A study of acetylene and acetylide carbonyl and diphosphine substituted ruthenium trinuclear clusters: Synthesis and structural characterization

Article abstract of DOI:10.1016/j.poly.2012.10.013

The synthesis and structural characterization of the acetylene and acetylide carbonyl ruthenium clusters: [Ru₃(CO)₉(μ-CO) {μ₃-η²-(//)-HCCR}] [R = C₆H ₄-4-CH₃ (1a), C₆H₃-2,5-(CH ₃)₂ (1b), C₆H₂-2,4,5-(CH ₃)₃ (1c), C₆H₄-4-^tBu (1d), C₆H₄-4-COH (1e), C₆H₄-4- NH₂ (1f)] and [Ru₃(CO)₉(μ-H) {μ₃-η²-(⊥)-CCR}] [R = C₆H ₄-4-CH₃ (2a), C₆H₃-2,5-(CH ₃)₂ (2b), C₆H₂-2,4,5-(CH ₃)₃ (2c), C₆H₄-4-^tBu (2d), C₆H₄-4-COH (2e), C₆H₄-4- NH₂ (2f)] are described. Compounds 1a-f were obtained under very mild conditions from the known [Ru₃(CO)₁₀(NCMe)₂] activated cluster in the presence of the monosubstituted phenylacetylenes; in all cases, the alkynes are coordinated to the metallic fragment as acetylene groups in a μ₃-η² parallel fashion without breaking the C_(sp)-H bond of the triple bond. In solution compounds of the 1 series slowly transformed to the acetylide derivatives (2), where the acetylene group undergoes an oxidative addition and a rearrangement of the -CC- coordinated fragment to a μ₃-η² perpendicular coordination mode of the C-C axis by breaking the C_(sp)-H bond to give a hydride ligand in each case. The diphosphines substituted derivatives [Ru₃(CO)₇(μ-diphosphine)(μ-H){μ₃- η²-(⊥)-CCR}] [diphosphine = dppe; R = C₆H ₄-4-CH₃ (3a), C₆H₃-2,5-(CH ₃)₂ (3b), C₆H₂-2,4,5-(CH ₃)₃ (3c) and diphosphine = dfppe; R = C₆H ₄-4-CH₃ (4a), C₆H₃-2,5-(CH ₃)₂ (4b), C₆H₂-2,4,5-(CH ₃)₃ (4c)] were obtained from the reaction of the [Ru ₃(CO)₁₀(diphosphine)] cluster (diphosphine = dppe or dfppe) with the terminal alkyne, respectively. All compounds have been characterized in solution by infrared spectroscopy and multinuclear magnetic resonance. The solid state structures of the acetylide compounds 2b-d and 3b have been established by single crystal X-ray diffraction studies; the -CC- fragment was observed in a μ₃-η² perpendicular coordination mode.

Full text of DOI:10.1016/j.poly.2012.10.013

Polyhedron 52 (2013) 170–182
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
A study of acetylene and acetylide carbonyl and diphosphine substituted
ruthenium trinuclear clusters: Synthesis and structural characterization
Micaela Hernández-Sandoval a, Gloria Sánchez-Cabrera a, María J. Rosales-Hoz b, Marco A. Leyva b,
Verónica Salazar a, José G. Alvarado-Rodríguez a, Francisco J. Zuno-Cruz a,
⇑
a Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, km 4.5 Carretera Pachuca–Tulancingo, Pachuca Hgo., 42184 México, Mexico
b Departamento de Química, Centro de Investigación y Estudios Avanzados del I.P.N., Apdo. Postal 14-740, 07000 México DF, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
Available online 23 October 2012
The synthesis and structural characterization of the acetylene and acetylide carbonyl ruthenium clusters:
[Ru3(CO)9(l-CO){l3-g
2-(//)-HC„CR}] [R = C6H4-4-CH3 (1a), C6H3-2,5-(CH3)2 (1b), C6H2-2,4,5-(CH3)3 (1c),
C6H4-4-tBu (1d), C6H4-4-COH (1e), C6H4-4-NH2 (1f)] and [Ru3(CO)9( 2-(\)-C„CR}] [R = C6H4-4-
l-H){l3-g
Dedicated to Alfred Werner on occasion of
the 100th Anniversary of his Nobel prize in
Chemistry.
CH3 (2a), C6H3-2,5-(CH3)2 (2b), C6H2-2,4,5-(CH3)3 (2c), C6H4-4-tBu (2d), C6H4-4-COH (2e), C6H4-4-NH2
(2f)] are described. Compounds 1a–f were obtained under very mild conditions from the known
[Ru3(CO)10(NCMe)2] activated cluster in the presence of the monosubstituted phenylacetylenes; in all
cases, the alkynes are coordinated to the metallic fragment as acetylene groups in a l3-g
2 parallel fashion
Keywords:
Ruthenium
Clusters
Acetylene
Acetylides
without breaking the C(sp)–H bond of the triple bond. In solution compounds of the 1 series slowly
transformed to the acetylide derivatives (2), where the acetylene group undergoes an oxidative addition
and a rearrangement of the –C„C– coordinated fragment to a l3
the C–C axis by breaking the C(sp)–H bond to give a hydride ligand in each case. The diphosphines
substituted derivatives [Ru3(CO)7( -diphosphine)( -H){l3
2-(\)-C„CR}] [diphosphine = dppe;
-g
2 perpendicular coordination mode of
l
l
-g
R = C6H4-4-CH3 (3a), C6H3-2,5-(CH3)2 (3b), C6H2-2,4,5-(CH3)3 (3c) and diphosphine = dfppe; R = C6H4-
4-CH3 (4a), C6H3-2,5-(CH3)2 (4b), C6H2-2,4,5-(CH3)3 (4c)] were obtained from the reaction of the
[Ru3(CO)10(diphosphine)] cluster (diphosphine = dppe or dfppe) with the terminal alkyne, respectively.
All compounds have been characterized in solution by infrared spectroscopy and multinuclear magnetic
resonance. The solid state structures of the acetylide compounds 2b–d and 3b have been established by
single crystal X-ray diffraction studies; the –C„C– fragment was observed in a l3-
g2 perpendicular
coordination mode.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
In the field of alkyne-substituted trimetallic clusters the most
common structural arrangements found are those in which the –
The metal cluster compounds containing terminal alkynes have
showed a great stability as well as a wide versatility in reactivity;
these features have prompted their continuous synthesis and
structural studies. For example, it is well known that an organic
group stabilizes the metal cluster framework, avoiding its possible
fragmentation. A number of saturated triruthenium-alkynyl clus-
C„C– group use to cap a delta cluster either in a l3
or l3
2-(\) perpendicular coordination mode [1,7,8,10,11]. When
a terminal alkyne R–C„C–H is coordinated to trinuclear ruthe-
nium cluster derivatives via an oxidative addition as a l3
2-(\)
-g
2-(//) parallel
-
g
-
g
acetylide, the products are generally stable; however, the variation
in electronic properties of either the cluster or the R-substituent
may change the bonding interactions and, therefore, the cluster
stabilization. Other observed bonding modes include a less stable
ters of general formula [Ru3(CO)10
(l3-g
2-RC„CR)] or [Ru3(CO)9
(l-H)(l3-g
2-C„CR)] has been synthesized from the direct reaction
of alkynes with [Ru3(CO)12] [1–3], or by displacement of labile li-
gands by the alkyne in activated precursors, such as [Ru3(CO)10
(NCMe)2] [4–6]. Several structural studies on terminal alkynes
with dodecacarbonyltriruthenium or some activated derivatives
have shown that the carbon–carbon triple bond adopts a variety
of bonding modes keeping intact the carbon skeleton [1,3,7–10].
l3-
g2 parallel coordination mode of the alkyne, the 1,2-H migra-
tion to form a vinylidene (@C@CHR) group, or a mode of reactivity
that involves the scission of the triple bond (C„C) to yield two
alkylidyne ligands coordinated in a l3
-g-CR mode. [12,13].
Moreover, it has been proposed that most unstable l3
-g
2-(//)
coordination mode of the alkynes could be achieved by incorpora-
tion of diphosphines, as dppm, due to an enhanced back-bonding
ability of the metal induced by the bidentate ligand [5,14,15],
⇑
Corresponding author. Tel.: +52 771 7172000x2204, cell: +52 1771 1625212;
fax: +52 771 7172000x6502.
which can help in stabilizing the binding mode l3-g
2-(//) parallel
of the alkyne.
E-mail address: fjzuno@uaeh.edu.mx (F.J. Zuno-Cruz).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.10.013

