Mono- and bis-acetylidoruthenium(II) complexes by controlled metathesis of methylruthenium complexes with acetylenes

Article abstract of DOI:10.1021/om7004063

Acetylido methyl ruthenium(II) complexes, trans-Ru(C≡CR)(CH ₃)(dmpe)₂, were synthesized in a single metathesis reaction from trans-Ru(CH₃)₂(dmpe)₂ at ambient temperature; at elevated temperatures the reaction yields trans-Ru(C≡CR) ₂(dmpe)₂. Addition of a second terminal acetylene to a methanol solution of trans-Ru(C≡CR)(CH₃)(dmpe)₂ results in the formation of trans-Ru(C≡CR)(C≡CR′)(dmpe) ₂.

Full text of DOI:10.1021/om7004063

4776
Organometallics 2007, 26, 4776-4780
Mono- and Bis-acetylidoruthenium(II) Complexes by Controlled
Metathesis of Methylruthenium Complexes with Acetylenes
Leslie D. Field,*,† Alison M. Magill,† Timothy K. Shearer,† Scott J. Dalgarno,§ and
Peter Turner‡
School of Chemistry, UniVersity of New South Wales, Sydney, Australia, 2052, Department of Chemistry,
UniVersity of Missouri-Columbia, Columbia, Missouri 65211, and School of Chemistry, The UniVersity of
Sydney, Sydney, Australia, 2006
ReceiVed April 27, 2007
Acetylido methyl ruthenium(II) complexes, trans-Ru(CtCR)(CH3)(dmpe)2, were synthesized in a single
metathesis reaction from trans-Ru(CH3)2(dmpe)2 at ambient temperature; at elevated temperatures the
reaction yields trans-Ru(CtCR)2(dmpe)2. Addition of a second terminal acetylene to a methanol solution
of trans-Ru(CtCR)(CH3)(dmpe)2 results in the formation of trans-Ru(CtCR)(CtCR′)(dmpe)2.
in the presence of sodium hexafluorophosphate and a base,
represents a significant breakthrough. The reaction may be
performed in a stepwise manner, allowing the isolation of
alkynyl complexes bearing two unique acetylide moieties.
The metathesis reaction of acetylenes with transition-metal
alkyl complexes to yield alkynyl complexes is well-established
for rhodium(I) complexes,9 but is also known for cobalt(I)10
and platinum(II).11 We have described the synthesis of acetyli-
doiron(II) complexes by the photochemical metathesis of
methyl-iron(II) complexes12 and now wish to report a related
route to mono- and bis-acetylido complexes of ruthenium(II)
involving thermal metathesis of a dialkylruthenium complex.
Introduction
Since the mid-1980s “rigid-rod” transition-metal σ-alkynyl
complexes have come under increasing scrutiny1,2 due to their
potential applications as nonlinear optical,3 electronic com-
munication (“molecular wire”),4 luminescent,5 or liquid crystal-
line materials.6 This potential is mainly due to their high
stability, the possibility of extended π-electron conjugation, and
the relatively rigid, linear structure of the complexes.1
Traditionally, transition-metal σ-alkynyl complexes have been
synthesized by the reaction of metal alkynides (MCtCR; M )
Li, Na, Mg, SnR3, etc.) with transition-metal halides (LnMXn′;
X ) Cl, Br, I).1,7 When used for the synthesis of polymeric
metal-alkynyl complexes, these methods often result in uncon-
trolled multiple condensations yielding high molecular weight
material. The controlled formation of dimeric, trimeric, and
oligomeric complexes would allow the properties of the material
(e.g., solubility and crystal packing) to be more easily tuned.
The development of methods allowing controlled polymerization
is therefore highly desirable. To this end, the reaction scheme
reported by Dixneuf et al.,8 in which a dichlororuthenium
phosphine complex is allowed to react with a terminal alkyne
Results and Discussion
The previously unreported trans-Ru(CH3)2(dmpe)2 (1) (dmpe
) 1,2-bis(dimethylphosphino)ethane) was synthesized by a
modification of the procedure reported for the synthesis of cis-
Ru(CH3)2(dmpe)2.13 Treatment of trans-RuCl2(dmpe)2 with
MeLi in benzene, followed by recrystallization of the product
from pentane, gave trans-Ru(CH3)2(dmpe)2 in moderate yield.
