-Me2(RC„C)Au(L)
could not be isomerized upon prolonged heating in polar
solvents. This is in contrast to results by Kochi et al. who
were able to thermally isomerize trialkylgold(III) complexes
and anions are fully separated and show no unusual details
(Fig. 3). The structure of the anion is known from previous
studies of the tetra(n-butyl)ammonium salt [14]. In stacks
of alternating cations and anions along the a-axis
(Fig. 4), the anions are separated by the cations and thus
not aggregated through aurophilic bonding (Au–Au
˚
7.708 A). There is also no evidence for arene p–p stacking.
3. Discussion
The present study has shown that oxidative addition of
alkynyl halides (chloro- and dichloro-ethyne, phenylethy-
nyl iodide) to lithium dimethylaurate(I), Li+[MeAuMe]ꢀ,
in diethylether solutions (containing PPh3) offers no pre-
parative advantages for the synthesis of alkynylgold(III)

O. Schuster, H. Schmidbaur / Inorganica Chimica Acta 359 (2006) 3769–3775
3773
R2R0Au(L) [23], and also to the stability towards isomeriza-
tion of the alkenyl compound 1 (above). It therefore
appears that in their cis/trans-preference the alkynyl com-
plexes are notably different from the alkyl and alkenyl
analogues.
4.1.2. Addition of Cl–C„C–Cl, containing residual starting
material H(Cl)C@CCl2, to Li+[MeAuMe]ꢀ/PPh3
(Ph3P)AuCl (300 mg, 0.6 mmol) in 80 mL of diethyl-
ether and 0.75 mL of an 1.6 M solution of MeLi
(1.2 mmol) were employed together with an excess of ca.
0.1 mol of the C2Cl2/C2HCl3 mixture. Complex 1 was
obtained as the main product; 263 g (45% yield), colourless
crystals, m.p. 125–126 ꢁC with decomposition. Calc. for
C22H22AuCl2P (585.23): C, 45.15; H, 3.79; Cl, 12.12.
Found: C, 45.06; H, 3.75; Cl, 13.19%. NMR: dP 26.2, s,
dH 0.14, d, J = 6.2, 6H, Me; 6.74, d, J = 15.6, 1H, CHCl;
7.43–7.66, m, 15H, Ph. dC 9.7, d, J = 4.7, Me; 113.8, d,
J = 3.1, CHCl; 117.4, d, J = 55.5, i-Ph; 129.2, d,
J = 11.4, m-Ph; 132.0, d, J = 2.6, p-Ph; 134.8, d, J = 11.4,
o-Ph; AuCCl not observed.
4. Experimental
General: All experiments were carried out in an atmo-
sphere of dry and pure nitrogen. Solvents were dried, dis-
tilled and saturated with nitrogen, and glassware was
oven-dried and filled with nitrogen. Standard equipment
was used throughout. NMR: Jeol JNM-GX 270 and 400;
1
chemical shifts in d values rel. residual H and 13C reso-
nances of the CD2Cl2 solvent converted to int. TMS, and
ext. 85% aqueous H3PO4 for 31P, respectively. (Ph3P)AuCl
[29], HC„CCl [30], ClC„CCl [17], Li[C„CH] [31] and
Li[C„CMe] [31] were prepared as described in the litera-
ture, all other reagents are commercially available.
4.1.3. Addition of Cl–C„C–Cl to Li+[MeAuMe]ꢀ/PPh3
The same process with purified C2Cl2 reagent gave very
low yields (<10%) of (Ph3P)AuMe and (Ph3P)AuCl.
4.1. Preparation of the lithium diorganoaurate(I) solutions
and oxidative addition
4.1.4. Addition of Ph–C„C–I to Li+[MeAuMe]ꢀ/PPh3
(Ph3P)AuCl (79 mg, 0.16 mmol); 0.2 mL of a 1.6 M
solution of MeLi (0.32 mmol) in diethylether; PhC„C–I
(68 mL, 0.30 mmol). Products: (Ph3P)AuMe, (Ph3P)AuI
(dP 39.7, s); cis-Me2(PhC„C)Au(PPh3) (dP 26.1, s; dH
0.32, d, J = 8.2, 3H, Mecis; 1.38, d, J = 9.2, 3H, Metrans);
cis-Me2AuI(PPh3) (dP 29.3, s; dH 1.13, d, J = 8.2, 3H,
Metrans; 1.49, d, J = 9.1, 3H, Mecis); (Ph3P)AuMe3;
Ph3PMe+ (dP 21.7, s; dH 3.1, d, J = 13.4, Me).
