Bis(metallaethynyl) ketones: Synthesis and structure of {(Ph 3P)AuC≡C}2CO and attempted transmetalation: Formation and structure of [1,3-{Ru(dppe)Cp}2{ c -COC(OMe)CHCCH}] PF6

Article abstract of DOI:10.1021/om200659t

The bis(metallaethynyl) ketone {(Ph₃P)AuC≡C}₂CO (1), obtained from (Me₃SiC≡C)₂CO, AuCl(PPh ₃), and NaOMe, forms an Au???Au-bonded dimer in the solid state (Au???Au = 2.9825(3) A). The ES-MS contains ions [2M + X]⁺ (X = Na, K, Au), but the lack of the ion [2M] ⁺ and NMR evidence suggest that the dimeric structure is not preserved in solution. Compound 1 reacts with RuCl(dppe)Cp to afford the unusual dimetal-substituted pyrylium complex [1,3-{Ru(dppe)Cp}₂{c-COC(OMe) CHCCH}]PF₆ (2). The molecular structure of 2 is also reported, together with a proposed route for its formation.

Full text of DOI:10.1021/om200659t

ARTICLE
pubs.acs.org/Organometallics
Bis(metallaethynyl) Ketones: Synthesis and Structure of {(Ph P)Au-
3
C;C} CO and Attempted Transmetalation: Formation and Structure
2
of [1,3-{Ru(dppe)Cp} {c-COC(OMe)CHCCH}]PF
2
6
†
,†
‡
§
†
David J. Armitt, Michael I. Bruce,* Jonathan C. Morris, Brian K. Nicholson, Christian R. Parker,
|
|
†
Brian W. Skelton, and Natasha N. Zaitseva
†
School of Chemistry & Physics, University of Adelaide, Adelaide, South Australia 5005, Australia
School of Chemistry, University of New South Wales, Sydney, New South Wales 2052, Australia
‡
§
Department of Chemistry, University of Waikato, Hamilton, New Zealand
Centre for Microscopy, Characterisation and Analysis, University of Western Australia, Crawley, Western Australia 6009, Australia
S Supporting Information
b
ABSTRACT:
The bis(metallaethynyl) ketone {(Ph P)AuCtC} CO (1), obtained from (Me SiCtC) CO, AuCl(PPh ), and NaOMe, forms an
3
2
3
2
3
+
Au Au-bonded dimer in the solid state (Au Au = 2.9825(3) Å). The ES-MS contains ions [2M + X] (X = Na, K, Au), but the
lack of the ion [2M] and NMR evidence suggest that the dimeric structure is not preserved in solution. Compound 1 reacts with
RuCl(dppe)Cp to afford the unusual dimetal-substituted pyrylium complex [1,3-{Ru(dppe)Cp} {c-COC(OMe)CHCCH}]PF
3
3 3
3 3 3
+
2
6
(2). The molecular structure of 2 is also reported, together with a proposed route for its formation.
’
INTRODUCTION
Compounds containing redox-active metalꢀligand fragments
linked by unsaturated hydrocarbon chains continue to attract
’ RESULTS AND DISCUSSION
a). Synthesis and Molecular Structure of {(Ph P)AuC;C} -
(
3
2
CO (1). The gold-containing bis(ethynyl) ketone {(Ph P)-
1
,2
3
attention,
particularly those containing redox-active end
AuCtC} CO (1) apparently has not been previously described
3
ꢀ6
2
groups capping ꢀ{C(sp)} ꢀ chains.
The effects of inserting
n
and was synthesized in 50% yield by a rather sluggish aurodesi-
some group X into a ꢀ(CtC) ꢀ chain on the electronic com-
x
lylation reaction between (Me SiCtC) CO and AuCl(PPh )
3
2
3
munication between the end groups along the chain has been the
object of recent studies: for example, where X = aryl, naphthyl,
in THFꢀMeOH in the presence of NaOMe (Scheme 1). An
i
3
alternative approach from (Pr SiCtC) CO, AuCl(PPh ), and
7
2
3
anthryl.