Stereochemically, trans-Ru(CH3)2(dmpe)2 is relatively stable at
room temperature; however, irradiation with UV light for 15
min or sublimation resulted in quantitative isomerization and
isolation of cis-Ru(CH3)2(dmpe)2. Once formed, the cis complex
shows no tendency to revert to the trans-isomer over time; the
cis-isomer is clearly the thermodynamically more stable isomer,
but there is a considerable activation barrier to cis/trans
isomerization. Crystals of 1 suitable for X-ray diffraction were
grown by slow evaporation of a benzene solution (Figure 1,
Table 1). The asymmetric unit contains two half complex
* To whom correspondence should be addressed. Fax: +61 2 9385 2700.
Tel: +61 2 9385 8008. E-mail: L.Field@unsw.edu.au.
† University of New South Wales.
§ University of Missouri-Columbia.
‡ University of Sydney.
(1) Long, N. J.; Williams, C. K. Angew. Chem., Int. Ed. 2003, 42, 2586-
2617, and references therein.
(2) Manners, I. Angew. Chem., Int. Ed. Engl. 1996, 35, 1603-1621, and
references therein.
(3) (a) Powell, C. E.; Humphrey, M. G. Coord. Chem. ReV. 2004, 248,
725-756. (b) Cifuentes, M. P.; Powell, C. E.; Morrall, J. P.; McDonagh,
A. M.; Lucas, N. T.; Humphrey, M. G.; Samoc, M.; Houbrechts, S.;
Asselberghs, I.; Clays, K.; Persoons, A.; Isoshima, T. J. Am. Chem. Soc.
2006, 128, 10819-10832. (c) Cifuentes, M. P.; Humphrey, M. G. J.
Organomet. Chem. 2004, 689, 3968-3981. (d) Lind, P.; Bostrom, D.;
Carlsson, M.; Eriksson, A.; Glimsdal, E.; Lindgren, M.; Eliasson, B. J. Phys.
Chem. A 2007, 111, 1598-1609.
(8) See for example: (a) Touchard, D.; Haquette, P.; Guesmi, S.;
LePichon, L.; Daridor, A.; Toupet, L.; Dixneuf, P. H. Organometallics 1997,
16, 3640-3648. (b) Touchard, D.; Guesmi, S.; Le Pichon, L.; Daridor, A.;
Dixneuf, P. H. Inorg. Chim. Acta 1998, 280, 118-124. (c) Touchard, D.;
Haquette, P.; Pirio, N.; Toupet, L.; Dixneuf, P. H. Organometallics 1993,
12, 3132-3139. (d) Touchard, D.; Morice, C.; Cadierno, V.; Haquette, P.;
Toupet, L.; Dixneuf, P. H. J. Chem. Soc., Chem. Commun. 1994, 859-
860.
(4) (a) Paul, F.; Lapinte, C. Coord. Chem. ReV. 1998, 180, 431-509.
(b) Low, P. J. Dalton Trans. 2005, 2821-2824.
(5) (a) Yam, V. W. W.; Wong, K. M. C. Top. Curr. Chem. 2005, 257,
1-32. (b) Yam, V. W. W. J. Organomet. Chem. 2004, 689, 1393-1401.
(6) (a) Kaharu, T.; Matsubara, H.; Takahashi, S. J. Mater. Chem. 1991,
1, 145-146. (b) Kaharu, T.; Matsubara, H.; Takahashi, S. J. Mater. Chem.
1992, 2, 43-47. (c) Varshney, S. K.; Rao, D. S. S.; Kumar, S. Mol. Cryst.
Liq. Cryst. 2001, 357, 55-65.
(9) Zargarian, D.; Chow, P.; Taylor, N. J.; Marder, T. B. J. Chem. Soc.,
Chem. Commun. 1989, 540-544.
(10) Klein, H. F.; Karsch, H. H. Chem. Ber. 1975, 108, 944-955.
(11) Ozawa, F.; Mori, T. Organometallics 2003, 22, 3593-3599.
