Bis(acetylido) complexes of ruthenium(II) bearing monodentate phosphane ligands

Article abstract of DOI:10.1002/ejic.200800495

Terminal acetylenes react with cis-RuMe₂(PMe₃) ₄ to form the bis(acetylido) complexes cis/trans-Ru(C≡CR) ₂(PMe₃)₄ in good yield. The structures of trans-2 (R = Ph), cis-3 (R = p-C₆

Full text of DOI:10.1002/ejic.200800495

FULL PAPER
DOI: 10.1002/ejic.200800495
Bis(acetylido) Complexes of Ruthenium(II) Bearing Monodentate Phosphane
Ligands
Leslie D. Field,*[a] Alison M. Magill,[a] Scott J. Dalgarno,[b,c] and Paul Jensen[d]
Keywords: Alkyne ligands / Phosphane ligands / Ruthenium
Terminal acetylenes react with cis-RuMe2(PMe3)4 to form the
bis(acetylido) complexes cis/trans-Ru(CϵCR)2(PMe3)4 in
good yield. The structures of trans-2 (R = Ph), cis-3 (R = p-
C6H4-OMe), trans-4 (R = p-C6H4-Me), cis-6 (R = Me), trans-
7 (R = SiMe3) and cis-8 (R = H) were determined by X-ray
crystallography.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
metal acetylido complexes include the reaction of alkynyl-
stannanes with metal halides,[12] and the reaction of low-
valent metals with terminal alkynes[13,14] or alkynyl(phenyl)-
iodonium reagents.[15]
Introduction
Transition-metal σ-acetylido complexes, particularly
those with an oligomeric or polymeric structure, have be-
come an increasingly important class of compounds in or-
ganometallic chemistry. Interest stems from the potential
applications of these complexes in many areas of material
science, notably in the fields of nonlinear optics,[1,2] lumi-
nescence,[3] liquid-crystalline materials,[4] and molecular
electronics.[5–7] The metal acetylide fragment possesses a π-
bonding system that facilitates electronic communication
between the conjugated organic ligand and the metal centre,
with the possibility of extended π-electron conjugation con-
ceivably providing a mechanism for electronic communica-
tion between remote metal centres.[6,7] Additionally, the
presence of transition metals in a polymer or oligomer
backbone allows the electrochemical and spectroscopic
properties to be tuned through changes in the metal ion
and ancillary ligands.[7,8]
The reaction of alkyl transition-metal complexes and ter-
minal alkynes by a σ-bond metathesis with concomitant
loss of methane has been used to prepare complexes of
RhI[14,16] and CoI.[17] We have previously reported the suc-
cessful synthesis of unsymmetrically substituted iron(II)
bis(acetylido) complexes by a σ-bond metathesis reaction
between trans-Fe(CϵCR)Me(dmpe)2 and a terminal al-
kyne,[18] and more recently have shown that the stepwise
reaction of trans-RuMe2(dmpe)2 firstly with one acetylene
then with another can lead to sequential reaction of the
methyl groups, and this provides a synthetic approach to
both symmetrical and unsymmetrical bis(acetylido) com-
plexes in good yield.[19]
In this paper we examine the σ-bond metathesis reaction
of cis-RuMe2(PMe3)4 with terminal acetylenes as a clean
and effective route to ruthenium bis(acetylides) Ru(CϵCR)2-
(PMe3)4.
The reaction of terminal acetylenes with simple iron(II)
and ruthenium(II) precursors e. g. MH2(dmpe)2 [M = Fe,
Ru; dmpe
=
1,2-bis(dimethylphosphanyl)ethane] is
known[9,10] to yield symmetrical bis(acetylido) complexes,
whereas the deprotonation of (vinylidene)ruthenium(II)
complexes has emerged as a powerful and versatile route
for the formation of both symmetrical and unsymmetical
Results and Discussion
Acetylido complexes, Ru(CϵCR)2(PMe3)4, were synthe-
bis(acetylido) complexes.[2,11] Other routes to transition- sised by the addition of a terminal acetylene to cis-Ru-
Me2(PMe3)4 (1), in thf or acetone at 40 °C (Scheme 1).