M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
171
Herein we report the synthesis and structural characterization
of one new series of l3
g2 acetylene (1a–f) and three new series
of l3
g2 acetylide (2a–f, 3a–c and 4a–c) triruthenium clusters.
CO and one absorption band attributed to the bridging carbonyl li-
gand from 1830 to 1844 cmꢀ1. The series 2 display just one
(CO)
-
m
-
pattern in the terminal region, similar to those previously reported
in similar clusters [7,16–18]. In the 1H NMR spectra of series 1, a
signal at high frequencies was observed, with chemical shifts rang-
ing from 8.75 to 8.36 ppm; these data are similar to those observed
All compounds were characterized in solution by infrared and 1H,
13C{1H}, 31P{1H} and 19F{1H} NMR spectroscopy and by 2D-hetero-
nuclear correlation experiments for the complete assignment of
carbon atoms. The molecular structures of compounds 2b–d and
3b in the solid state were determined by single crystal X-ray dif-
fraction studies.
in is structural complexes [Ru3(CO)9(l-CO){l3-g
2-(//)-HC„CR}]
t
(R = SiMe3, 9.18; SiPh3, 8.95; Bu, 8.31; H, 8.59; COH, 9.18 ppm),
which were assigned to the terminal hydrogen atoms of the paral-
lel alkynes [6,18]. In the 1H NMR spectra of series 2, the hydride
signals were observed at lower frequencies ranging from ꢀ20.36
toꢀ20.61 ppm, observing a rough tendency accordingly to the sub-
stituents on the phenyl ring following the order c > b > f > d > a > e.
These data indicate that the electronic density increment in the
cluster produces d displacements to higher frequencies. Table 1
shows the full assignment of 1H and 13C NMR for all signals belong-
ing to the different aromatic rings in the series 1 and 2.
2. Results and discussion
The activated cluster [Ru3(CO)10(NCMe3)2] reacts with an excess
of a given terminal alkyne RC„CH at room temperature [R = C6H4-
4-CH3 (a), C6H3-2,5-(CH3)2 (b), C6H2-2,4,5-(CH3)3 (c), C6H4-4-tBu
(d), C6H4-4-COH (e), C6H4-4-NH2 (f)], Scheme 1; the reaction was
monitored by color changes and corroborated by thin layer chro-
matography (tlc) observing the formation of two compounds in
each reaction. The compounds were isolated by preparative tlc
using a mixture of hexane:CHCl3 (80:20 v/v). The major product
obtained in the series was identified as the parallel acetylene clus-
The information obtained from the 13C{1H} NMR spectra of the
alkynyl ligands coordinated in either a parallel or perpendicular
mode allowed us to perform an analysis of the d(C ) + d(Cb) addi-
a
tion and d(C ) ꢀ d(Cb) subtraction of the
a and b carbon chemical
shifts, which have been proposed to be related to the total charge
a
ter 1 of general formula [Ru3(CO)9(l-CO){l3-g
2-(//)-HC„CR}] in
moderate yields (1a, 44%; 1b, 47%; 1c, 45%; 1d, 44%; 1e, 43%; 1f,
alteration in the C„C triple bond and its polarization, respectively
[7,18,19]. The d(C ) + d(Cb) data of the free ligands, the parallel
a
28%); the minor compound corresponds to the perpendicular acet-
ylide cluster 2 [Ru3(CO)9(l-H){l3-g
2-(\)-C„CR}] (2a, 19%; 2b,
derivatives (1a–f), and the acetylide compounds (2a–f) span from
156.9 to 163.9, 308.3 to 329.1, and 254.4 to 258.2 ppm, respec-
tively, indicating that, upon coordination, the largest change in
charge occurs in the parallel derivatives, while these are reduced
in the acetylide compounds. These evidence can be explained in
terms of the alkynyl coordination mode; in a parallel mode the
23%; 2c, 21%; 2d, 28%; 2e, 17%; 2f, 19%). The compounds 2a and
f have been previously reported [16,17]. It is noteworthy that in
chloroform solution the series of clusters 1 rapidly convert to clus-
ters 2 in less than 2 h at room temperature, indicating the low sta-
bility of the parallel derivatives. The transformation can also be
performed even at 0 °C.
r
:r
:p
interactions of the C„C fragment with the metal core pro-
duce the largest alteration in charge, while the change in coordina-
The infrared spectra of clusters 1 are very similar in the car-
bonyl region; all of them display bands in the region of terminal
tion, due to the breaking the C–H bond by the
r:p:p interactions,
H
R
R
Cα
Cβ
Cβ
Cα
Ru
(CO)3
Ru
(CO)3
Ru
H
(CO)3
Ru
Ru
(CO)3
(CO)3
Ru
(CO)3
C
O
R
5
6
(2a)
(2b)
(1a)
CH3
4
1
4´
2
3
CH3
5´
5
6
(1b)
4
1
3
2
H3C
2´
CH3
5
5´
6
(2c)
(2d)
(1c)
(1d)
CH3
4
1
4´
3
2
H3C
2´
5
6
C(CH3)3
1
4
4´
4´´
3
5
2
O
6
(2e)
(2f)
(1e)
(1f)
C
4
1
1
4´
H
2
3
5
6
NH3
4
2
3
Scheme 1. Structures of acetylene and acetylide ruthenium cluster series 1 and 2.