(12) Field, L. D.; Turnbull, A. J.; Turner, P. J. Am. Chem. Soc. 2002,
124, 3692-3702.
(7) Ren, T. Organometallics 2005, 24, 4854-4870.
(13) Chatt, J.; Hayter, R. G. J. Chem. Soc. 1963, 6017-6027.
10.1021/om7004063 CCC: $37.00 © 2007 American Chemical Society
Publication on Web 08/15/2007

Mono- and Bis-acetylidoruthenium(II) Complexes
Organometallics, Vol. 26, No. 19, 2007 4777
Scheme 1
Figure 1. Molecular projection of trans-Ru(CH3)2(dmpe)2 (1) with
thermal ellipsoids shown at the 50% probability level. Only a single
molecule of the unit cell and the major component of the disordered
phosphorus atoms are shown.
resonance at -1.29 ppm, again slightly upfield from the
corresponding resonance in 1. The identity of complex 3a was
unequivocally assigned by X-ray crystallography as trans-Ru-
(CtCPh)(CH3)(dmpe)2 (Figure 2, Table 1). The complex
exhibits a distorted octahedral geometry, with the methyl and
acetylide ligands occupying mutually trans positions.
Table 1. Selected Bond Lengths (Å) and Angles (deg) for 1,
3a, and 3b
The analogous reaction of 1 with tert-butylacetylene afforded
trans-Ru(CtCtBu)(CH3)(dmpe)2 (3b) when carried out at room
temperature; however, in this case 8 days were required for the
reaction to reach completion. If the reaction mixture was heated
1
3a
3b
Ru-C(1)
2.236(3)
N/A
N/A
2.286(1)
2.285(1)
N/A
N/A
N/A
84.29(4)
N/A
2.247(2)
2.069(2)
1.198(2)
2.3048(6)
2.3010(5)
2.2927(5)
2.2962(5)
179.10(7)
90.29(5)
177.5(2)
2.2213(8)
2.0682(8)
1.221(1)
2.2881(2)
2.2871(3)
2.2914(2)
2.2989(3)
178.50(4)
84.28(1)
Ru-C(2)
C(2)-C(3)
Ru(1)-P(1)
15
at reflux, trans-Ru(CtCtBu)2(dmpe)2 (2b) was the sole
Ru(1)-P(2)
product, with 3b being observable as an intermediate by 31P-
{1H} NMR spectroscopy. The observed differences in the
reactivity of 1 with phenyl- and tert-butylacetylene are unlikely
to be the result of differences in the steric requirements of the
ligands and may involve the formation of stabilizing π interac-
tions between the aryl substituents of the acetylene and the metal
center in 1. Alternatively, the observed difference in reactivity
may be ascribed to the differences in the respective acidities of
the starting acetylenes.
Crystals of 3b suitable for X-ray analysis were grown by slow
evaporation of a toluene solution. The complex is isostructural
with 3a, with some slight differences in bond lengths (Figure
2). The ruthenium-acetylide bond distances in 3a and 3b are
identical within experimental error (2.069(2) and 2.0682(8) Å,
respectively); however, the ruthenium-methyl bond is slightly
elongated in 3a (2.247(2) vs 2.2213(8) Å, respectively). The
carbon-carbon triple bond of the acetylide unit is longer in 3b
than 3a (1.221(1) and 1.198(2) Å, respectively). The metal-
acetylide bond in 3a (2.069(2) Å) is longer than the bonds
observed in the bis-acetylide complex trans-Ru(CtCPh)2-
(dmpe)2 (2.042(5) and 2.044(5) Å)15 and significantly longer
than in the analogous iron(II) complex, Fe(CtCPh)CH3(dmpe)2
(1.923(3) Å).12 Similarly, the metal-methyl bond in 3a is
significantly longer than in the iron complex (2.247(2) vs 2.144-
(3) Å).
Both 3a and 3b have potential as starting materials in the
preparation of unsymmetrically substituted bis-acetylidoruthe-
nium(II) complexes bearing two different acetylide moieties by
a controlled exchange of the methyl group with a second
acetylide. In an attempt to exploit this potential and thereby
prepare trans-Ru(CtCPh)(CtCtBu)(dmpe)2, a benzene solution
of 3a was allowed to react with excess tert-butylacetylene.