[
NBu ]F in THF gave 1 in 27% yield. Complex 1 was obtained as
4
We have begun a study of the effects of the insertion of groups
a white crystalline solid and was identified from elemental
such as CdCH , or the strongly electron-withdrawing CdO or
CdC(CN) , into the carbon chain. The transmetalation reac-
tion, whereby a gold(I) phosphine group isreplacedby ruthenium,
is a useful route to alkynylruthenium complexes. Accordingly,
2
microanalysis and its spectroscopic features, the IR spectrum
8
ꢀ1
2
containing ν(CtC) and ν(CO) bands at 2106 and 1593 cm
,
respectively. The latter band is at an energy significantly lower
9,10
ꢀ1
than those found in the precursor (Me SiCtC) CO (1622 cm )
3
2
we have investigated the use of {(Ph P)AuCtC} CO (1), syn-
3
2
thesized here for the first time, as a possible source of the bis-
(
ruthenaethynyl) ketone {Cp(dppe)RuCtC} CO. However, the
Received: July 21, 2011
Published: September 29, 2011
2
product proved to be an unprecedented dimetallapyrylium complex.
r 2011 American Chemical Society
5452
dx.doi.org/10.1021/om200659t
|Organometallics 2011, 30, 5452–5456

Organometallics
ARTICLE
Scheme 1. Synthesis of {(Ph P)AuCtC} CdO (1)
C(1,5) with J(CP) = 24, 134 Hz, respectively). However, there is
only one Au(PPh ) resonance at δ 40.7, while the ES-MS spec-
3
2
3
P
+
trum of a solution in MeOH included only monomeric [M + H]
+
and [M + Na] ions at m/z 995 and 1017, respectively. The
+
dimeric ion [2M] was not detected, and with the NMR results,
this suggests that facile dissociation of the dimer occurs in solu-
+
tion. The aggregate ions [2M + X] (X = Na, K, Au), [(2M + Na) -
+
+
PPh ] , and [M + Au(PPh ) ] were also present and probably
3
3 2
result from interactions of the cationic metal centers with the
carbonyl groups. The compositions of these ions were confirmed
by high-resolution measurements.
(
b). Reaction between RuCl(dppe)Cp and {(Ph P)AuC;C} -
3
2
CO (1). Transmetalation reactions between Au(CtCR)(PPh )
3
and haloꢀmetal centers, [M]X, give [M]CtCR and AuX-
10,11
(
PPh ).
Treatment of {(Ph P)AuCtC} CO (1) with
3 2
3
RuCl(dppe)Cp and [NH ]PF (used to provide the counteran-
4
6
ion in the product) in methanol at reflux, followed by addition of
DBU, afforded the bright yellow solid 2 (Scheme 2). However,
the lack of any ν(CtC) or ν(CO) bands in the IR spectrum,
31
together with the P NMR spectrum (below), suggested that the
desired {[Cp(dppe)Ru]CtC} CO had not formed, with this
2
supposition being confirmed by a single-crystal structure deter-
mination of 2.
A plot of the cation in 2 is shown in Figure 2. The struc-
ture determination revealed that 2 has the formulation
[
1,3-{Ru(dppe)Cp} {μ-c-COC(OMe)CHCCH}]PF , contain-
2 6
ing a pyrylium ring bearing two Ru(dppe)Cp groups at the 1,3-
positions. These groups have the usual pseudo-octahedral geometry
(
RuꢀP = 2.236ꢀ2.264(1) Å, RuꢀC(cp) = 2.25 Å (average),
PꢀRuꢀP = 84.39, 83.75(4)°, PꢀRuꢀC = 84.3ꢀ93.3(1)°).
Within the pyrylium ligand, electron delocalization results in
longer than normal CdC bonds (C(1)ꢀC(2) = 1.393(6) Å,
C(4)ꢀC(5) = 1.353(6) Å) with C(2)ꢀC(3) and C(3)ꢀC(4)
(
1.416(6), 1.428(6) Å) being shorter than CꢀC bonds, con-
sistent with the pyrylium ligand displaying aromaticity. Bonds to
the ring O atom C(1,5)ꢀO(6) are 1.393(5) and 1.341(5) Å, res-
pectively, the latter being the same as C(5)ꢀO(5), while the
terminal ether C(51)ꢀO(5) bond length (1.437(5) Å) is consi-
derably longer. Bond angles within the ring range from 114.0(4)
to 129.1(4)°, with C(5)ꢀO(5)ꢀC(51) being 115.5(3)°.