The reactions are complete within 2 h and, in general,
[a] School of Chemistry, University of New South Wales,
High St., Kensington 2052, Australia
Fax: +61-2-9385-8008
afford a mixture of cis and trans isomers, from which either
the cis isomer or the trans isomer may be recrystallised ex-
clusively. In the 1H NMR spectrum of the reaction mixture,
methane can be observed (signal at δ = 0.15 ppm) as a reac-
tion byproduct, and this is consistent with the σ-bond me-
tathesis mechanism for the formation of the metal ace-
tylides. With the exception of 7, the cis isomers tend to pre-
dominate in the crude reaction mixtures. Once isolated, the
complexes are quite stable towards both air and moisture
E-mail: L.Field@unsw.edu.au
[b] School of Engineering and Physical Sciences – Chemistry, Her-
iot–Watt University,
Riccarton, Edinburgh EH14 4AS, UK
[c] Department of Chemistry, University of Missouri – Columbia,
Columbia, Missouri 65211, USA
[d] School of Chemistry, University of Sydney,
Sydney 2006, Australia
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
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Eur. J. Inorg. Chem. 2008, 4248–4254

Bis(acetylido) Complexes of RuII with Monodentate Phosphane Ligands
Scheme 1.
and may be handled briefly without precautions; for pro-
longed storage, an inert gas is preferred.
Attempts to prepare the terminal acetylido complex
Ru(CϵCH)2(PMe3)4 by the deprotection of 7 with tetra-n-
butylammonium fluoride in thf were unsuccessful. In-
creased stability of the carbon–silicon bond in complexes
bearing trimethylsilylacetylide ligands has been observed
for other ruthenium complexes,[6,20,21] and has been attrib-
uted to either steric protection of the silyl group[6,21–23] or
an increase in the vinylidene character of the ligand brought
about by the donor effects of the phosphane ligands.[6] Sub-
sequently, cis/trans-Ru(CϵCH)2(PMe3)4 (8) was success-
fully synthesised by direct reaction of acetylene with cis-
RuMe2(PMe3)4 (Scheme 2).
Figure 1. Crystal structures of cis-Ru[CϵC(p-C6H4-OMe)]2(PMe3)4
(3), cis-Ru(CϵCMe)2(PMe3)4 (6) and cis-Ru(CϵCH)2(PMe3)4 (8).
Thermal ellipsoids are shown at the 50% probability level, hydro-
gen atoms have an arbitrary radius of 0.1 Å.
Scheme 2.
The complexes 3, 6 and 8 were crystallised as their cis
isomers, whereas the complexes 2, 4 and 7 were crystallised
as their trans isomers. ORTEP[24] depictions of the com-
plexes are given in Figures 1 and 2, together with selected
core bond lengths in Table 1.
The complexes all exhibit a distorted octahedral coordi-
nation environment. The trans complexes 2, 4 and 7 exhibit
a staggering of the phosphane ligands around the coordina-
Figure 2. Crystal structures of trans-Ru(CϵCPh)2(PMe3)4 (2),
trans-Ru[CϵC(p-C6H4-Me)]2(PMe3)4 (4) and trans-Ru(CϵCSi-
Me3)2(PMe3)4 (7). Hydrogen atoms on phosphane ligands have
been removed for clarity. Thermal ellipsoids are shown at the 50%
probability level, hydrogen atoms have an arbitrary radius of 0.1 Å.
tion plane, with trans P–Ru–P angles between 161.12(3) and trans P–Ru–P bond angles to approximately 161°, whereas
163.45(1)°. This arrangement, which allows for reduction in the equatorial cis P–Ru–P bond angles are of the order of
steric strain between the PMe3 ligands, has been reported 97°. The Ru–P bond lengths (average 2.34 Å) are typical of
previously for trans-Ru(N3)2(PMe3)4.[25] Similarly, the cis other ruthenium(II) complexes bearing trialkylphosphane
complexes 3, 6 and 8 show a significant narrowing of the ligands,[25,26] and vary little upon changing the geometry
Eur. J. Inorg. Chem. 2008, 4248–4254
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L. D. Field, A. M. Magill, S. J. Dalgarno, P. Jensen
FULL PAPER
Table 1. Selected bond lengths [Å] and angles [°] for 2–4 and 6–8.