Under ambient conditions no reaction was observed; however,
if the reaction mixture was heated or irradiated with UV light,
the desired mixed acetylide product was formed but in conjunc-
tion with appreciable amounts of both trans-Ru(CtCPh)2-
(dmpe)2 and trans-Ru(CtCtBu)2(dmpe)2.
Ru(1)-P(3)
Ru(1)-P(4)
C(1)-Ru(1)-C(2)
P(2)-Ru(1)-P(1)
C(2)-C(3)-C(4)
178.3(1)
molecules, the metal centers of which reside on symmetry
inversion sites. Significant residual electron density peaks in
the vicinity of the phosphorus atoms were modeled as minor
occupancy phosphorus sites associated with a second orientation
of the complexes; the associated carbon sites were not resolved.
The Ru-CH3 bond distances (Ru(1)-C(1), 2.236(3) Å; Ru-
(2)-C(8), 2.225(3) Å) are significantly longer than in cis-Ru-
(CH3)2(PNP) (PNP ) (tBuPCH2SiMe2)2N-) (Ru-CH3, 2.075(2)
and 2.149(3) Å),14 reflecting the stronger trans influence of a
methyl group in comparison to an amido nitrogen. Dimethyl-
ruthenium(II) complexes are rare in the crystallographic litera-
ture, and 1 represents, to the best of our knowledge, the first
example of a structurally characterized octahedral dimethylru-
thenium(II) complex.
When heated, the reaction of trans-Ru(CH3)2(dmpe)2 (1) with
excess phenylacetylene in benzene proceeds smoothly to yield
the known15 complex trans-Ru(CtCPh)2(dmpe)2 (2a). When
monitored by 31P{1H} NMR spectroscopy, the reaction pro-
ceeded via a single intermediate, 3a, which was the sole product
when the reaction was carried out at room temperature for 24
h. In the absence of external heating, the reaction will not
progress past this initial stage (Scheme 1). It is interesting to
note that the cis-stereoisomer of Ru(CH3)2(dmpe)2 failed to react
under identical conditions.
Pure 3a could be obtained after removal of the solvent in
Vacuo and recrystallization from pentane. The 1H and 31P{1H}
NMR spectra of 3a are indicative of a trans-substituted product,
with a single resonance in the 31P{1H} NMR spectrum occurring
at 43.4 ppm, slightly upfield of the resonance displayed by 1.
1
The H NMR spectrum shows a phosphorus-coupled methyl
(14) Ingleson, M. J.; Pink, M.; Huffman, J. C.; Fan, H.; Caulton, K. G.
Organometallics 2006, 25, 1112-1119.
(15) Field, L. D.; George, A. V.; Hockless, D. C. R.; Purches, G. R.;
White, A. H. J. Chem. Soc., Dalton Trans. 1996, 2011-2016.
When the reaction was performed in methanol containing a
small amount of benzene to solubilize the starting materials, a
single complex with trans geometry was formed, as evidenced

4778 Organometallics, Vol. 26, No. 19, 2007
Field et al.
Figure 2. Molecular projection of trans-Ru(CtCPh)(CH3)(dmpe)2 (3a) (left) and trans-Ru(CtCtBu)(CH3)(dmpe)2 (3b) (right) showing
50% displacement ellipsoids for the non-hydrogen atoms, hydrogen atoms having arbitrary radii of 0.1 Å.
Scheme 2
likely reflecting the differing trans influences of the two
acetylides. These metal-carbon bond distances are appreciably
larger than those observed in both trans-Ru(CtCPh)2(dmpe)2
(2.042(5)/2.044(5) Å)15 and Ru(CtCtBu)(CO)(PPh3)(η5-C5H5)
(2.032(3) Å);13 however, the CtC bond distances of 4a are
midway between those observed for these two complexes
(1.226(7)/1.221(6) and 1.197(4) Å, respectively).