172
M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
Table 1
1H and 13C{1H} NMR data for compound series 1 and 2.
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
a
a
a
a
0
1a 8.75 (s, 1H, H )
178.7 (s, 1C, Cb)
145.6 (s, 1C, C(1))
138.7 (s, 1C, C(4))
[313.3]
{ꢀ44.1}
2a
2b
7.46 (HAA , 2H, H(2,6))
166.8 (s, 1C, C )
139.0 (s, 1C, C(4))
[258.2]
{75.4}
a
a
0
0
7.58 (HAA , 2H, H(3,5))
7.17 (HBB , 2H, H(3,5))
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 131.2 (s, 2C, C(2,6))
2.38 (s, 3H, CH3(4 ))
ꢀ20.52 (s, 1H, M–H–M)
0
0
0
0
0
7.32 (HBB , 2H, H(2,6))
0
0
0
0
0
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 134.6 (s, 1C, C )
131.0 (s, 1C, C(1))
129.9 (s, 2C, C(3,5))
91.4 (s, 1C, Cb)
a
0
2.54 (s, 3H, CH3(4 ))
129.2 (s, 2C, C(3,5)
126.0 (s, 2C, C(2,6)
0
0
21.3 (s, 1C, C4 )
21.5 (s, 1C, C(4) )
1b 8.36 (m, 1H, H )
176.7 (s, 1C, Cb)
[323.4]
{ꢀ30.0}
7.24 (s, 1H, H(6))
167.5 (s, 1C, C )
[255.7]
{79.3}
a
a
7.07 (d, 1H, H(4))
146.7 (s, 1C, C )
7.15 (d, 1H, H(3))
136.2 (s, 1C, C(5))
135.7 (s, 1C, C(1))
133.2 (s, 1C, C(2))
132.5 (s, 1C, C(6))
130.0 (s, 1C, C(3))
129.5 (s, 1C, C(4))
88.2 (s, 1C, Cb)
a
3J1 H = 8.0
135.5 (s, 1C, C(1))
133.0 (s, 1C, C(5))
130.7 (s, 1C, C(3))
129.0 (s, 1C, C(2))
127.7 (s, 1C, C(6))
127.6 (s, 1C, C(4))
3J1 H = 8.0
1
1
H–
H–
6.89 (d, 1H, H(3))
7.03 (d, 1H, H(4))
3J1 H = 8.0
3J1 H = 8.0
1
1
H–
H–
0
6.82 (s, 1H, H(6))
2.37 (s, 3H, CH3(2 ))
2.27 (s, 3H, CH3(5 ))
2.51 (s, 3H, CH3(2 ))
2.33 (s, 3H, CH3(5 ))
ꢀ20.40 (s, 1H, M–H–M)
0
0
0
0
0
21.8 (s, 1C, C(2 ))
22.5 (s, 1C, C(2 ))
0
0
21.1 (s, 1C, C(5 ))
21.0 (s, 1C, C(5 ))
1c 8.44 (s, 1H, H )
178.0 (s, 1C, Cb)
[323.7]
{ꢀ32.3}
2c
7.20 (s, 1H, H(6))
7.05 (s, 1H, H(3))
167.0 (s, 1C, C )
[255.4]
{78.6}
a
a
7.28 (s, 1H, H(3))
7.01 (s, 1H, H(6))
2.42 (s, 3H, CH3(2 ))
2.26 (s, 3H, CH3(5 ))
2.23 (s, 3H, CH3(4 ))
145.7 (s, 1C, C )
137.6 (s, 1C, C(5))
136.2 (s, 1C, C(2))
134.9 (s, 1C, C(4))
133.0 (s, 1C, C(6))
131.4 (s, 1C, C(3))
131.0 (s, 1C, C(1))
88.4 (s, 1C, Cb)
a
0
138.1 (s, 1C, C(1))
137.7 (s, 1C, C(4))
134.9 (s, 1C, C(5))
133.8(s, 1C, C(2))
133.5 (s, 1C, C(3))
131.0 (s, 1C, C(6))
2.49 (s, 3H, CH3(2 ))
0
0
2.27 (s, 3H, CH3(5 ))
0
0
2.24 (s, 3H, CH3(4 ))
0
ꢀ20.36 (s, 1H, M–H–M)
0
0
20.0 (s, 1C, C(2 ))
22.2 (s, 1C, C(2 ))
0
0
19.8 (s, 1C, C(5 ))
19.6 (s, 1C, C(5 ))
0
0
19.1 (s, 1C, C(4 ))
19.4 (s, 1C, C(4 ))
0
1d 8.57 (s, 1H, H )
175.3 (s, 1C, Cb)
149.3 (s, 1C, C(4))
143.2 (s, 1C, C(1))
[308.3]
{ꢀ42.3}
2d
7.50 (HAA , 2H, H(2,6))
164.0 (s, 1C, C )
149.8 (s, 1C, C(4))
[254.9]
{73.1}
a
a
0
0
7.29 (HBB , 2H, H(3,5))
7.38 (HBB , 2H, H(3,5))
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 129.3 (s, 2C, C(2,6))
1.35 (s, 9H, H(400)
ꢀ20.49 (s, 1H, M–H–M)
0
0
0
0
0
7.13 (HAA , 2H, H(2,6))
0
0
0
0
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 133.0 (s, 1C, C )
129.2 (s, 1C, C(1))
124.6 (s, 2C, C(3,5))
90.9 (s, 1C, Cb)
a
1.30 (s, 9H, H(400))
124.1 (s, 2C, C(3,5))
124.0 (s, 2C, (C2,6))
0
0
36.1 (s, 1C, C(4 ))
36.3 (s, 1C, C(4 ))
32.7 (s, 3C, C(400))
191.5 (s, 1C, COH)
173.7 (s, 1C, Cb)
154.8 (s, 1C, C(4)
32.8 (s, 3C, C(400))
191.2 (s, 1C, COH)
1e 9.96 (s, 1H, COH)
[314.0]
{ꢀ33.4}
2e 10.02 (s, 1H, COH)
[254.4]
{76.6}
0
8.73 (s, 1H, H )
7.88 (HAA , 2H, H(3,5))
165.5 (s, 1C, C )
a
a
0
0
7.78 (HAA , 2H, H(3,5))
7.69 (HBB , 2H, H(2,6))
141.9 (s, 1C, C(4))
0
0
0
0
0
7.27 (HBB , 2H, H(2,6))
140.3 (s, 1C, C )
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 135.9 (s, 1C, C(1))
a
0
0
0
0
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 135.9 (s, 1C, C(1)
130.3 (s, 2C, C(3,5))
–20.61 (s, 1H, M–H–M)
131.6 (s, 2C, C(3,5))
130.5 (s, 2C, C(2,6))
88.9 (s, 1C, Cb)
126.9 (s, 2C, C(2,6))
0
1f
8.41 (s, 1H, H )
181.9 (s, 1C, Cb)
[329.1]
{ꢀ34.7}
2f
7.37 (HAA , 2H, H(3,5))
165.0 (s, 1C, C )
147.1 (s, 1C, C(4))
[257.5]
{72.5}
a
a
0
0
7.04 (HAA , 2H, H(2,6))
147.2 (s, 1C, C )
6.63 (HBB , 2H, H(2,6))
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 132.7 (s, 2C, C(3,5))
a
0
0
0
0
0
6.54 (HBB , 2H, H(3,5))
144.8 (s, 1C, C4)
0
0
0
0
JAB, JA B = 8.1, JAA = 6.4, JBB = 2.0 128.1 (s, 2C, C(2,6)
3.88 (a, 2H, NH2)
ꢀ20.42 (s, 1H, M–H–M)
122.4 (s, 1C, C(1))
115.1 (s, 2C, C(2,6))
92.5 (s, 1C, Cb)
3.78 (br, 2H, NH2)
125.4 (s, 1C, C1)
120.1 (s, 2C, C(3,5))
In CDCl3. s = singlet, d = doublet, br = broad.
reduces this alteration. On the other hand, the d(C ) ꢀ d(Cb) data in
behavior has been observed in the CH group of the acetylene ligand
when compared to the free ligand; these trends could be due to a
diamagnetic deshielding effect produced by the metallic cluster.
a
the free ligands range from 1.5 to 9.4 ppm; the largest polarization
upon coordination was found in the acetylide derivatives due to
the C–H bond breaking, as observed from the d(C ) ꢀ d(Cb) data
In order to stabilize the alkynyl parallel coordination l3
binding mode in these complexes, by taking advantage of a bulky
-ligand previously attached to the metallic cluster, the reactions
of [Ru3(CO)10 -diphosphine)] clusters [diphosphine: dppe = 1,
-g
2-(//)
a
(72.5–79.3 ppm for the acetylide compounds; 30.0–44.1 ppm for
the parallel alkynyl derivatives). The analysis of the overall data
did not show a clear tendency; neither charge alteration nor bond
polarization could be correlated with the electronic properties of
the substituents in the phenyl rings. Nevertheless, we observed
that the presence of the aromatic systems reduces the charge alter-
ation and increases the bond polarization in the perpendicular
derivatives when our compounds were compared with the com-
l
(l
2-bis(diphenylphosphino)ethane or dfppe = 1,2-bis(dipentafluoro
phenylphosphino)ethane] with methyl-substituted aryl alkynes
(ligands a to c, Scheme 2) were studied. Thus, we firstly carried
out the reaction of [Ru3(CO)10(l-dppe)] with one equivalent of a
terminal alkyne HC„CR [R = C6H4-4-CH3 (a), C6H3-2,5-(CH3)2 (b),
pound [Ru3(CO)9(l-H){l3-g
2-(\)-C„CtBu}], where there is an
electron donating group directly attached to the triple bond,
C6H2-2,4,5-(CH3)3 (c)] in hot toluene for 1 h. The reaction yielded,
however, exclusively the l3
formula [Ru3(CO)7( -dppe)(l-H){l3-g
2-(\)-C„CR}] in moderate
-g
2-(\) acetylide cluster of general
[(d(C ) + d(Cb) = 278.2 and d(C ) ꢀ d(Cb) = 56.4 ppm] [18].
l
a
a
The chemical shifts of the ipso C1 atom of the substituted aro-
matic rings in the parallel acetylene clusters 1 were found at higher
frequencies (135.5–149.4 ppm) in comparison with the same car-
bon atom in the acetylide derivatives (122.4–35.9 ppm). A similar
yields (3a, 62%; 3b, 59%; 3c, 65%). Some other milder reaction
conditions were also tested; nevertheless, the starting diphosphine
cluster remained unchanged. We also studied the reaction of
[Ru3(CO)10(l-dfppe)], a more Lewis acidic cluster, with one