2
3
4
6
7
8
Ru–C
2.053(3)
2.061(3)
1.219(4)
1.226(4)
n/a
2.046(4)
2.060(3)
1.205(5)
1.202(5)
2.3531(9)
2.3421(9)
2.348(1)
2.365(1)
2.056(1)
2.061(1)
1.220(2)
1.219(2)
n/a
2.064(1)
2.070(2)
1.205(2)
1.202(2)
2.3601(5)
2.3302(5)
2.3405(5)
2.3423(4)
2.050(2)
2.052(2)
1.221(2)
1.224(2)
n/a
2.035(9)
2.086(8)
1.21(2)
1.17(1)
2.342(2)
CϵC
Ru–Pax
Ru–Peq
2.3297(9)
2.3333(8)
2.3461(9)
2.3521(8)
179.4(1)
n/a
2.3230(4)
2.3347(4)
2.3427(4)
2.3448(4)
178.20(5)
n/a
2.3340(4)
2.3343(4)
2.3345(4)
2.3359(4)
179.70(6)
n/a
2.343(2)
2.339(3)
C–Ru–C
Pax–Ru–Pax
Peq–Ru–Peq
87.3(1)
161.04(3)
97.38(4)
89.00(6)
162.70(2)
97.767(2)
86.4(3)
161.2(1)
98.21(8)
161.12(3),
162.27(3)
163.45(1),
162.20(1)
162.84(2),
162.60(2)
from trans to cis. The carbon–carbon triple bond lengths ported previously for ruthenium(II)[29] and other transition
are also reasonably consistent, and the CϵC bond lengths metals.[18,30]
are comparable to those previously reported for related ace-
DFT calculations show that the trans isomer of
tylido complexes, trans-Ru(CϵCPh)2(dppe)2 [1.194(7) and Ru(CϵCMe)2(PMe3)4 (6) is only about 7.6 kJmol–1 more
1.207(7) Å],[27] trans-Ru(CO)2(PEt3)2(CϵCPh)2 [1.200(4) Å][22] stable than the cis isomer (Figure 3). The calculated geome-
and trans-Ru(CO)2(PEt3)2(CϵCSiMe3)2 [1.221(2) Å].[21]
tries compare well with those observed in the solid state,
The ruthenium–acetylide bond lengths in both the cis with both cis and trans isomers calculated to exhibit distor-
complexes 3, 6, and 8 and the trans complexes 2, 4 and tions from ideal octahedral geometries.
7 are generally comparable to the bond lengths in related
complexes, trans-Ru(CO)2(CϵCPh)2(PEt3)2 [2.074(3) Å],[22]
trans-Ru(CO)2(CϵCH)2(PEt3)2 [2.078(1) Å][22] and trans-
Ru(CϵCPh)2(dmpe)2 [2.042(5) and 2.044(5) Å],[10] al-
though one Ru–C bond of complex 8 is considerably short-
ened at 2.035(9) Å.
The symmetric nature of the products in solution is con-
firmed by the 31P{1H} NMR spectra, which exhibit a sing-
let resonance for the trans-substituted products, and two
triplets for the cis-substituted products. The PMe3 reso-
nances of the cis complexes all exhibit second-order behav-
iour in their 1H NMR spectra, with one resonance typically
appearing as a filled-in doublet.[28] The other PMe3 reso-
nance typically appears as a broadened triplet.
Ultraviolet irradiation of a [D6]benzene solution of cis-
Figure 3. Calculated structures of trans-Ru(CϵCMe)2(PMe3)4 (left)
Ru(CϵCMe)2(PMe3)4 (6) results in complete conversion to
and cis-Ru(CϵCMe)2(PMe3)4 (right).