Complex 4b is isostructural with 4a with the alkynyl units
occupying mutually trans positions. In this case, the ruthenium-
acetylide (2.064(5), 2.070(5) Å) and carbon-carbon triple bond
lengths (1.215(6), 1.207(7) Å) are identical within experimental
error, while a significant distortion from linearity is observed
in the acetylide units, particularly in the trimethylsilyl-substituted
case, which exhibits a C(9)-C(10)-Si(1) bond angle (165.6-
(5)°) significantly reduced from the expected 180°. Similar
bending of the alkynyl core has been reported previously.16
In summary, we have developed a route to mono-acetyli-
domethyl- and bis-acetylidoruthenium complexes involving
controlled thermal metathesis from a dialkylruthenium complex.
The controlled nature of this reaction allows the synthesis of
complexes bearing two different acetylide ligands and results
in the isolation of a pure product after minimal workup. We
are currently investigating the application of this synthetic
approach in the stepwise synthesis of dinuclear and trinuclear
acetylide-bridged ruthenium complexes.
by 31P{1H} NMR spectroscopy (Scheme 2). Formation of the
product was complete within 30 min and did not require heat
or UV irradiation. While we are still studying the role of
methanol in this reaction, it is possible that this more acidic
solvent promotes protiodemethylation of the complex to yield
methane and a ruthenium methoxide complex, with the meth-
oxide ligand then acting as a more effective leaving group that
can be displaced by the terminal acetylide.
The related unsymmetrically substituted complex trans-Ru-
(CtCPh)(CtCSiMe3)(dmpe)2 (4b) was prepared in an analo-
gous fashion from 3a and (trimethylsilyl)acetylene. The iden-
tities of these complexes were established unequivocally by
X-ray diffraction studies (Figure 3, Table 2).
Complex 4a exhibits a distorted octahedral geometry with
the acetylide ligands occupying mutually trans positions. The
phosphine ligands and the tert-butyl substituent are disordered,
and it was necessary to restrain some phosphorus-carbon bond
lengths to maintain chemical meaning within the disorder model
for some of the metal ligands. Figure 3 shows only a single
representation of the disordered ligands. The metal-acetylide
bond distances (Ru(1)-C(8) 2.056(4) Å, Ru(1)-C(9) 2.074(4)
Å) and to a lesser extent the CtC distances (C(7)-C(8) 1.219-
(6) Å, C(9)-C(10) 1.208(6) Å) exhibit significant differences,
Experimental Section
All syntheses and manipulations involving air-sensitive com-
pounds were carried out using standard vacuum line and Schlenk
techniques under an atmosphere of dry nitrogen or argon. Diethyl
ether, tetrahydrofuran, petroleum ether, toluene, and benzene were
(16) (a) Bruce, M. I.; Hambley, T. W.; Snow, M. R.; Swincer, A. G. J.
Organomet. Chem. 1982, 235, 105-112. (b) Pedersen, A.; Tilset, M.;
Folting, K.; Caulton, K. G. Organometallics 1995, 14, 875-888. (c)
Bykowski, D.; McDonald, R.; Tykwinski, R. R. ArkiVoc 2003, 21-29.

Mono- and Bis-acetylidoruthenium(II) Complexes
Organometallics, Vol. 26, No. 19, 2007 4779
Figure 3. Molecular projection of trans-Ru(CtCPh)(CtCtBu)(dmpe)2 (4a) (left) and trans-Ru(CtCPh)(CtCSiMe3)(dmpe)2 (4b) (right)
showing 50% displacement ellipsoids for the non-hydrogen atoms, hydrogen atoms having arbitrary radii of 0.1 Å. In the case of 4a, only
one component of the disordered atoms is shown.
Table 2. Selected Bond Lengths (Å) and Angles (deg) for 4a
and 4b
methyllithium (3.5 equiv, 32 mmol, 1.6 M solution in diethyl ether).
The mixture was stirred for 48 h, the solvent was removed, and
the product was extracted into pentane (3 × 50 mL). The solvent
was removed, and the product, trans-Ru(CH3)2(dmpe)2 (1) (1.54
g, 40%), was dried under vacuum to give an off-white solid. The
product was recrystallized from pentane. Anal. Calcd for C14H38P4-
Ru: C, 38.98; H, 8.88. Found: C, 39.04; H, 8.72. MS (ESI): m/z
431 (8%) [M - 1], 401 (100) [M - 1 - 2 × CH3]. HRMS:
431.08908 (calcd for M - 1: 431.08873). 1H{31P} NMR (300.17
MHz, C6D6): δ 1.30 (s, 8H, 4 × P-CH2), 1.17 (s, 24H, 8 ×
P-CH3), -1.20 (s, 6H, Ru-CH3). 31P{1H} NMR (121.51 MHz,
C6D6): δ 46.74 (s). 13C{1H,31P} NMR (125.76 MHz, C6D6): δ
31.1 (CH2), 15.1 (CH3), -24.0 (Ru-CH3).