Figure 1. Plot of a molecule of {[(Ph P)AuCtC] CO} (1) (H atoms
3
2
2
The RuꢀC(1,3) bond lengths are 2.030(4) and 2.073(4) Å,
consistent with RuꢀC single bonds in both cases. Further, the
RuꢀP distances (2.260, 2.264(1) Å), which usually indicate a
positive charge of the metal center by a lengthening over values
found in analogous neutral derivatives, show only a small increase
in the Ru(1)ꢀP(1,2) bond lengths from those found in neutral
omitted for clarity). Selected bond distances (Å) and angles (deg):
Au(1) Au(3) = 2.9825(3), Au(1)ꢀP(1) = 2.281(2), Au(1)ꢀC(11) =
3
3 3
2
.031(6), C(11)ꢀC(12) = 1.184(9), C(12)ꢀC(13) = 1.448(10),
C(13)ꢀO(13) = 1.219(8); P(1)ꢀAu(1)ꢀC(11) = 179.3(2), Au(1)ꢀ
C(11)ꢀC(12) = 168.6(6), C(11)ꢀC(12)ꢀC(13) = 175.4(8), C(12)ꢀ
C(13)ꢀC(14) = 115.3(6), C(12)ꢀC(13)ꢀO(13) = 122.5(6).
12
complexes, e.g., 2.240 and 2.250(1) Å in Ru(CtCPh)(dppe)Cp.
ꢀ
1 11
or in (HCtC) CO (1669 cm ), perhaps reflecting the donor
Consequently, these data, together with lengthening of the
C(1)ꢀC(2) and shortening of the C(2)ꢀC(3) bonds, suggest
that the positive charge is located within the pyrylium ring.
Spectroscopic data are consistent with the solid-state struc-
ture. The IR spectrum contains ν(CdC) and ν(CdO) bands
2
power of the Au(PPh ) substituent.
3
The X-ray-determined structure of 1 (Figure 1) consists of
dimeric molecules, the halves of which are linked by a short
aurophilic Au Au interaction (2.9825(3) Å). Each half of the
molecule has the expected structure, with AuꢀC(sp) bond
lengths between 1.985 and 2.031(6) Å, CtC triple bond lengths
between 1.180 and 1.210(9) Å, and CdO bond lengths of 1.219
and 1.220(8) Å. The PꢀAuꢀCtCꢀC moieties are essentially
linear, with angles at atoms within the chains being between
3
3 3
ꢀ1
ꢀ1
between 1567 and 1015 cm and a ν(PF) band at 836 cm ,
31
while the P NMR spectrum displays two singlets for the two
Ru(dppe)Cp groups at δ 93.0 and 90.9 and a septet at δ ꢀ142.2
P
P
1
13
(PF ). The H and C NMR spectra showed the expected peaks
6
for the ancillary ligands, together with a singlet at δ 5.05 assi-
H
1
68.6 and 179.3(2)°. The central PAuCCC(O)CCAuP atoms of
gned to the C(4) proton. The OMe group resonates at δ 2.58
H
each half are essentially planar, with the dihedral angle between
the planes of the two moieties being 92.59(4)°.
and δ 54.78, the former being at a field considerably higher than
C
1
that found in related compounds Fe{c-CdCHCR CPhCC-
(OMe)}(CO) Cp (R = H, R = H, Ph; R = Me, R = H), in
1
3
R
1
1
The C NMR spectra contains two doublet resonances for
2
the C(sp) carbon atoms (δ 105.06 for C(2,4) and 139.20 for
which the OMe group lies between the Fe and pyrylium O
C
5
453
dx.doi.org/10.1021/om200659t |Organometallics 2011, 30, 5452–5456

Organometallics
ARTICLE
a
Scheme 2. Formation of [1,3-{Ru(dppe)Cp} {μ-c-COC(OMe)CHCCH}]PF (2)
2
6
a
Crystallographic numbering for 2 shown.