M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
173
R
R´
5
6
R´
(3a)
(4a)
H
F
CH3
4´
R
4
1
Cα
(CO)2
Ru
Cβ
Ru
2
3
R´
CH3
5´
P(2)
H2C
5
6
(CO)3
(3b)
(4b)
H
F
4
1
CH2
3
Ru
(CO)2
H
2
2
H3C
2´
CH3
P(1)
5
5´
R´
6
(3c)
(4c)
H
F
CH3
4´
4
1
R´
3
H3C
2´
Scheme 2. Structures of acetylide-diphosphine ruthenium cluster series 3 and 4.
equivalent of a terminal alkyne a–c, in THF at 60 °C for 1 h, result-
2.1. X-ray diffraction studies
ing, once again, in the formation of the analogous acetylide com-
pounds observed for the 3a–c series [Ru3(CO)7(
g
l
-dfppe)(
l
-H){l3
-
Single crystal X-ray diffraction studies were carried out; they al-
lowed us to confirm the solid state structures of the 2b–d and 3b
compounds. ORTEP diagrams of the structures are shown in Figs. 1–
4 and Table 4 collects some selected bond lengths and angles. Com-
pound 2c contains two crystallographically independent molecules
in the asymmetric unit; both are essentially identical and only one
of the two molecules is showed in Fig. 2; the compound 2d dis-
plays a positional disorder. The structures of these compounds
showed the perpendicular coordination of the acetylide group. In
compounds 2b–2d the Ru(1)–Ru(2) distances range from
2.7973(3) to 2.8074(11) Å while the dppe derivative 3b has the
2-(\)-C„CR}] (4a, 60%; 4b, 65%; 4c, 63%), Scheme 2. Milder reac-
tion conditions were needed in order to obtain these clusters due
to the electronic properties of the perfluorated diphosphine. Under
the reaction conditions explored, we were unable to obtain the
clusters bearing the parallel coordination mode of the alkyne. An
inverse method of synthesis of compounds 3a–c and 4a–c was at-
tempted, i.e. the addition of the corresponding diphosphine to the
acetylide complexes 2a–c in a 1:1 stoichiometric ratio; however,
no reaction was observed, in spite of the different reaction condi-
tions used such as MeCN/CH2Cl2 with Me3NO as activating agent
at room temperature, [Ph2CO]ꢀ catalyst in THF at room tempera-
ture or refluxing hexane.
longest bond distance 2.8086(7) Å. This Ru(1)–Ru(2) bond is
l-
bridged by a coordinated hydride ligand, confirmed by 1H NMR
data in solution (see above). Similar distances have been reported
for the structures of the analogous compounds: 2a (2.7925(9) Å)
Table 2 shows the 1H and 13C{1H} NMR spectroscopic data of the
diphosphine compounds 3a–c and 4a–c. The hydride signals for
the dppe series were observed, in average, at higher frequencies
(ꢀ19.60 ppm) than the dfppe series (ꢀ20.26 ppm) or CO 2a–c
series (ꢀ20.43 ppm), which agrees with the presence of a better
[16], [Ru3(CO)9(l-H){l3-g
2-(\)-C„CR}] [R = SiMe3 (2.7955 Å);
SiPh3 2.7960 Å) [18], and the longest one for compound 2f
(2.8113 Å) [17]. The other two bond distances Ru(2)–Ru(3) and
Ru(3)–Ru(1) are significantly different; the longest distances range
from 2.8121(6) to 2.8484(6) Å and the shorter from 2.7827(11) to
2.7973(6) Å. The largest difference between the shortest and the
longest bonds is observed in 3b (0.06 Å). These bond distances
r
-donor ligand. The analysis and comparison of the d(C ) + d(Cb)
a
data in these series showed that the charge alteration increases
from compounds 2a–c to 3a–c to 4a–c, [d(C ) + d(Cb): 254.4–
a
258.2 ppm at CO series, 261.6–263.7 ppm at dppe series, and
264.8–266.6 ppm at dfppe series]. This charge alteration is related
to the presence of different ligands attached to the clusters where
the electron donating properties of these ligands alter the charge
on the metal in the order CO < dppe < dfppe. On the other hand,
are shorter than the2 reported Ru–Ru bond distance in [Ru3(CO)12
(2.854 Å av.) [21].
]
All the C(1)–C(2) distances ranging from 1.292(8) to 1.314(8) Å
in the acetylide fragments are close to the normal C–C double bond
distance (Csp2–Csp2 1.34 Å [22]) reflecting the change in hybridiza-
tion of these carbons upon coordination. The C@C bond distance
reported for compound 2f is 1.314(6) Å; thus we observe that the
bond distance increases in the order 2b < 2c < 2d < 2f ffi 3b, which
can be related to the polarization in the C–C bond of the coordi-
nated acetylide.
The Ru(3)–C(1)–C(2) angles of the acetylide clusters are in the
152.9(4)–156.4(2)° range, while the C(1)–C(2)–C(3) angles are
somewhat smaller [143.6(5)–145.2(6)°]. The C(1)–C(2)–C(3) angles
increase according to 3b (143.6(5)°) < 2c (144.4° av) ffi 2d (144.3°
av) < 2b (145.2(6)°) ffi 2f (145.5(4)° [17]; this trend can be associ-
ated with a decrease in the number of substituents in the phenyl
rings, as well as with the type of the substituent. In the case of
3b, the coordination of the dppe ligand, with a larger steric
hindrance than the carbonyl substituents, causes a smaller angle.
The angles formed by the C(1)–C(2) vector and the plane formed
by the three metal atoms in the acetylide compounds have differ-
ent values [17.36(3)–20.21(2)°] depending on the phenyl ring sub-
stituents; the order observed was 3b < 2b < 2d < 2c (19.83° av),
and this situation is probably also associated with the inherent
hindrance properties of the ligands. On the other hand, the type
the d(C ) ꢀ d(Cb) data showed that the largest polarization of the
a
C„C bonds is present when the perfluorated diphosphine is coor-
dinated to the cluster, showing a dfppe > dppe ffi CO tendency,
[d(C ) ꢀ d(Cb): 72.5–79.3 ppm for the CO series, 75.5–78.2 ppm
a
for the dppe series, and 79.4–81.7 ppm for dfppe series)], this trend
can be related to the electron withdrawing properties of the fluo-
rinated rings in the diphosphine. The ipso C1 carbon atoms in the
diphosphine acetylide derivatives were found at similar frequen-
cies (132.3–136.0 ppm) than their analogous CO acetylides, 1a–c.
The 31P{1H} and 19F{1H} NMR data are showed in Table 3. It was
observed for compounds 3a–c, (dppe series) that the chemical shift
of the phosphorus atom P(2) attached to the ruthenium atom
bonded to the C of the acetylide through the
r-bond, is shifted
a
to higher frequencies, due to an increase in electron density on this
metal atom. The tendency is reversed when the fluorinated diphos-
phine was used in clusters 4a–c; the signal for P(2) is observed at
lower frequencies than the phosphorus atom P(1); this may be re-
lated to the presence of a more Lewis acidic diphosphine. The
19F{1H} spectra of compounds 4a–c showed signals in the charac-
teristic ortho, para and meta regions, for the four non-equivalent
phenyl rings [20].