trans-Ru(CϵCMe)2(PMe3)4 within 2 h, as evidenced by
31P{1H} NMR spectroscopy. Similarly,
a
sample of
In the stepwise reaction of trans-RuMe2(dmpe)2 with
cis/trans-Ru[CϵC(p-C6H4-Me)]2(PMe3)4 (4) containing phenylacetylene to yield firstly trans-Ru(CϵCPh)Me(dmpe)2
72% cis isomer underwent complete isomerisation to trans then trans-Ru(CϵCPh)2(dmpe)2,[19] the second metathesis
upon exposure to UV irradiation for 90 min, whereas irra- reaction is clearly the rate-limiting step, and the intermedi-
diation of trans-Ru(CϵCSiMe3)2(PMe3)4 (7) failed to yield ate (acetylido)(methyl) complex can be isolated. The reac-
any of the cis isomer. At room temperature, trans- tion of cis-RuMe2(PMe3)4 with terminal alkynes is signifi-
Ru(CϵCMe)2(PMe3)4 (6) shows little tendency to revert cantly faster and yields only the doubly substituted product.
back to the cis complex when left undisturbed in solution No evidence for (acetylido)(methyl) complexes, cis/trans-
for several months (Ͻ4% could be observed by NMR after Ru(CϵCR)Me(PMe3)4, was observed by 31P{1H} NMR
three months). Heating of a photochemically generated spectroscopy at 40 °C or at room temperature.[31] In the
sample of trans-Ru(CϵCPh)2(PMe3)4 (2) to 75 °C in [D8]- case of complexes bearing PMe3 ligands, substitution of the
toluene resulted in slow reconversion to the cis isomer, with second methyl group is significantly faster than substitution
a mixture containing approximately 78% trans and 22% cis of the first.
obtained after about 12 h. Kinetic analysis of the thermal
It is conceivable that the different reactivities of cis-Ru-
trans/cis isomerisation gives a ∆G‡ value of 117.6 kJmol–1 Me2(PMe3)4 and trans-RuMe2(dmpe)2 may arise from the
at 75 °C. Photoisomerisation of octahedral complexes, and inclusion of bidentate phosphanes in the latter, although
the thermally reversible nature of this process, has been re- the possibility that stereochemistry may be important can-
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Eur. J. Inorg. Chem. 2008, 4248–4254

Bis(acetylido) Complexes of RuII with Monodentate Phosphane Ligands
(operating at 200.13 MHz for 1H) instruments at 300 K, unless
not be easily ruled out. As trans-RuMe2(PMe3)4 is a seem-
ingly unknown compound,[32] we studied the reactivity of
cis-RuMe2(dmpe)2 to determine what effect both chelation
and stereochemistry have on the reactivity of dimethylru-
thenium starting materials.
An excess of phenylacetylene was added to the complex
cis-RuMe2(dmpe)2. No reaction occurred after heating to
40 °C for 15 h. The substitution of monodentate phospha-
nes for chelating phosphanes does have a significant influ-
1
otherwise stated. H and 13C NMR spectra were referenced to re-
sidual solvent resonances, whereas 31P NMR spectra were refer-
enced to external H3PO4. IR spectra were recorded with a Shim-
adzu 8400 series FTIR instrument. UV irradiation of metal com-
plexes was performed by using an Oriel 300 W high-pressure mer-
cury vapour lamp with the incident beam directed through a water-
filled jacket to filter IR radiation. Complexes subject to irradiation
were dissolved in [D6]benzene (ca. 0.1  solution) in thin-walled
5-mm NMR tubes fitted with concentric teflon valves. Terminal
ence on the reactivity of the starting material. If the mecha- acetylenes were purchased from Aldrich and used as received. cis-
[34]
RuMe2(PMe3)4 (1) was prepared from trans-RuCl2(PMe3)4
and
nism does involve the dissociation of a phosphane ligand
prior to acetylide coordination and subsequent elimination
of methane,[18] then this observation is not unexpected.
The failure of cis-RuMe2(dmpe)2 to undergo any reac-
tion at 40 °C also contrasts with the behaviour of trans-
Me2Mg in thf. The NMR spectra of this complex corresponded
with that reported in the literature.[35] cis-RuMe2(dmpe)2 was pre-
pared according to a literature procedure.[36]
cis/trans-Ru(CϵCPh)2(PMe3)4 (2): Phenylacetylene (0.40 mL,
RuMe2(dmpe)2. The stereochemistry of the complex, i.e. the 3.64 mmol) was added to a solution of cis-RuMe2(PMe3)4 (1,
0.148 g, 0.340 mmol) in thf (10 mL). The mixture was warmed to
40 °C for 2 h, after which time the volatiles were removed in vacuo.