a
Scheme 3. Proposed Mechanisms for the Formation of 2
Figure 2. Plot of the cation of [1,3-{Ru(dppe)Cp} {c-COC-
2
6
(OMe)CHCCH}]PF (2) (H atoms omitted for clarity). Selected bond
distances (Å) and angles (deg): Ru(1)ꢀP(1,2) = 2.260, 2.264(1),
Ru(2)ꢀP(3,4) = 2.242, 2.236(1), Ru(1)ꢀC(1) =2.030(4), Ru(2)ꢀC(3) =
2
1
.073(4), C(1)ꢀC(2) = 1.393(6), C(2)ꢀC(3) = 1.416(6), C(3)ꢀC(4) =
.428(6), C(4)ꢀC(5) = 1.353(6), C(1)ꢀO(6) = 1.393(5), C(5)ꢀ
O(5,6) = 1.341(5), 1.341(5), C(51)ꢀO(5) = 1.437(5); P(1)ꢀ
Ru(1)ꢀP(2) = 84.39(4), P(3)ꢀRu(2)ꢀP(4) =83.75(4),P(1,2)ꢀRu(1)ꢀ
C(1) = 93.3(1), 85.4(1), P(3,4)ꢀRu(2)ꢀC(3) = 84.3(1), 92.4(1),
Ru(1)ꢀC(1)ꢀC(2) = 128.2(3), Ru(1)ꢀC(1)ꢀO(6) = 117.1(1), C(1)ꢀ
C(2)ꢀC(3) = 126.0(4), C(2)ꢀC(3)ꢀC(4) = 114.0(4), C(3)ꢀC(4)ꢀ
C(5) = 120.1(4), C(2)ꢀC(1)ꢀO(6) = 114.2(4), C(4)ꢀC(5)ꢀO(6) =
1
23.0(4)°.
1
3
atoms. The C(2)H signal falls within the aromatic region, as
do the resonances for C(2,4), which lie between δ 127 and
C
1
43.5. The two RuꢀC(1,3) triplets are at δ 212.88 and 215.51.
C
+
The ES-MS contains ion clusters at m/z 1239 (M ) and 565
+
([Ru(dppe)Cp] ).
This is an interesting structure: while there has been a
14
significant amount of work on aromatic pyrylium cations, there
are relatively few reports of transition-metal derivatives containing
6
pyrylium ligands. Pyrylium cations with Cr(CO) (η -C H ꢀ),
a
3
6 5
[
Ru] = Ru(dppe)Cp.
5
15
(
Mn orRe)(CO) (η -C H ꢀ), Co (CO) (μ-alkynyl), or ferro-
3
5
4
2
6
1
5,16
cenyl
substituents were investigated by Caro’s group. Other
17
ferrocenyl derivatives are known. Cationic manganese and iron
and PhCtCCO Et, followed by reaction with PPh , and is the
2 3
20
13,18
5
complexes have been described,
while (η -pyranyl)Mn(CO)3
only complex of this type which has been structurally characterized.
and 2-ferrocenylpyrylium cations have been obtained from cyclo-
manganated chalcones and alkynes. A platinum(II) complex
Previous syntheses of metal complexes containing pyrylium
ligands have proceeded from alkynes containing esters or other
carbonyl groups via cyclization reactions involving CꢀC and
19
containing a related carbenoid ligand, cis-PtCl (PPh ){c-CC-
2
3
19,20
(
CO Et)CPhC(CO Et)CPhO}, was obtained from PtCl (CO)
CꢀO bond formation.
In the present case, the stereochemistry
2
2
2
2
5
454
dx.doi.org/10.1021/om200659t |Organometallics 2011, 30, 5452–5456

Organometallics
ARTICLE
of the precursor bis(ethynyl) ketone suggests that intramolecular
reactions of this type would be difficult. Two possible mechan-
isms for the formation of 2 are shown in Scheme 3. Although the
metal centers in Scheme 3 are depicted as [Ru] = Ru(dppe)Cp,
in accord with the structure of the isolated product 2, we cannot
be certain at what stage the transmetalation of the bis(metallaethynyl)
ketone occurs. However, the presence of the ruthenium center
would activate the alkynyl group to the reactions proposed, while
recent studies have demonstrated the ability of gold(I) (here pre-
sent in solution after transmetalation) to catalyze the rearrange-
The mixture was stirred at room temperature under N
2
for 2 h and then
concentrated under vacuum. The residue was dissolved in the minimum
volume of CH Cl , MeOH (40 mL) was added, and the mixture was
2
2
swirled for a few minutes. The resulting precipitate was collected, rinsed
with MeOH, and dried to afford 1 (114 mg, 50%) as an off-white solid.