174
M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
Table 2
1H and 13C{1H} NMR data for compound series 3 and 4.
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
a
a
a
a
0
3a 7.99 (m, 1H, Hp)
7.79 (m, 1H, Hp)
7.51 (m, 4H, Ho,m
7.47 (m, 4H, Ho,m
0
207.7 (d, 1C, CO)
[263.7]
{75.5}
4a 7.13 (HAA , 2H, H(2,6))
205.7 (br, 1C, CO)
202.5 (br, 1C, CO)
[266.6]
{79.4}
31
2J1
P = 12.5
6.92 (HBB , 2H, H(3,5))
0
H–
0
0
0
0
)
)
203.8 (d, 1C, CO)
JAB, JA B = 8.1, JAA = 6.4, JBB = 1.9 198.7 (br, 1C, CO)
2.92 (m, 2H, CH2)
2.25 (s, 3H, CH3 4 )
1.87 (m, 2H, CH2)
31
2J1
P = 8.6
198.2 (br, 1C, CO)
194.6 (br, 1C, CO)
189.6 (br, 1C, CO)
187.7 (br, 1C, CO)
H–
0
7.07 (HAA , 2H, H(2,6))
201.4 (s,br, 1C, CO)
200.5 (br, 1C, CO)
6.86 (m, 1H, Hp)
0
6.76 (HBB , 2H, H(3,5))
197.8 (d, 1C, CO)
ꢀ20.34 (AXY, 1H, M–H–M)
JAB, JA B = 8.1, JAA = 6.4, JBB = 1.9 2J1
P = 13.3
2J1
3J1
P(1) = 46.9
P(2) = 1.8
173.0 (s, 1C, C )
31
31
0
0
0
0
H–
H–
H–
a
31
6.68 (m, 1H, Hp)
2.29 (m, 2H, CH2)
2.27 (s, 3H, CH3(4 ))
1.75 (m, 2H, CH2)
192.0 (br, 1C, CO)
190.1 (br, 1C, CO)
149.6 (m, 4C, Co)
147.1 (m, 4C, Co)
145.8 (m, 2C, Cp)
143.8 (m, 2C, Cp)
142.6 (m, 2C, Ci)
0
169.6 (s, 1C, C )
a
139.3 (d, 1C, Ci)
31
ꢀ19.62 (AXY, 1H, M–H–M)
1J1
P = 47.4
H–
31
2J1
3J1
P(1) = 31.3
P(2) = 1.8
136.9 (d, 1C, Ci)
139.4 (m, 4C, Cm
138.6 (m, 2C, Ci)
)
H–
H–
31
31
1J1
P = 46.3
H–
136.0 (s, 1C, C(4))
138.0 (s, 1C, C(4))
136.8 (m, 4C, Cm
132.6 (s, 1C, C(1))
130.9 (s, 2C, C(2,6))
129.4 (s, 2C, C(3,5))
93.6 (s, 1C, Cb)
135.1 (d, 2C, Co)
)
31
2J1
P = 13.1
H–
134.5 (d, 1C, Ci)
31
1J1
P = 43.7
H–
134.5 (s, 1C, C(1))
133.7 (d, 2C, Co)
27.1 (d, 1C, CH2)
31
31
2J1
P = 10.1
1J13
P = 27.0
C–
H–
132.7(d, 1C, Ci)
24.0 (d, 1C, CH2)
31
31
1J1
P = 49.5
1J13
P = 25.3
C–
H–
0
131.3 (d, 2C, Cp)
21.2 (s, 1C, C(4 ))
31
4J1
P = 3.4
H–
131.0 (s, 2C, C(2,6))
130.0 (d, 2C, Cm
)
31
3J1
P = 9.3
H–
129.8 (d, 2C, Cp)
31
4J1
P = 3.3
H–
129.5 (d, 2C, Cm
)
31
3J1
P = 8.7
H–
129.3 (s, 2C, C(3,5))
129.1 (d, 2C, Co)
31
2J1
P = 11.4
H–
128.9 (d, C, Cm
)
31
3J1
P = 10.8
H–
128.7 (d, 2C, Co)
31
2J1
P = 13.8
H–
127.9 (d, 2C, Cm
)
31
3J1
P = 9.3
H–
94.1 (s, 1C, Cb)
26.0 (d, 1C, CH2)
31
1J1
P = 28.8
H–
21.5 (d, 1C, CH2)
31
1J1
P = 22.2
H–
0
21.3 (s, 1C, C(4 ))
3b 7.99 (m, 1H, Hp)
7.80 (m, 1H, Hp)
208.1 (d, 1C, CO)
[261.8]
{78.2}
4b 7.09 (d, 1H, H(4))
204.5 (br, 1C, CO)
202.7 (br, 1C, CO)
198.6 (br, 1C, CO)
198.2 (br, 1C, CO)
194.9 (br, 1C, CO)
189.7 (br, 1C, CO)
187.3 (br, 1C, CO)
[264.8]
{81.4}
31
2J1
P = 10.3
6.89 (d, 1H, H(3))
H–
1
7.52 (m, 8H, Ho,m
7.46 (m, 8H, Ho,m
)
)
203.9 (d, 1C, CO)
3J1 H = 7.8
H–
31
2J1
P = 8.7
6.73 (s, 1H, H(6))
2.98 (m, 2H, CH2)
2.58 (s, 3H, CH3(5 ))
2.14 (s, 3H, CH3(2 ))
1.99(m, 2H, CH2)
H–
6.92 (d, 1H, H(4))
6.78 (m, 1H, Hp)
6.69 (m, 1H, Hp)
6.61 (d, 1H, H(3))
3J1H-1H = 8.0
6.48 (s, 1H, H(6))
2.73 (s, 3H, CH3(5 ))
2.38 (m, 2H, CH2)
1.94 (s, 3H, CH3(2 ))
201.3 (br, 1C, CO)
0
200.5 (d, 1C, CO)
31
2J1
P = 9.9
0
H–
198.1 (d, 1C, CO)
173.3 (s, 1C, C )
a
31
2J1
P = 11.7
ꢀ20.24 (AXY, 1H, M–H–M)
149.6 (m, 4C, Co)
147.1 (m, 4C, Co)
146.1 (m, 2C, Cp)
143.8 (m, 2C, Cp)
141.4 (m, 2C, Ci)
H–
31
192.3 (br, 1C, CO)
189.7 (br, 1C, CO)
2J1
3J1
P(1) = 46.5
P(2) = 2.1
H–
H–
31
0
170.0 (s, 1C, C )
a
0
139.3 (d, 1C, Ci)
31
1.78 (m, 2H, CH2)
1J1
P = 47.2
139.4 (m, 4C, Cm
138.8 (m, 2C, Ci)
136.9 (m, 4C, Cm)
)
H–
ꢀ19.56 (AXY, 1H, M–H–M)
136.8 (d, 1C, Ci)
31
31
2J1
3J1
P(1) = 30.6
P(2) = 1.6
1J1
P = 47.6
H–
H–
H–
31
136.0 (s, 1C, C(1))
135.2 (s, 1C, C(2))
136.6 (s, 1C, C(5))
135.8 (s, 1C, C(1))
134.6 (s, 1C, C(2))
131.2 (s, 1C, C(6))
130.0 (s, 1C, C(3))
128.0 (s, 1C, C(4))
91.7 (s, 1C, Cb)
135.1 (d, 2C, Co)
31
2J1
P = 13.1
H–
134.5(d, 1C, Ci)
31
1J1
P = 42.3
H–
134.5 (s, 1C, C(5))
133.9 (d, 2C, Co)
27.2 (d, 1C, CH2)
31
31
2J1
P = 11.1
1J13
P = 29.7
C–
H–