4a
4b
Ru(1)-C(8)
2.056(4)
2.074(4)
1.219(6)
1.208(6)
176.8(4)
177.1(4)
175.3(4)
2.064(5)
2.070(5)
1.215(6)
1.207(7)
174.1(4)
176.8(4)
178.6(5)
Ru(1)-C(9)
C(7)-C(8)
C(9)-C(10)
Ru(1)-C(8)-C(7)
Ru(1)-C(9)-C(10)
C(8)-C(7)-C(1)
C(9)-C(10)-X
178.8(5) (X ) C(11))
165.6(5) (X ) Si(1))
dried and degassed by refluxing over standard drying agents under
an atmosphere of dry nitrogen and were freshly distilled prior to
use. All other solvents were dried according to standard methods.
THF-d8 and benzene-d6 were dried over sodium benzophenone ketyl
and vacuum transferred into ampules prior to use.
trans-Ru(CH3)(CtCPh)(dmpe)2 (3a). Phenylacetylene (0.5 mL,
4.5 mmol) was added to a solution of trans-Ru(CH3)2(dmpe)2 (1)
(0.20 g, 0.46 mmol) in benzene (70 mL). The solution was stirred
for 24 h at room temperature. The solvent was removed under
vacuum to give crude trans-Ru(CH3)(CtCPh)(dmpe)2 (3a) (0.23
g, 95%) as a pale brown solid, which was recrystallized from
pentane. Anal. Calcd for C21H40P4Ru: C, 48.74; H, 7.79. Found:
C, 48.75; H, 7.76. MS(ESI): m/z 519 [M + 1]+ (8%), 504 [M +
1 - CH3]+ (35), 417 [M + 1 - CCPh]+ (8), 401 [M - CH3 -
CCPh]+ (100). HRMS: 519.118778 (calc for M + 1 519.12038).
1H{31P} NMR (400.13 MHz, C6D6): δ 7.40 (m, 2H, ArH), 7.16
(m, 2H, ArH), 7.01 (m, 1H, ArH), 1.49 (s, 12H, 4 × P-CH3),
1.40 (m, 4H, 2 × P-CH2), 1.25 (m, 4H, 2 × P-CH2), 1.07 (s,
12H, 4 × P-CH3), -1.30 (s, 3H, Ru-CH3). 31P{1H} NMR (161
MHz, C6D6): δ 43.5 (s). 13C{1H,31P} NMR (100.6 MHz, C6D6):
δ 133.9 (RuCtC), 131.8 (ArC), 130.5 (ArCH), 128.1 (ArCH),
122.2 (ArCH), 109.2 (RuCtC), 30.4 (P-CH2), 17.3 (P-CH3), 13.0
Nuclear magnetic resonance spectra were recorded on a Bruker
1
DMX500 (operating at 500.13, 125.92, and 202.45 MHz for H,
13C, and 31P, respectively), Bruker AVANCE DRX400 (operating
at 400.13, 125.76, and 161.98 MHz for 1H, 13C, and 31P,
respectively), or Bruker DPX300 (operating at 300.13 and 121.49
MHz for 1H and 31P, respectively) at 300 K unless otherwise stated.
1H and 13C NMR spectra were referenced to residual solvent
resonances, while 31P NMR spectra were referenced to external
H3PO4. Infrared spectra were recorded on a Shimadzu 8400 series
FTIR. UV irradiation of metal complex was performed using an
Oriel 300 W high-pressure mercury vapor lamp with the incident
beam directed through a water-filled jacket to filter infrared
radiation.