Anal. Calcd for C H Au OP (M 720): C, 49.51; H, 3.04. Found: C,
51 30
2
2
r
ꢀ
1
4
9.49; H, 3.07. IR (Nujol, cm ): ν(CH) 3052, ν(CtC) 2106,
ν(CdO) 1593, ν(CdC) 1480, 1435; other bands at 1170, 1101,
1
1
027, 998, 745, 730, 710, 693. H NMR (CDCl ): δ 7.45ꢀ7.55
3
13
(30H, m). C NMR (CDCl
3
): δ 105.06 (J(CP) = 24 Hz, tCC(O)),
21
128.91ꢀ134.21 (Ph), 139.20 (J(CP) = 134 Hz, tCAu), 160.66 (s, CO).
ment of propargylic esters and syntheses of pyrones from termi-
3
1
22
3 3
P NMR (CDCl ): δ 40.7 (AuPPh ). ES-MS (MeOH, m/z found
nal alkynes and propiolic esters.
+
(
calcd)): 2185.087 (2185.187), [2M + Au] ; 2011.132 (2011.210),
Pathway A envisages attack of methoxide on the vinylidene 3,
+
+
+
[2M + Na] ; 1453.146 (1453.167), [M + Au(PPh
(
(
[
3
)] ; 1033.080
formed by protonation ([NH ] ) of the bis(ruthenaethynyl)
+
+
4
1033.073), [M + K] ; 1017.103 (1017.100), [M + Na] ; 995.127
995.118), [M + H] ; 721.168 (721.148), [Au(PPh ) ] ; also 2027,
2M + K] ; 1749, [(2M + Na) ꢀ PPh ] ; 1715, [M + Au(PPh ) ] .
ketone, to give intermediate 4. Intramolecular attack on C then
+
+
α
3
2
affords acetal 5. Rearrangement by opening the oxetene ring
would result in formation of the product 2 directly. Alternatively,
rapid addition of MeOH to generate the hemiacetal (pathway B)
+
+
+
3
3 2
i
(
b). A solution of (Pr
3
SiCtC)
2
CO (0.10 g, 0.26 mmol) and AuCl-
(
PPh
3
) (0.25 g, 0.51 mmol) in THF (10 mL) was cooled to 0 °C and
4
is followed by a 1,3-shift of one metallaalkynyl group to C of the
α
[
NBu ]F (1 M in THF, 0.56 mL, 0.56 mmol) was added dropwise,
other, with concomitant isomerization to the corresponding
allene. Tautomerization followed by cyclization via attack of
followed by 1 drop of water, and the solution was stirred at 0 °C for 1 h
and then concentrated under vacuum. Isolation of the product as above
afforded 1 (69 mg, 27%).
the ester carbonyl at C of the remaining metallaalkynyl group
α
and protonation affords the observed product 2.
[
1,4-{Cp(dppe)Ru} {c-COC(OMe)CHCCH}]PF (2). To a mix-
2
6
ture of {(Ph
3
P)AuCtC}
2
CO (124 mg, 0.125 mmol), RuCl(dppe)Cp
4 6
(150 mg, 0.250 mmol), and [NH ]PF (43 mg, 0.263 mmol) was added
’
CONCLUSIONS
MeOH (14 mL), and the mixture was refluxed for 3.5 h, during which
time the solution darkened in color. DBU (2ꢀ3 drops) was added to the
reaction mixture, and after 1 h a yellow precipitate started to form.
Solvent was removed and the residue purified by flash column chroma-
tography (silica, initially CH Cl and then a CH Cl ꢀacetone gradient
This paper describes the synthesis and characterization of
{
(Ph P)AuCtC} CO (1), which is a dimer by an Au Au
3 2
3 3 3
interaction in the solid state. Attempted transmetalation of 1 with
RuCl(dppe)Cp did not give the desired bis(ruthenaethynyl)
ketone but instead the unprecedented binuclear pyrylium com-
plex 2. The molecular structures of 1 and 2 have been determined
from single-crystal X-ray diffraction studies. A plausible mechan-
ism is proposed for the formation of 2; further work is necessary
to elucidate the route to 2 in detail.