M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
175
Table 2 (continued)
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
a
a
a
a
132.5(d, 1C, Ci)
24.4 (d, 1C, CH2)
31
31
1J1
P = 48.0
1J13
P = 23.3
C–
H–
0
132.3 (s, 1C, C(6))
131.4 (s, 1C, Cp)
21.4 (s, 1C, C(5 ))
0
20.5 (s, 1C, C(2 ))
131.2 (d, 1C, Cp)
31
4J1
P = 1.8
H–
130.0 (d, 2C, Cm
)
31
3J1
P = 10.0
H–
129.8 (d, 1C, Cp)
31
4J1
P = 2.3
H–
129.1 (d, 2C, Cm
)
31
3J1
P = 9.9
H–
129.1(s, 1C, Cp)
129.0 (s, 1C, C(4))
128.8 (d, 2C, Co)
31
2J1
P = 12.8
H–
128.7 (d, 2C, Co)
31
3J1
P = 12.1
H–
128.5 (d, 2C, Cm
)
31
2J1
P = 10.5
H–
127.6(d, 2C, Cm
)
31
3J1
P = 9.9
H–
127.1 (s, 1C, C(3))
91.8 (s, 1C, Cb)
25.7 (d, 1C, CH2)
31
1J1
P = 26.9
H–
21.4 (d, 1C, CH2)
31
1J1
P = 25.0
H–
0
20.8 (s, 1C, C(5 ))
0
14.2 (s, 1C, C(2 ))
3c 7.91 (m, 1H, Hp)
7.71 (m, 1H, Hp)
208.2 (d, 1C, CO)
[261.6]
{77.6}
4c 6.98 (s, 1H, H(3))
6.67 (s, 1H, H(6))
204.6 (br, 1C, CO)
202.8 (br, 1C, CO)
198.7 (br, 1C, CO)
198.1 (br, 1C, CO)
195.1 (br, 1C, CO)
189.9 (br, 1C, CO)
187.4 (br, 1C, CO)
[264.8]
{81.7}
31
2J1
P = 12.3
H–
7.44 (m, 8H, Ho,m
7.36 (m, 8H, Ho,m
6.73 (s, 1H, H(3))
6.59 (m, 1H, Hp)
6.48 (m, 1H, Hp)
6.36 (s, 1H, H(6))
2.62 (s, 3H, CH3(2 ))
2.30 (m, 2H, CH2)
2.07 (s, 3H, CH3(4 ))
)
)
203.9 (d, 1C, CO)
2.97 (m, 2H, CH2)
2.55 (s, 3H, CH3(2 ))
2.21 (s, 3H, CH3(4 ))
2.06 (s, 3H, CH3(5 ))
31
2J1
P = 7.2
0
H–
0
201.4 (s,br, 1C, CO)
0
200.6 (d, 1C, CO)
31
2J1
P = 8.6
1.95 (m, 2H, CH2)
H–
198.1 (d, 1C, CO)
ꢀ20.21 (AXY, 1H, M–H–M)
172.9 (s, 1C, C )
a
31
31
2J1
P = 12.3
H–
2J1
3J1
P(1) = 46.6
P(2) = 2.1
149.7 (m, 4C, Co)
147.2 (m, 4C, Co)
146.1 (m, 2C, Cp)
143.7 (m, 2C, Cp)
141.3 (m, 2C, Ci)
0
H–
31
192.3 (br, 1C, CO)
189.8 (br, 1C, CO)
H–
0
0
1.76 (s, 3H, CH3(5 ))
1.67 (m, 2H, CH2)
169.6 (s, 1C, C )
a
139.4 (d, 1C, Ci)
31
ꢀ19.62 (AXY, 1H, M–H–M)
1J13
P = 48.3
139.4 (m, 4C, Cm
138.8 (m, 2C, Ci)
)
C–
31
2J1
3J1
P(1) = 30.6
P(2) = 1.8
136.9 (d, 1C, Ci)
H–
H–
31
31
1J13
P = 48.9
137.0 (s, 1C, C(1))
136.8 (m, 4C, Cm
C–
135.1 (d, 2C, Co)
)
31
2J13
P = 12.9
136.4 (s, 1C, C(6))
134.3 (s, 1C, C(3))
131.9 (s, 1C, C(4))
131.3 (s, 1C, C(5))
131.7 (s, 1C, C(2))
91.9 (s, 1C, Cb)
C–
134.9 (s, 1C, C(2))
134.7 (s, 1C, C(4))
134.2 (d, 1C, Ci)
31
1J13
P = 50.7
C–
133.9 (d, 4C, Co)
31
2J13
P = 11.0
27.2 (d, 1C, CH2)
C–
31
133.7 (s, 1C, C(6))
133.2 (s, 1C, C(1))
133.1 (s, 1C, C(5))
1J1
P = 29.6
H–
24.3 (d, 1C, CH2)
31
1J1
P = 24.6
H–
0
132.6 (d, 1C, Ci)
21.2 (s, 1C, C(2 ))
31
1J13
P = 48.3
19.2 (s, 1C, C(4 ))
0
C–
0
131.4 (d, 1C, Cp)
131.1 (d, 1C, Cp)
130.6 (s, 1C, C(3))
18.9 (s, 1C, C(5 ))
130.0 (d, 2C, Cm
)
31
3J13
P = 9.4
C–
129.7 (d, 1C, Cp)
129.1 (d, 2C, Co)
31
3J13
P = 10.1
C–
128.9 (d, 2C, Co)
31
3J13
P = 8.2
C–
128.5 (d, 2C, Cm
)
)
31
3J13
P = 9.8
C–
128.2 (s, 1C, Cp)
127.6 (d, 2C, Cm
31
3J13
P = 9.0
C–
92.0 (s, 1C, Cb)
(continued on next page)

176
M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
Table 2 (continued)
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
1H d(ppm) J(Hz)
13C{1H} d(ppm) J(Hz) [C + Cb] {C ꢀ Cb}
a
a
a
a
25.8 (d, 1C, CH2)
31
1J13
P = 25.2
C–
0
22.5 (s, 1C, C(2 ))
21.5 (d, 1C, CH2)
31
1J13
P = 28.6
C–
0
19.4 (s, 1C, C(4 ))
0
19.1 (s, 1C, C(5 ))
In CDCl3, s = singlet, d = doublet, m = multiplet, br = broad. o, ortho; p, para; m, meta; i, ipso.
Table 3
31P{1H} and 19F{1H} NMR data for compound series 3 and 4.
31P{1H} d(ppm)
31P{1H} d(ppm)
19F{1H} d(ppm) J(Hz)
3a
57.7 (s) P(2)
44.7 (s) P(1)
4a
26.4 (s) P(1)
22.6 (s) P(2)
ꢀ126.7 (d, 2F, Fo)
ꢀ127.5 (d, 2F, Fo)
ꢀ129.9 (br, 2F, Fo)
ꢀ148.7 (t, 1F, Fp)
ꢀ149.5 (t, 1F, Fp)
19
3J19
Fm = 20.0
Fp–
ꢀ132.0 (d, 2F, Fo)
–156.4 (br, 2F, Fm)
19
3J19
Fm = 19.2
ꢀ157.5 (m, 4F, Fm
)
)
Fo–
–143.8 (t, 1F, Fp)
ꢀ145.1 (t, 1F, Fp)
ꢀ127.3 (d, 2F, Fo)
ꢀ127.7 (d, 2F, Fo)
ꢀ130.5 (br, 2F, Fo)
ꢀ158.1 (br, 2F, Fm
3b
3c
56.3 (s) P(2)
45.7 (s) P(1)
4b
4c
26.2 (s) P(1)
22.7 (s) P(2)
ꢀ145.2 (t, 1F, Fp)
ꢀ148.8 (t, 1F, Fp)
-148.9 (t, 1F, Fp)
19
ꢀ132.0 (d, 2F, Fo)
3J19
Fm = 20.7
Fp–
19
3J19
Fm = 15.5
–157.7 (br, 2F, Fm)
-158.3 (m, 6F, Fm)
Fo–
–143.9 (t, 1F, Fp)
ꢀ127.2 (d, 2F, Fo)
ꢀ127.6 (d, 2F, Fo)
ꢀ130.4 (br, 2F, Fo)
56.3 (s) P(2)
45.8 (s) P(1)
26.5 (s) P(1)
22.6 (s) P(2)
ꢀ148.8 (t, 1F, Fp)
ꢀ149.7 (t, 1F, Fp)
19
3J19
Fm = 23.0
Fp–
ꢀ132.0 (d, 2F, Fo)
–157.5 (br, 2F, Fm
ꢀ158.2 (m, 4F, Fm
ꢀ158.6 (br, 2F, Fm
)
)
)
19
3J19
Fm = 17.3
Fo–
–143.8 (t, 1F, Fp)
ꢀ145.1 (t, 1F, Fp)
In CDCl3. s = singlet, d = doublet, m = multiplet, br = broad. o, ortho; p, para; m, meta.
of substituents on C(2) does not affect the perpendicular relation
between the C(1)–C(2) and Ru(1)–Ru(2) vectors, with an average
of 89.37°; this value is slightly smaller than those reported for
the l3-g
2-(//) parallel coordination of the acetylene, showing that
the changes in electronic properties of the cluster, at least with this
two diphosphines, is not enough to isolate this parallel coordina-
tion of the alkyne. The X-ray structures of compounds 2b–d and
the analogous compounds [Ru3(CO)9(l-H){l3-g
2-(\)-C„CR}]
(R = SiMe3, 89.7°; SiPh3, 89.81°) [18].
3b showed the thermodynamically stable l3-g
2-(\) perpendicular
For compound 3b, the P(2) of the diphosphine is roughly located
in the plane of the metal atoms [P(2)–Ru3 triangular plane dis-
tance: 0.502 Å], with a dihedral angle P(2)–Ru(2)–Ru(3)–Ru(1) of
167.03(5)°; however the P(1) is located above the metal triangle
plane [ca. 1.267 Å] with a dihedral angle P(1)–Ru(1)–Ru(2)–Ru(3)
mode of the acetylide, without significant changes in structural
parameters.
4. Experimental
of 146.18(4)o. In 3b is observed an intramolecular
p-stacking inter-
4.1. General procedures and materials
action between a phenyl ring of the diphosphine dppe and the
acetylide ring with a distance of 3.859 Å between centroids. The
Ru–P and Ru–C bond lengths agree with the normal values for
ruthenium(0).
[Ru3(CO)10(NCMe3)2] [4], [Ru3(CO)10
(l-dppe)] [23] and
[Ru3(CO)10 -dfppe)] [20] were prepared by published methods.
(l
All chemicals were purchased from Aldrich Company and used
as received except for Me3NO. Trimethylamine N-oxide (5 g,
0.065 mmol) was dried using dry DMF (100 mL); the mixture was
distilled until reach a volume of 15–20 mL. The resulting needles
of the oxide were washed three times with freshly distilled DMF
(4 mL) and the residue was filtrated. The white needles were
repeatedly sublimed in high vacuum at 100 °C by means of an oil
bath until dry bright white needles were obtained. All reactions
were performed under a nitrogen atmosphere by using standard
Schlenk techniques. Solvents were dried by the standard proce-
dures prior to use. Commercial tlc plates (silica gel 60 F254) were
used to monitor the progress of the reactions. Infrared spectra were
recorded as a solid thin film on a CsI window on a GX PERKIN Elmer
2000 FT-IR spectrometer or in NaCl cells on a PERKIN Elmer 16FPCF-
PIR spectrophotometer. NMR spectra were measured on a JEOL 400
and VARIAN 400 spectrometers in CDCl3, with 1H and 13C spectra
relative to SiMe4, 31P spectra relative to 85% aq. H3PO4 and 19F
3. Conclusions
The synthesis of the parallel acetylene and perpendicular acet-
ylide ruthenium trinuclear carbonyl and diphosphine clusters was
achieved. In solution, the acetylene 1a–f compounds rapidly con-
vert into the acetylide 2a–f clusters, showing the low stability of
the l3- p:r:r ligand donation.
g2 coordination mode based on a
The analysis of the 13C{1H} chemical shifts of the C and Cb
a
atoms in conjunction with the addition and subtraction of the indi-
vidual chemical shifts, was used to propose the change in polariza-
tion or charge on the triple bond due to variations in the aryl
substituents, in the modes of coordination, and in the changes of
the substituents on the ruthenium cluster.
Under the reaction conditions used, the presence of the diphos-
phine dppe or dfppe did not produce the desired stabilization of