The pale yellow product was washed with pentane and dried in
vacuo. Yield: 0.155 g (75%). The product contained approximately
97% cis-Ru(CϵCPh)2(PMe3)4 and 3% trans-Ru(CϵCPh)2(PMe3)4.
Characterisation data were consistent with that reported pre-
viously.[37,38] UV irradiation of a [D6]benzene solution for 3 h fol-
lowed by slow cooling gave crystals of trans-Ru(CϵCPh)2(PMe3)4
suitable for X-ray diffraction.
relative disposition of the methyl groups, is a factor that
also significantly influences the rate of reaction.
In the case of the trans complexes, substitution of one
methyl group by an acetylide ligand may result in a “deacti-
vation” of the remaining methyl group. In contrast, the in-
clusion of one acetylide group in the cis complex is less
likely to alter the strength of the remaining metal–alkyl
bond; thus, if there is sufficient energy present to overcome
the energy barrier to the first metathesis step, the second
step will also occur.
cis-Ru[CϵC-(p-C6H4OMe)]2(PMe3)4 (3): Prepared as described for
2
from RuMe2(PMe3)4 (0.154 g, 0.354 mmol) and (4-meth-
oxyphenyl)acetylene (0.46 mL, 3.55 mmol). The crude product con-
tained approximately 91% cis-Ru[CϵC(p-C6H4OMe)]2(PMe3)4 and
9% trans-Ru[CϵC(p-C6H4OMe)]2(PMe3)4. Yield: 0.175 g (74%).
Crystals suitable for X-ray diffraction were obtained by layering a
benzene solution of the complex with pentane. 1H NMR
(400 MHz, [D8]thf): δ = 7.04 (AAЈ of AAЈXXЈ, 4 H, ArH), 6.63
(XXЈ of AAЈXXЈ, 4 H, ArH), 3.67 (s, 6 H, OCH3), 1.60 [m, 18 H,
P(CH3)3], 1.43 [m, 18 H, P(CH3)3] ppm. 31P{1H} NMR (162 MHz,
Conclusions
A method for the preparation of symmetrically substi-
tuted bis(acetylido)ruthenium(II) complexes has been de-
veloped, entailing a σ-bond metathesis reaction between
cis-RuMe2(PMe3)4 and a terminal acetylene. Several of the
product complexes were isolated and crystallographically
2
2
[D8]thf): δ = –11.8 (t, JPP = 29.3 Hz), –15.4 (t, JPP = 29.3 Hz)
characterised and found to exhibit a significantly distorted ppm. 13C{1H,31P} NMR (100 MHz, [D8]thf): δ = 156.8, 131.4,
125.7, 125.1, 113.8, 107.3, 55.2, 23.2, 21.5 ppm. MS (ESI): m/z (%)
octahedral coordination environment. Inclusion of mono-
dentate phosphane ligands significantly enhances the rate
of reaction with terminal acetylenes when compared to
complexes bearing bidentate phosphanes. A change in ge-
ometry of the dimethylruthenium complex from cis to trans
results in significantly different patterns of reactivity.
= 593 (70) [M – PMe3]+, 517 (100) [M – 2 PMe3]+. IR (Fluorolube,
NaCl cell): νmax = 2075 (νCC) cm–1. C30H50O2P4Ru (667.69): calcd.
˜
C 53.97, H 7.55; found C 53.97, H 7.67.
cis/trans-Ru[CϵC(p-C6H4Me)]2(PMe3)4 (4): Prepared as described
for 2 from cis-RuMe2(PMe3)4 (0.199 g, 0.456 mmol) and p-ethyn-
yltoluene (235 µL, 1.85 mmol). The product contained approxi-
mately 72% cis-Ru[CϵC(p-C6H4Me)]2(PMe3)4 and 28% trans-
Ru[CϵC(p-C6H4Me)]2(PMe3)4. Yield: 0.146 g (52%). cis-4: 1H
NMR (500 MHz, [D8]thf): δ = 7.02 (AAЈ of AAЈXXЈ, 4 H, ArH),
6.86 (XXЈ of AAЈXXЈ, 4 H, ArH), 2.22 (s, C-CH3), 1.60 [m, 18 H,
P(CH3)3], 1.44 [m, 18 H, P(CH3)3] ppm. 31P{1H} NMR (121 MHz,
Experimental Section
General: All syntheses and manipulations involving air-sensitive
compounds were carried out by using standard vacuum-line and
Schlenk techniques under dry nitrogen or argon. Diethyl ether,
tetrahydrofuran, petroleum ether, toluene and benzene were dried
and degassed by refluxing in the presence of standard drying
agents[33] under dry nitrogen, and were freshly distilled prior to use.