2
2
2
2
(
up to 2% acetone)) to give a yellow fraction, which afforded
[1,4-{Cp(dppe)Ru} {c-COC(OMe)CHCCH}]PF (2; 104 mg, 60%)
2
6
as a bright yellow solid. X-ray-quality crystals were grown from CH Cl /
2
2
hexane. Anal. Calcd for C H F O P Ru (M (cation) 1238, mol wt
6
8
63
6
2
5
2
r
ꢀ
1
1383): C, 59.05; H, 4.59. Found: C, 58.98; H, 4.63. IR (CH Cl , cm ):
2
2
ν(CdC) 1573vs, 1483w, 1451s, 1435s, 1400 m, 1385s. IR
ꢀ
1
(
Nujol, cm ): ν(CdC) 1567 m, 1306 w, 1262 m, 1097 m, 1015 m,
’
EXPERIMENTAL SECTION
1
ν(PF) 836 s. H NMR (d -acetone): δ 2.58 (s, 3H, OMe), 2.74, 2.90
6
(
2m, 4 ꢁ CH
CH), 7.01ꢀ7.71 (m, 41H, Ph + CH). C NMR (d
6.66 (m, CH P), 54.78 (s, OMe), 64.66 (OC(OMe)C), 86.37, 86.92
2
, 2 ꢁ dppe), 4.24, 4.89 (2s, 2 ꢁ 5H, 2 ꢁ Cp), 5.05 (s, 1H,
General Considerations. All reactions were carried out under dry
13
6
-acetone): δ 25.98ꢀ
nitrogen, although normally no special precautions to exclude air were
taken during subsequent workup. Common solvents were dried, distilled
under nitrogen, and degassed before use. Separations were carried out
by preparative thin-layer flash chromatography on silica gel (Davisil,
2
2
(
1
2s, Cp), 127.29ꢀ143.52 (m, Ph + C(2,4)), 212.88, 215.51 (2t, J(CP) =
3
1
4, 16 Hz, respectively, RuꢀC). P NMR (d
6
-acetone): δ 93.0, 90.9
).
(
2s, 2 ꢁ 2P, 2 ꢁ Ru(dppe)Cp), ꢀ142.2 (sept, J(PF) = 705 Hz, 1P, PF
6
4
0ꢀ63 micron).
+
+
ES-MS (MeOH, m/z): 1239, M ; 565, [Ru(dppe)Cp] .
Instruments. IR spectra were measured with a Bruker IFS28 FT-IR
Structure Determinations. Diffraction data were measured at
00 K using an Oxford Diffraction Xcalibur or Gemini diffractometer
spectrometer. Nujol mull spectra were obtained from samples mounted
between NaCl discs. NMR spectra were obtained with a Varian 2000
1
1
13
31
fitted with monochromatic Mo Kα (λ = 0.710 73 Å) (1) or Cu Kα
radiation (λ = 1.541 84 Å) (2). Following analytical (1) or multiscan (2)
absorption corrections and solution by direct methods, the structures
were refined by full-matrix least squares on F . Anisotropic displacement
parameter forms were refined for the non-hydrogen atoms, hydrogen
atom treatment following a riding model. Conventional residuals R1 and
instrument ( H at 300.13 MHz, C at 75.47 MHz, P at 121.503 MHz)
at 298 K. Samples were dissolved in CDCl or d -acetone contained in
mm sample tubes. Chemical shifts are given in ppm relative to internal
3
6
5
1
13
2
tetramethylsilane for H and C NMR spectra and external H
3
PO
4
for
3
1
P NMR spectra. Electrospray mass spectra (ES MS; positive-ion mode)
were obtained with Fisons Platform II and Bruker MicroTOF (high
resolution) spectrometers. Solutions in MeOH or MeCN were injected
into a via a 10 mL injection loop; nitrogen was used as the drying and
2
wR2 on F are given. Neutral atom complex scattering factors were used
2
6
within the SHELXL 97 program system. Pertinent results are given in
the figures (which show non-hydrogen atoms with 50% probability ampli-
tude displacement ellipsoids and hydrogen atoms with arbitrary radii of
0.1 Å) and in their accompanying captions. For 2, the site occupancy of
the CH Cl molecule was refined to 0.589(5).