M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
177
Fig. 1. ORTEP view of compound 2b (30% probability).
spectra referred to CFCl3. Mass spectrometric measurements
performed by direct insertion were recorded on a HR-LC 1100/
MSD TOF Agilent Technology equipment at CINVESTAV-México.
compounds were separated on tlc chromatographic plates [eluent:
hexane:CHCl3 (80:20 v/v)]. The yellow first band was identified as
the
HC„CR}] (2) and the orange second band corresponded to parallel
derivatives [Ru3(CO)9( -CO){l3
2-(//)-HC„CR}] (1). Note: It was
perpendicular
derivatives
[Ru3(CO)9(l-CO){l3-g
2-(\)-
4.2. Synthesis of compound [Ru3(CO)10(MeCN)2]
l
-g
not possible to obtain adequate elemental analysis for compounds
1a–f; due to their inherent instability; they continually are transform
to compounds 2a–f, respectively.
A solution of dry trimethylamine N-oxide, Me3NO, (13.2 mg,
0.176 mmol) in acetonitrile (4.00 mL) was added dropwise to a
solution of [Ru3(CO)12] (50.0 mg, 0.0780 mmol) in dichloromethane
(40.0 mL)/acetonitrile (10.0 mL) at ꢀ78 °C, in a dry ice–acetone
bath, over a period of 15 min. Then, the solution was removed from
the dry ice bath and it was slowly warmed to room temperature,
4.3.1. [Ru3(CO)9(
[Ru3(CO)9( -H){l3
4-Ethynyltoluene (16.0
2-(//)-HC„C C6H4-4-CH3}] (1a); yield: 44.0%, 18.0 mg orange so-
lid. IR (CO): 2097(m), 2061(sh), 2055(vs), 2029(w), 2015(sh),
1881(w) cmꢀ1. [Ru3(CO)9( 2-(\)-C„CC6H4-4-CH3}] (2a);
-H){l3
l
-CO){l3
2-(\)-C„C C6H4-4-CH3}] (2a)
L, 0.126 mmol). [Ru3(CO)9(
-g
2-(//)-HC„C C6H4-4-CH3}] (1a) and
l
-g
l
l-CO){l3-
where the complete conversion of [Ru3(CO)12] into [Ru3(CO)10
-
g
(NCMe)2] (52.0 mg, 0.0780 mmol) had occurred after 15 min
approximately (tlc monitored).
m
l
-g
yield: 21.0%, 8.40 mg, yellow solid. IR
m(CO): 2097(w), 2073(m),
4.3. General procedure for the synthesis of compounds 1a–f and 2a–f
2053(m), 2022(vs), 1986(w) cmꢀ1. HR–MS (ESI–TOF); [M+H]ꢀ for
(C18H7O9Ru3) Calc. 672.7225, found +672.7220 amu. Anal. Calc. for
An excess of the corresponding alkyne HC„CR was added to the
solution of [Ru3(CO)10(NCMe)2] (52.0 mg, 0.0780 mmol) freshly
prepared; the solution was stirred at room temperature under N2
for 30 min displaying a color change, from yellow to red. The sol-
vent was removed under reduced pressure, and the resulting resi-
due was dissolved in a small amount of dichloromethane. The
C18H8O9Ru3 (671.46): C, 32.20; H, 1.20. Found: C, 32.15; H, 1.18%.
4.3.2. [Ru3(CO)9(
[Ru3(CO)9( -H){l3
l-CO){l3-g
2-(//)-HC„C C6H3-2,5-(CH3)2}] (1b) and
l
-g
2-(\)-C„C C6H3-2,5-(CH3)2}] (2b)
1-Ethynyl-2,5-dimethylbenzene (18.0 L, 0.126 mmol).
[Ru3(CO)9( -CO){l3
2-(//)-HC„CC6H3-2,5-(CH3)2}] (1b); yield:
l
l
-g