All other solvents were dried according to standard methods. [D8]-
thf and [D6]benzene were dried with sodium benzophenone ketyl
and vacuum-transferred into ampoules prior to use. NMR spectra
were recorded with Bruker DMX600 (operating at 600.13, 150.92
and 242.95 MHz for 1H, 13C and 31P, respectively), Bruker AV-
2
2
[D6]benzene): δ = –11.72 (t, JPP = 29.1 Hz), –15.24 (t, JPP
=
29.1 Hz) ppm. 13C{1H,31P} NMR (125 MHz, [D8]thf): δ = 132.5
(ArC), 130.9 (ArCH), 129.7 (ArC), 129.09 (ArCH), 119.8
(RuCϵC), 108.3 (RuCϵC), 23.44 [P(CH3)3], 21.73 [P(CH3)3], 21.41
1
(CH3) ppm. trans-4: H NMR (500 MHz, [D8]thf): δ = 6.97 (AAЈ
of AAЈXXЈ, 4 H, ArH), 6.85 (XXЈ of AAЈXXЈ, 4 H, ArH), 2.21
(s, C-CH3), 1.58 [s, P(CH3)3] ppm. 31P{1H} NMR (121 MHz, [D6]-
benzene): δ = –7.02 (s) ppm. 13C{1H,31P} NMR (125 MHz, [D8]-
thf): δ = 132.4 (ArC), 130.8 (ArCH), 129.6 (ArC), 129.1 (ArCH),
ANCE DRX400 (operating at 400.13, 100.62 and 161.98 MHz for 120.0 (RuCϵC), 108.7 (Ru-CϵC), 21.38 (CH3), 20.42 [br.,
1H, 13C and 31P, respectively), Bruker DPX300 (operating at 300.13
P(CH3)3] ppm. MS (ESI): m/z (%) = 637 (8) [M+], 561 (100) [M –
1
and 121.49 MHz for H and 31P, respectively) or Bruker DPX200 PMe ]+, 485 (18) [M – 2 PMe ]+. IR (KBr): νmax = 2077 (νCC) cm–1.
˜
3
3
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L. D. Field, A. M. Magill, S. J. Dalgarno, P. Jensen
FULL PAPER
C30H50P4Ru (635.69): calcd. C 56.68, H 7.93; found C 56.55, H
7.88. Ultraviolet Irradiation of a [D6]benzene solution for 90 min
followed by slow concentration gave crystals suitable for X-ray dif-
fraction.
2 h resulted in complete conversion to trans-Ru(CϵCMe)2-
5
(PMe3)4. 1H NMR (300 MHz, [D6]benzene): δ = 2.11 (q, JPH
=
1.9 Hz, 6 H, CCH3), 1.45 [br. s, 36 H, P(CH3)3] ppm. 31P{1H}
NMR (121 MHz, [D6]benzene): δ = –5.62 (s) ppm. Slow concentra-
tion of a benzene solution gave crystals suitable for X-ray diffrac-
tion.
cis/trans-Ru(CϵCtBu)2(PMe3)4 (5): Prepared as described for 2
from RuMe2(PMe3)4 (0.172 g, 0.394 mmol) and tert-butylacetylene
(120 µL, 0.974 mmol) in acetone (4 mL). The crude product con-
tained approximately 82% cis-Ru(CϵCtBu)2(PMe3)4 and 18%
trans-Ru(CϵCtBu)2(PMe3)4. Concentration of the solution by half
and cooling to –20 °C resulted in precipitation of needle-shaped
white crystals. These were collected and dried in vacuo. Yield:
0.139 g (61%). cis-5: 1H NMR (300 MHz, [D8]thf): δ = 1.52 [m, 18
H, P(CH3)3], 1.35 [m, 18 H, P(CH3)3], 1.13 [s, 18 H, C(CH3)3] ppm.