Following the literature procedures, a suitable quantity
of (Ph3P)AuCl was suspended in diethylether and treated
with a solution of two equivalents of the organolithium
reagent (MeLi, RC„CLi) in diethylether at 25 ꢁC with stir-
ring. (Ph3P)AuCl was rapidly dissolved to give a turbid, col-
ourless solution of Li+[R0AuR0]ꢀ with R0 = Me or RC„C
which contained one equivalent of Ph3P. After cooling to
ꢀ75 ꢁC, equimolar quantities of the alkynyl, alkenyl or
alkyl halides were slowly added. After a given time (below)
the reaction mixtures were allowed to warm to room tem-
perature and stirred for 2 h. The solvent was evaporated
in a vacuum and the residue extracted with 3 · 10 mL of
water to remove the lithium halides. The residue was taken
up with dichloromethane, the solution filtered through dry
MgSO4, and the products precipitated by addition of pen-
tane. Alternatively, (Ph3P)AuMe was used instead of
(Ph3P)AuCl and treated with only one equivalent of organo-
lithium reagent under the same conditions. The solutions of
Li[RAuR] thus obtained are free of chloride.
4.1.5. Addition of MeI to Li+[HC„CAuC„CH]ꢀ/PPh3
(Ph3P)AuCl (100 mg, 0.2 mmol) in 25 mL of diethyl-
ether; LiC„CH (6 mg, 0.4 mmol); MeI (71 mg, 0.5 mmol);
colourless precipitate, 53 mg (51% yield), m.p. 145–146 ꢁC.
Calc. for C23H20AuP (524.10): C, 52.68; H, 3.84. Found: C,
52.29; H, 3.43%. NMR: dP 22.0, s, dH 2.0, s, 2H, „C–H;
3.0, d, J = 13.1, 3H, Me; 7.64–7.96, m, 15H, Ph. dC 11.1,
d, J = 57.6, Me; 87.8, s, „CH; 119.1, d, J = 88.8, i-Ph;
130.8, d, J = 13.7, o-Ph; 133.5, d, J = 10.4, m-Ph; 135.6,
d, J = 2.6, p-Ph; AuC„ not observed. IR(KBr):
2219 cmꢀ1, m(C„C); 3273 cmꢀ1, m(„C–H). Small amounts
of the by-product cis-Me2(HC„C)Au- (PPh3) were identi-
fied by dP 26.5, s.
4.1.1. Addition of Cl–C„CH to Li+[MeAuMe]ꢀ/PPh3
(Ph3P)AuMe (76 mg, 0.16 mmol) was dissolved in
20 mL of diethylether and 0.1 mL of a 1.6 M solution of
MeLi in diethylether (0.16 mmol) added with stirring at
25 ꢁC. After cooling to ꢀ75 ꢁC an excess of freshly pre-
pared gaseous ClC„CH was condensed into the reaction
mixture over a period of 45 min and the flask kept at this
temperature for 12 h. After warming to room temperature
and evaporation of the solvent the work-up gave a colour-
less precipitate consisting of (Ph3P)AuMe (NMR: dP 48.0,
s; dH 0.43, d, J = 7.7 Hz, Me); (Ph3P)AuCl (dP 33.3, s);
(Ph3P)AuMe3 (dP 28.9, s; dH ꢀ0.05, d, J = 6.7, Mecis;
1.02, d, J = 8.9, Metrans); cis-Me2(HC„C)Au(PPh3) (dP
26.5, s).
4.1.6. Addition of MeI to Li+[MeC„CAuC„CMe]ꢀ/PPh3
(Ph3P)AuCl (100 mg, 0.2 mmol); LiC„CMe (18 mg,
0.4 mmol); MeI (71 mg, 0.5 mmol); colourless, microcrys-
talline product, 49 mg (44% yield), m.p. 109–110 ꢁC.
Calc. for C25H24AuP Æ 0.7CH2Cl2 (611.85): C, 50.45; H,
4.18%. Found: C, 50.69; H, 4.04%. NMR: dP 21.7, s,
dH 1.69, s, 6H, MeC„; 3.1, d, J = 13.4, 3H, MeP;
7.68–7.93, m, 15H, Ph. dC 5.1, s, MeC; 11.0, d,
J = 57.0, MeP; 96.6, s, MeC; 119.2, d, J = 89.3, i-Ph;
130.9, d, J = 13.7, o-Ph; 133.6, d, J = 10.4, m-Ph;
135.7, d, J = 2.6, p-Ph; Au–C not observed. IR(KBr):
2119 cmꢀ1, m(C„C). Small amounts of cis-Me2(MeC„)
Au(PPh3): dP 26.3, s.