Terminal acetylenes were purchased from Aldrich and used as
received.
trans-Ru(CH3)2(dmpe)2 (1). A solution of trans-RuCl2(dmpe)2
(4.25 g, 9.0 mmol) in benzene (150 mL) was treated with
(P-CH3). IR: νCtC (Nujol) 2044 cm-1
.
trans-Ru(CH3)(CtCtBu)(dmpe)2 (3b). tert-Butylacetylene (2.0
mL, 16.2 mmol) was added to a solution of trans-Ru(CH3)2-

4780 Organometallics, Vol. 26, No. 19, 2007
Table 3. Crystal Data and Refinement Details for 1, 3a, 3b, 4a, and 4b
Field et al.
1
3a
3b
4a
4b
empirical formula
M
C14H38P4Ru
431.39
C21H40P4Ru
517.48
C19H44P4Ru
497.49
C26H46P4Ru
583.58
C25H46SiP4Ru
599.66
temp (K)
cryst syst
space group
unit cell dimensions
a (Å)
150(2)
monoclinic
P21/c (#14)
150(2)
monoclinic
P21/n (#14)
150(2)
triclinic
P1h (#2)
173(2)
monoclinic
P21/c
173(2)
monoclinic
C2/c
12.825(3)
12.607(3)
13.035(4)
90
93.952(4)
90
2103(1)
4
1.363
9.091(2)
8.867(2)
31.194(6)
90
95.538(3)
90
2502.7(9)
4
1.373
9.4092(3)
9.6418(3)
15.5081(5)
79.873(2)
79.755(2)
70.210(2)
1292.53(7)
2
1.278
0.855
44 221
13 885
18.807(4)
10.809(2)
15.165(3)
90
102.438(4)
90
3010(1)
4
1.288
39.173(12)
10.478(3)
15.255(5)
90
100.810(7)
90
6151(3)
8
1.295
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
F(calc) (g cm-3
)
µ(Mo KR) (mm-1
)
1.040
20 479
5058
0.886
23 810
5936
0.745
19 390
6634
0.768
16 973
6745
N
Nind
N
obs (I > 2σ(I))
4495
0.0449
0.1237
5203
0.0248
0.0626
11 857
0.0220
0.0552
4438
0.0471
0.1025
4564
0.0588
0.1249
R1(F)a
wR2(F2)b
a R1 ) ∑||Fo| - |Fc||/∑|Fo| for Fo > 2σ(Fo). wR2 ) (∑w(Fo2 - Fc )2/∑(wFc )2)1/2 all reflections w ) 1/[σ2(Fo ) + (0.04P)2 + 5.0P] where P ) (Fo
+
b
2
2
2
2
2
2Fc )/3.
(dmpe)2 (1) (0.70 g, 1.41 mmol) in benzene (50 mL). The solution
(RuCtCtBu), 109.1 (RuCtCPh), 102.3 (RuCtCtBu), 33.7 (C-
(CH3)3), 30.4 (P-CH2), 29.8 (C-(CH3)3), 16.0 (P-CH3), 15.6 (P-
was stirred at room temperature for 7 days. The solvent was
removed under vacuum, and the crude product, trans-
Ru(CH3)(CtCtBu)(dmpe)2 (3b) (0.73 g, 90%), was obtained as a
beige solid. The product was recrystallized from cold pentane.
MS(ESI): m/z 499 [M + 1]+ (4%), 483 [M + 1 - CH3]+ (10),
417 [M + 1 - CCtBu]+ (7), 401 [M - CH3 - CCtBu]+ (100).
HRMS: 499.152120 (calcd for M + 1 499.151538). 1H{31P} NMR
(400.13 MHz, C6D6): δ 1.51 (s, 12H, 4 × P-CH3), 1.46 (m, 4H,
2 × P-CH2), 1.36 (s, 9H, C-(CH3)3), 1.27 (m, 4H, 2 × P-CH2),
1.11 (s, 12H, 4 × P-CH3), -1.30 (s, 3H, Ru-CH3). 31P{1H} NMR
(161 MHz, C6D6): δ 43.4 (s). 13C{1H,31P} NMR (75.47 MHz,
C6D6): δ 113.5 (RuCtC), 105.0 (RuCtC), 34.0 (C-(CH3)3), 30.6
(P-CH2), 30.0 (C-(CH3)3), 17.1 (P-CH3), 13.3 (P-CH3), -23.9
CH3). IR: νCtC (Nujol) 2054 cm-1
.