trans-Ru(CϵCSiMe3)2(PMe3)4 (7): Prepared as described for 2
from RuMe2(PMe3)4 (0.406 g, 0.932 mmol) and (trimethylsilyl)-
acetylene (0.50 mL, 3.54 mmol) in acetone (4 mL). The product
contained approximately 7% cis-Ru(CϵCSiMe3)2(PMe3)4 and 93%
trans-Ru(CϵCSiMe3)2(PMe3)4. Yield: 0.328 g (59%). Crystals suit-
able for X-ray diffraction were grown by slow concentration of a
benzene solution of the product. 1H NMR (200 MHz, [D6]ben-
zene): δ = 1.40 [s, 36 H, P(CH3)3], 0.32 [s, 18 H, Si(CH3)3] ppm.
31P{1H} NMR (162 MHz, [D6]benzene): δ = –8.4 (s) ppm.
13C{1H,31P} NMR (100 MHz, [D6]benzene): δ = 157.0 (RuCϵC),
110.5 (RuCϵC), 19.5 [br., P(CH3)3], 2.3 [Si(CH3)3] ppm. IR (Fluo-
2
31P{1H} NMR (121 MHz, [D8]thf): δ = –8.70 (t, JPP = 30.0 Hz),
2
–11.4 (t, JPP = 30.0 Hz) ppm. 13C{1H} NMR (75 MHz, [D6]ben-
2
2
zene): δ = 111.9 (t, JPC = 12.1 Hz), 104.5 (dd, JPC = 88.2,
1
23.0 Hz), 33.3 [C(CH3)3], 30.0 [C(CH3)3], 23.3 [t, JPC = 9.6 Hz,
P(CH3)3], 21.4 [t, 1JPC = 15.4 Hz, P(CH3)3] ppm. trans-5: 1H NMR
(300 MHz, [D8]thf): δ = 1.49 [br. s, 36 H, P(CH3)3], 1.10 [s, 18 H,
C(CH3)3] ppm. 31P{1H} NMR (121 MHz, [D8]thf): δ = –3.41 (s)
ppm. MS (ESI): m/z (%) = 493 (12) [M – PMe3]+, 417 (100) [M – 2
rolube, NaCl cell): ν
= 1985 (νCC) cm–1. Spectroscopic charac-
˜
max
terisation was consistent with that previously reported.[37] Slow
concentration of a benzene solution gave crystals suitable for X-
ray diffraction.
PMe ]+. IR (CCl , NaCl cell): νmax = 2091 (νCC) cm–1. C24H54P4Ru
˜
3
4
cis-Ru(CϵCH)2(PMe3)4 (8): Prepared as described for 6 from Ru-
Me2(PMe3)4 (0.403 g, 0.925 mmol) and acetylene. The product con-
tained approximately 94% cis-Ru(CϵCH)2(PMe3)4 and 6% trans-
Ru(CϵCH)2(PMe3)4. The product was recrystallised from pentane
(567.66): calcd. C 50.78, H 9.59; found C 50.82, H 9.33.
cis-Ru(CϵCMe)2(PMe3)4 (6): Propyne was bubbled through a
warm (40 °C) solution of RuMe2(PMe3)4 (0.155 g, 0.355 mmol) in
thf (20 mL) for 1 h. The mixture was filtered, and the volatiles were
removed in vacuo to yield an off-white powder. The product con-
tained Ͼ99% cis-Ru(CϵCMe)2(PMe3)4. Yield: 0.117 g (68%). This
was recrystallised from pentane to yield crystals suitable for X-ray
1
to yield the cis isomer exclusively. Yield: 0.161 g (38%). H NMR
(300 MHz, [D6]benzene): δ = 2.08 (m, 2 H, CϵCH), 1.56 [m, 18
H, P(CH3)3], 1.15 [m, 18 H, P(CH3)3] ppm. 31P{1H} NMR
2
(202 MHz, [D6]benzene): δ = –12.3 (t, JPP = 29.4 Hz), –15.1 (t,
1
diffraction. H NMR (400 MHz, [D6]benzene): δ = 2.11 (m, 6 H,
2JPP = 29.4 Hz) ppm. 13C{1H} NMR (125 MHz, [D6]benzene): δ =
118.5 (m, RuCϵC), 92.3 (m, RuCϵC), 22.8 [m, P(CH3)3], 21.2 [m,
P(CH3)3] ppm. C16H38P4Ru (455.44): calcd. C 42.19, H 8.41; found
C 42.07, H 8.35.