2
3
nebulizing gas. Chemical aids to ionization were used as required.
Elemental analyses were performed by CMAS, Belmont, Victoria 3216,
Australia.
i
3
24
Reagents. The compounds (RCtC) CO (R = Me Si, Pr Si) and
RuCl(dppe)Cp were prepared by the cited methods.
2
3
2
2
25
Complex 1: [{(Ph P)AuCtC} CO] C H = C H Au O P C H ,
3 2 2 6 6 82 60 4 2 4 6 6
3
3
{
(Ph P)AuC;C} CO (1). (a). NaOMe (1 M in MeOH, 0.54 mL,
1
mol wt 2067.15, monoclinic, space group P2 /c, a = 17.6684(6) Å, b =
17.1866(6) Å, c = 25.4564(10) Å, β = 107.800(4)°, V = 7360.0(5) Å ,
F
3
2
3
0
0
.54 mmol) was added to a solution of (Me
3
SiCtC)
2
CO (50 mg,
ꢀ3
ꢀ1
.23 mmol) and AuCl(PPh ) (0.22 g, 0.45 mmol) in 1:1 THF (10 mL).
= 1.866 g cm , Z = 4, 2θ = 60°, μ = 8.085 mm (Mo Kα),
max
3
calcd
5
455
dx.doi.org/10.1021/om200659t |Organometallics 2011, 30, 5452–5456

Organometallics
ARTICLE
3
transmission (min/max) = 0.70, crystal 0.11 ꢁ 0.11 ꢁ 0.05 mm , 93 696
Low, P. J. Dalton Trans. 2009, 610. (b) Man, W. Y.; Bock, S.; Zaitseva,
N. N.; Bruce, M. I.; Low, P. J. J. Organomet. Chem. 2011, 696, 2172.
(11) Miller, F. A.; Harney, B. M. Spectrochim. Acta A 1971, 27, 1003.
reflections measured, 21 444 unique reflections (R = 0.087), 16 025
reflections with I > 2σ(I), R1 (I > 2σ(I)) = 0.053, wR2 (all data) = 0.097.
{c-COC(OMe)CHCCH}]PF
2 6
.589CH Cl = C H O P Ru .F P 0.589CH Cl , mol wt 1433.2,
int
(
12) Bruce, M. I.; Humphrey, M. G.; Snow, M. R.; Tiekink, E. R. T.
J. Organomet. Chem. 1986, 314, 213.
13) Shaw, M. J.; Afridi, S. J.; Light, S. L.; Mertz, J. N.; Ripperda, S. E.
Complex 2: [1,4-{Cp(dppe)Ru}
3
0
2
2
68 63
2
4
2
6
3
2
2
(
monoclinic, space group P2 /n, a = 17.6726(4) Å, b = 19.2342(4) Å, c =
1
3
ꢀ3
Organometallics 2004, 23, 2778.
1
9.8112(3) Å, β = 111.625(2)°, V = 6260.2(2) Å , Fcalcd = 1.521 g cm
,
ꢀ
1
(14) (a) Balaban, A. T.; Dinculescu, A. A.; Dorofeenko, G. N.;
Fischer, G. W.; Koblik, A. V.; Mezheritskii, V. V.; Schroth, W. Pyrylium
Salts: Synthesis, Reactions and Physical Properties; Academic: New York,
Z = 4, 2θmax = 134°, μ = 6.11 mm (Cu Kα), transmission (min/max) =
3
0
.74, crystal 0.13 ꢁ 0.10 ꢁ 0.07 mm , 56 740 reflections measured,
1
0 997 unique reflections (Rint = 0.048), 8651 reflections with I > 2σ(I),
1982. (b) Farcasiu, D.; Balaban, A. T.; Bologa, U. L. Heterocycles 1994,
R1 (I > 2σ(I)) = 0.041, wR2 (all data) = 0.107.