trans-Ru(CtCPh)(CtCSiMe3)(dmpe)2 (4b). trans-Ru(CH3)-
(CtCPh)(dmpe)2 (3a) (0.80 g, 1.54 mmol) was dissolved in
benzene (3 mL), and trimethylsilylacetylene (2.0 mL, 14.15 mmol)
was added. Methanol (3 mL) was added, and the reaction was left
stirring at room temperature for 45 min. The solvent and excess
acetylene were removed under reduced pressure. trans-Ru(CtCPh)-
(CtCSiMe3)(dmpe)2 (0.86 g, 93%) was recrystallized from cold
pentane. Anal. Calcd for C25H46SiP4Ru: C, 50.07; H, 7.73.
Found: C, 50.24; H, 7.80. 31P{1H} NMR (121.51 MHz, C6D6): δ
39.67 (s). 1H{31P} NMR (300.17 MHz, C6D6): δ 7.34 (d, 2H, CH),
7.13 (t, 2H, CH), 6.94 (t, 1H, CH), 1.43 (s, 12H, P-CH3), 1.38 (s,
12H, P-CH3), 1.41 (s, 8H, P-CH2), 0.29 (s, 9H, Si-CH3). 13C-
{1H,31P} NMR (125.76 MHz, THF-d8): δ 156.6 (Ru-CtCSiMe3),
132.6 (ipso-C), 131.0 (ArCH), 130.5 (Ru-CtCPh), 128.3 (ArCH),
123.0 (ArCH), 111.1 (CtCSiMe3), 110.1 (CtCPh), 31.02 (PCH2),
16.14 (PCH3), 15.79 (PCH3), 2.41 (Si(CH3)3). IR: νCtC (KBr) 2063,
1989 cm-1. MS (ESI): m/z 599.7 [M - 1]+ (22%), 528.9 [M -
SiMe3]+ (100), 502.9 [M - CCSiMe3]+ (10), 400.9 [M - CCSiMe3
- CCPh]+ (25).
(Ru-CH3). IR: νCtC (Nujol) 2067 cm-1
.
trans-Ru(CtCPh)(CtCtBu)(dmpe)2 (4a). trans-Ru(CH3)(Ct
CPh)(dmpe)2 (3a) (0.11 g, 0.21 mmol) was dissolved in benzene
(3 mL), and excess tert-butylacetylene (1.5 mL, 12.1 mmol) was
added. Methanol (3 mL) was added, and the reaction was stirred
at room temperature for 45 min. The volatile components were
removed under reduced pressure, to give crude trans-Ru(CtCPh)-
(CtCtBu)(dmpe)2 (0.12 g, 95%), which was recrystallized from
cold pentane. Anal. Calcd for C26H46P4Ru: C, 53.51; H, 7.95.
Found: C, 53.32; H, 8.00. MS (ESI): m/z 583.9 [M + 1]+ (5%),
538.9 (8), 530.9 (11), 511.0 (42), 502.9 [M - CCtBu]+ (100), 483.0
Acknowledgment. The authors thank the Australian Re-
search Council for financial support and the University of New
South Wales for a postgraduate scholarship (T.K.S.).
1
[M - CCPh]+ (71), 400.9 [M - CCtBu - CCPh]+ (12). H{31P}
NMR (300.17 MHz, C6D6): δ 7.34 (d, 2H, ArH), 7.13 (t, 2H, ArH),
6.94 (t, 1H, ArH), 1.46-1.41 (br m, 32H, 8 × P-CH3 + 4 ×
P-CH2), 1.31 (s, 9H, C-(CH3)3). 31P{1H} NMR (121.51 MHz,
C6D6): δ 40.45 (s). 13C{1H,31P} NMR (125.76 MHz, C6D6): δ
132.3 (ArC), 131.0 (RuCtCPh), 130.7, 128.3, 122.7 (ArCH), 114.8
Supporting Information Available: A CIF file giving crystal-
lographic data. This material is available free of charge via the
Internet at http://pubs.acs.org.
OM7004063