CCH3), 1.54 [m, 18 H, P(CH3)3], 1.16 [m, 18 H, P(CH3)3] ppm.
31P{1H} NMR (162 MHz, [D6]benzene): δ = –10.0 (t, JPP
=
2
2
29.1 Hz), –13.8 (t, JPP = 29.1 Hz) ppm. 13C{1H,31P} NMR
(100 MHz, [D6]benzene): δ = 106.0 (RuCϵC), 97.3 (RuCϵC), 23.3
[P(CH3)3], 21.6 [P(CH3)3], 7.3 (ϵCCH3) ppm. MS (ESI): m/z (%) Computational Details: Geometry optimisations were performed by
= 409.1 (100) [M – P(CH3)3]+, 395.1 (45), 333.0 (23) [M – using the B3LYP[39] density functional employing a general basis
2 P(CH ) ]+. IR (Fluorolube, NaCl cell): ν
= 2098 (νCC) cm–1. set consisting of LANL2DZ[40] and the associated effective core
˜
3 3
max
C18H42P4Ru (483.50): calcd. C 44.71, H 8.76; found C 44.57, H
8.87. UV irradiation of a [D6]benzene solution of this complex for
potential (ECP) on the metal atom, combined with the
6-31G(d)[41] basis set on the remaining atoms. Optimisations were
Table 2. Crystallographic and structure refinement data for 2–4, and 6–8.
2
3
4
6
7
8
Empirical formula C28H46P4Ru
C30H50O2P4Ru
667.65
orthorhombic
Pna21
36.7671(3)
13.1365(1)
13.9300(1)
90
6728.06(9)
8
C30H50P4Ru
635.65
C18H42P4Ru
483.47
C22H54P4RuSi2
599.78
C16H38P4Ru
455.41
orthorhombic
Pmc21
13.409(3)
8.8805(18)
18.601(4)
90
2215.0(8)
4
Formula mass
Crystal system
Space group
a [Å]
607.60
monoclinic
P21
15.25780(10)
10.58100(10)
18.7283(2)
92.4250(10)
3020.84(5)
4
monoclinic
P21/c (#14)
14.361(2)
13.801(2)
17.596(3)
110.195(2)
3273.1(9)
4
monoclinic
P21/n (#14)
9.940(2)
16.200(2)
15.248(2)
100.448(2)
2414.6(7)
4
monoclinic
P21/c (#14)
16.1250(10)
10.5815(7)
20.9015(13)
111.577(1)
3316.4(4)
4
b [Å]
c [Å]
β [°]
V [Å3]
Z
T [K]
123(2)
1.336
0.746
56.40
123(2)
1.318
0.680
55.00
150(2)
1.290
0.691
56.60
150(2)
1.330
0.913
56.70
150(2)
1.201
0.746
56.66
173(2)
1.366
0.991
54.28
ρcalcd. [gcm–3]
µ(Mo-Kα) [mm–1]
2θmax [°]
Total number of
reflections
Number of unique 14649
reflections
40287
56700
32020
23850
32562
6954
12904
7884
5827
7992
3690
R [F, IϾ2σ(I)]
Rw [F, IϾ2σ(I)]
CCDC-
0.0386
0.0557
677063
0.0365
0.0769
677064
0.0205
0.0577
677065
0.0199
0.0494
677066
0.0235
0.0639
677067
0.0529
0.1511
677068
4252
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 4248–4254

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Supporting Information (see footnote on the first page of this arti-
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for funding, and the Australian Partnership for Advanced Comput-
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Received: May 20, 2008
Published Online: August 15, 2008
4254
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Eur. J. Inorg. Chem. 2008, 4248–4254