37, 1165.
(
15) (a) Caro, B.; S ꢀe n ꢀe chal -Tocquer, M. C.; S ꢀe n ꢀe chal, D.; Marrec,
P.; Saillard, J.-Y.; Truiki, C.; Kahlal, S. Tetrahedron Lett. 1993, 34, 7259.
b) Salmain, M.; Malisza, K. L.; Top, S.; Jaouen, G.; S ꢀe n ꢀe chal-Tocquer,
’
ASSOCIATED CONTENT
(
S
Supporting Information. CIF files giving full details of
M. C.; S ꢀe n ꢀe chal, D.; Caro, B. Bioconjugate Chem. 1994, 5, 655. (c)
Malisza, K. L.; Top, S.; Vaissermann, J.; Caro, B.; S ꢀe n ꢀe chal-Tocquer,
M. C.; S ꢀe n ꢀe chal, D.; Saillard, J.-Y.; Triki, S.; Kahlal, S.; Britten, J. F.;
McGlinchey, M. J.; Jaouen, G. Organometallics 1995, 14, 5273. (d) Caro,
B.; Guen, F. R.; S ꢀe n ꢀe chal -Tocquer, M. C.; Prat, V.; Vaissermann, J.
J. Organomet. Chem. 1997, 543, 87. (e) Salmain, M.; Caro, B.; Le Guen-
Robin, F.; Blais, J. C.; Jaouen, G. ChemBioChem 2004, 5, 99.
b
the structure determinations for 1 and 2. This material is available
free of charge via the Internet at http://pubs.acs.org. Full details
of the structure determinations (except structure factors) have
also been deposited with the Cambridge Crystallographic Data
Centre as CCDC 805626 (1) and 797935 (2). Copies of this
information may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax, + 44
(16) Ba, F.; Cabon, N.; Robin-Le Guen, F.; Le Poul, P.; Le Poul, N.;
Le Mest, Y.; Golhen, S.; Caro, B. Organometallics 2008, 27, 6396.
(17) Krasnikov, V. V.; Andreichikov, Yu. P.; Kholodiva, N. V.;
Dorofeenko, G. N. Zh. Org. Khim. 1977, 13, 1566.
1
223 336 033; e-mail, deposit@ccdc.cam.ac.uk; web, www:
http://www.ccdc.cam.ac.uk).
(
(
18) Shaw, M. J.; Mertz, J. Organometallics 2002, 21, 3434.
19) (a) Tully, W.; Main, L.; Nicholson, B. K. J. Organomet. Chem.
’
AUTHOR INFORMATION
1
996, 507, 103. (b) Mace, W. J.; Main, L.; Nicholson, B. K. J. Organomet.
Corresponding Author
Chem. 2005, 690, 3340. (c) Prasad, N.; Main, L.; Nicholson, B. K.;
McAdam, C. J. J. Organomet. Chem. 2010, 695, 1961.
*
Fax: + 61 8 8303 4358. E-mail: michael.bruce@adelaide.edu.au.
(
20) Canziani, F.; Galimberti, F.; Garlaschelli, L.; Malatesta, M. C.;
Albinati, A.; Ganazzoli, F. J. Chem. Soc., Dalton Trans. 1983, 827.
21) Barluenga, J.; Riesgo, L.; Vicente, R.; Lopez, L. A.; Tomas, M.
(
’
ACKNOWLEDGMENT
J. Am. Chem. Soc. 2007, 129, 7772.
(22) Luo, T.; Dai, M.; Zheng, S.-L.; Schreiber, S. L. Org. Lett. 2011,
13, 2834.
The Australian Research Council is acknowledged for support
of this work, as is Johnson Matthey plc, Reading, U.K., for a
generous loan of RuCl nH O.
(23) Henderson, W.; McIndoe, J. S.; Nicholson, B. K.; Dyson, P. J.
J. Chem. Soc., Dalton Trans. 1998, 519.
3
3
2
(
24) Anthony, J.; Boldi, A. M.; Rubin, Y.; Hobi, M.; Gramlich, V.;
’
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dx.doi.org/10.1021/om200659t |Organometallics 2011, 30, 5452–5456