3774
O. Schuster, H. Schmidbaur / Inorganica Chimica Acta 359 (2006) 3769–3775
Table 1
Crystal data, data collection and structure refinement details for 1 and 2c
trans-Me2Au(PPh3)[trans-(Cl)C@C(Cl)H] (1)
22H22AuCl2P
[Ph3PMe][Au(C„CPh)2] (2c)
Empirical formula
M
C
C35H28AuP
676.51
585.23
Crystal system
Space group
monoclinic
P21/n
monoclinic
P21/c
˚
a (A)
10.2331(2)
20.4398(4)
10.4376(3)
90
91.667(1)
90
10.1034(2)
13.4080(2)
20.7363(5)
90
94.122(1)
90
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
2182.23(9)
1.781
2801.89(10)
1.604
qcalc (g cmꢀ3
)
Z
4
4
F(000)
1128
70.63
143
1328
53.29
143
l (Mo Ka) (cmꢀ1
T (K)
)
Reflections measured
75267
80526
Reflections unique (Rint
Refined parameters/restraints
)
4448 (0.045)
239/0
5722 (0.066)
334/0
R1 [I P 2r(I)]
wR2
0.0219
0.0488
0.0307
0.0637
a
Weighting scheme ꢀ3
˚
fin(max/min) (e A )
a = 0.0074; b = 3.1488
0.688/ꢀ1.086
2
a = 0.0147; b = 4.8486
0.693/ꢀ0.714
r
P
P
2
2
1=2
a
wR2 ¼ f ½wðF 2o ꢀ F 2c Þ ꢁ= ½wðF o2Þ ꢁg ; w ¼ 1=½r2ðF o2Þ þ ðapÞ þ bpꢁ; p ¼ ðF o2 þ 2F 2c Þ=3.
4.1.7. Addition of MeI to Li+[PhC„CAuC„CPh]ꢀ/PPh3
(Ph3P)AuCl (100 mg, 0.2 mmol); LiC„CPh (0.4 mL of
a 1.0 M solution in tetrahydrofuran, 0.4 mmol); MeI
(71 mg, 0.5 mmol); colourless crystals, 88 mg (65% yield),
m.p. 137–139 ꢁC. Calc. for C35H28AuP (676.51): C, 62.14;
H, 4.17. Found: C, 62.29; H, 4.23%. NMR: dP 21.5, s, dH
2.95, d, J = 13.1, 3H, Me; 6.93–7.54, m, 10H, Ph-C;
7.54–7.94, m, 15H, PhP. dC 10.3, d, J = 57.6, Me; 103.0,
s, Ph-C; 125.2, 127.4, 128.1, and 131.5, all s, for i-, o-, p-,
m-PhC; 118.6 (d, J = 89.3), 130.6 (d, J = 13.0), 133.2 (d,
10.9), and 135.6 (d, J = 2.6), for i-, o-, m-, and p-PhP.
IR(KBr): 2099 cmꢀ1, m(C„C).
5. Supplementary data
Important interatomic distances and angles are shown in
the corresponding figure captions. Anisotropic thermal
parameters and tables of interatomic distances and angles
have been deposited with the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK.
The data are available on request on quoting CCDS-
291993 and/or -291994.
Acknowledgements
This work was supported by Deutsche Forschungsgemein-
schaft, Fonds der Chemischen Industrie, and Heraeus
GmbH.
4.2. Crystal structure determinations
Specimens of suitable quality and size were mounted on
the ends of quartz fibers in F06206R oil and used for inten-
sity data collection on a Nonius DIP2020 diffractometer,
employing graphite-monochromated Mo Ka radiation.
Intensity data were corrected for absorption effects (DELABS
from PLATON). The structures were solved by a combination
of direct methods (SHELXS-97) and difference-Fourier syn-
theses and refined by full-matrix least-squares calculations
on F2 (SHELXL-97) [32]. The thermal motion of all non-
hydrogen atoms was treated anisotropically. Apart from
the alkene hydrogen atom of 1 which was found and
refined isotropically, all hydrogen atoms were calculated
and allowed to ride on their parent atoms with fixed isotro-
pic contributions. Further information on crystal data,
data collection and structure refinement are summarized
in Table 1.
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