178
M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
Fig. 2. ORTEP view of compound 2c (30% probability).
19.0%, 47.0 mg, orange solid. IR
2029(vs), 2013(sh), 1877(w) cmꢀ1
m
(CO): 2097(m), 2059(vs),
amu. Anal. Calc. for C20H12O9Ru3 (699.52): C, 34.34; H, 1.73. Found:
C, 34.65; H, 1.59%.
.
[Ru3(CO)9( -H){l3
l
-g
2-(\)-
C„C C6H3-2,5-(CH3)2}] (2b); yield: 23.0%, 9.20 mg, yellow solid.
m .
(CO): 2097(w), 2071(vs), 2053(vs), 2022(vs), 1990(m) cmꢀ1
4.3.4. [Ru3(CO)9(
[Ru3(CO)9( -H){l3
1-Ethynyl-4-terbutylbenzene (20.0
(CO)9( -CO){l3
2-(//)-HC„CC6H4-4-tBu}] (1d); yield: 44.0%,
17.7 mg, orange solid. IR (CO): 2097(m), 2050(vs), 2006(vs),
1874(w) cmꢀ1. [Ru3(CO)9( 2-(\)-C„CC6H4-4-tBu}] (2d);
-H){l3
yield: 28.0%, 11.2 mg, yellow solid. IR (CO): 2098(m), 2051(vs),
l
-CO){l3
2-(\)-C„CC6H4-4-tBu}] (2d)
L, 0.111 mmol). [Ru3
-g
2-(//)-HC„CC6H4-4-tBu}] (1d) and
IR
HR–MS (ESI–TOF); [M+H]ꢀ for (C19H9O9Ru3) Calc. 686.7382, found
+686.7384 amu. Anal. Calc. for C19H10O9Ru3 (685.49): C, 33.29; H,
1.47. Found: C, 33.54; H, 1.30%.
l
-g
l
l
-g
m
l
-g
-g
2-(//)-HC„CC6H2-2,4,5-(CH3)3}] (1c) and
m
4.3.3. [Ru3(CO)9(
[Ru3(CO)9( -H){l3
1-Ethynyl-2,4,5-trimethylbenzene
[Ru3(CO)9( -CO){l3
2-(//)-HC„CC6H2-2,4,5-(CH3)3}] (1c); yield:
45.0%, 18.0 mg, orange solid. IR (CO): 2096(m), 2049(vs),
2014(vs), 1874(w) cmꢀ1 2-(\)-C„CC6H2-
[Ru3(CO)9( -H){l3
l
-CO){l3
2-(\)-C„CC6H2-2,4,5-(CH3)3}] (2c)
(32.0 mg, 0.223 mmol).
2012(vs), 1970(m) cmꢀ1. HR–MS (ESI–TOF); [M+H]ꢀ for (C21H13O9-
Ru3) Calc. 714.7695, found +714.7702 amu. Anal. Calc. for C21H4O9-
Ru3 (713.53): C, 35.35; H, 1.98. Found: C, 34.79; H, 1.93%.
l
-g
l
-g
m
.
l
-
g
4.3.5. [Ru3(CO)9(
[Ru3(CO)9( -H){l3
4-Ethynylbenzaldehyde (20.0 mg, 0.153 mmol). [Ru3(CO)9
-CO){l3 (1e); yield: 43.0%,
2-(//)-HC„CC6H4-4-COH}]
l
-CO){l3
-g
-g
2-(//)-HC„C C6H4-4-COH}] (1e) and
2,4,5-(CH3)3}] (2c); yield: 21.0%, 8.40 mg, yellow solid. IR
m
(CO):
l
2-(\)-C„C C6H4-4-COH}] (2e)
2096(m), 2068(vs), 2049(vs), 2013(vs), 1983(s) cmꢀ1. MS (ESI–
TOF); [MꢀH]ꢀ for (C20H11O9Ru3) Calc. 700.7538, found +700.7549
(l
-g

M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
179
Fig. 3. ORTEP view of compound 2d (30% probability).
17.3 mg, orange solid. IR
2056(s), 2036(m), 2026(m), 2016(sh), 1954(w), 1884(vw, br)
cmꢀ1. [Ru3(CO)9( 2-(\)-C„CC6H4-4-COH}] (2e); yield:
-H){l3
17.0%, 6.80 mg, yellow solid. IR
m
(CO): 2098(vw), 2076(m), 2066(m),
solid. IR
m
(CO): 2095(m), 2046(vs), 2004(vs), 1830(w) cmꢀ1. [Ru3
2-(\)-C„CC6H4-4-NH2}] (2f); yield: 19.0%,
(CO)9( -H){l3-g
l
l
-
g
7.60 mg, yellow solid. IR m(CO): 2096 (m), 2067 (vs), 2048(vs),
m(CO): 2072(m), 2057(m),
2010(vs) cmꢀ1. Anal. Calc. for C17H7O9NRu3 (672.45): C, 30.36; H,
2027(s), 1992(w) cmꢀ1
.
HR–MS (ESI–TOF); [MꢀH]ꢀ for
1.04; N, 2.08. Found: C, 29.48; H, 1.39: N, 2.30%.
(C18H5O10Ru3) Calc. 686.7018, found +686.7030 amu. Anal. Calc.
for C18H6O10Ru3 (685.45): C, 31.54; H, 0.88. Found: C, 32.22; H,
0.86%.
4.4. General procedure for the synthesis of compounds 3a–c
A mixture of [Ru3(CO)10(l-dppe)] (50.0 mg, 0.0510 mmol) and
4.3.6. [Ru3(CO)9(
[Ru3(CO)9( -H){l3
4-Ethynyl-aniline (21.0 mg; 0.180 mmol). [Ru3(CO)9(
2-(//)-HC„C C6H4-4-NH2}] (1f); yield: 28.0%, 11.3 mg, orange
l
-CO){l3
-g
-
g
2-(//)-HC„C C6H4-4-NH2}] (1f) and
an excess of the corresponding alkyne HC„CR was refluxed in
30.0 mL of toluene at 90 °C under N2 for 1 h. The solvent was re-
moved under reduced pressure, and the resulting residue was dis-
solved in a minimal amount of chloroform and purified by means
l
2-(\)-C„C C6H4-4-NH2}] (2f)
l
-CO)
{
l3-g

180
M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
Fig. 4. ORTEP view of compound 3b (30% probability).
of tlc chromatographic plates [eluent: hexane:CH2Cl2 (50:50
v/v)], obtaining the compounds 3a–c in the first fraction of each
reaction.
HR–MS (ESI–TOF); [M + CO + H2O]+ for (C43H33O9P2Ru3) Calc.
1060.8735, found +1060.8759 amu. Anal. Calc. for C42H32O7P2Ru3
(1013.87): C, 49.76; H, 3.18. Found: C, 49.10; H, 3.27%.
4.4.1. [Ru3(CO)7(
1-Ethynyltoluene (18.0
-H){l3
2-(\)-C„C C6H4-4-CH3}] (3a); yield: 65.0%, 32.5 mg,
yellow solid. IR
(CO): 2059(s), 1998(vs), 1943(m), 1924(sh) cmꢀ1
l
-dppe)(
l
-H){l3
-
g
2-(\)-C„C C6H4-4-CH3}] (3a)
-dppe)
4.4.2. [Ru3(CO)7(
(3b)
l-dppe)(l-H){l3-g
2-(\)-C„C C6H3-2,5-(CH3)2}]
lL, 0.141 mmol). [Ru3(CO)7(
l
(l
-g
1-Ethynyl-2,5-dimethylbenzene (20.0
l
L, 0.140 mmol). [Ru3
(3b);
m
.
(CO)7( -dppe)( -H){l3 C6H3-2,5-(CH3)2}]
l
l
-g
2-(\)-C„C

M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
181
Table 4
Selected bond lengths (Å) and angles (°) for compounds 2b–d and 3b.
Compound
2b
2c1
2c2
2d
3b
Bond lengths
Ru(1)–Ru(2)
Ru(2)–Ru(3)
Ru(3)–Ru(1)
C(1)–C(2)
2.8074(11)
2.8143(11)
2.7827(11)
1.292(8)
1.470(8)
2.204(6)
2.268(6)
2.202(6)
2.259(5)
1.962(7)
2.7973(3)
2.8007(3)
2.7973(6)
2.8121(6)
2.8054(7)
1.303(6)
1.486(7)
2.208(5)
2.259(4)
2.199(5)
2.252(4)
1.948(4)
2.8086(7)
2.7932(3)
2.8224(3)
1.298(4)
1.465(4)
2.196(2)
2.263(2)
2.201(2)
2.306(3)
1.948(3)
2.8016(3)
2.8158(3)
1.303(4)
1.459(4)
2.202(2)
2.265(3)
2.201(3)
2.292(3)
1.952(3)
2.7879(7)
2.8484(6)
1.314(8)
1.477(6)
2.214(5)
2.247(5)
2.232(6)
2.282(6)
1.962(6)
C(2)–C(3)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(2)–C(1)
Ru(2)–C(2)
Ru(3)–C(1)
Bond angles
Ru(1)–Ru(2)–Ru(3)
Ru(2)–Ru(3)–Ru(1)
Ru(3)–Ru(1)–Ru(2)
Ru(3)–C(1)–C(2)
C(1)–C(2)–C(3)
59.339(17)
60.21(2)
60.453(17)
153.9(5)
60.645(8)
59.750(8)
59.605(8)
156.4(2)
60.345(8)
59.811(8)
59.844(8)
155.6(2)
60.017(15)
59.729(15)
60.254(13)
154.1(4)
61.188(16)
59.764(16)
59.048(16)
152.9(4)
145.2(6)
144.9(2)
143.9(3)
140.9(10)a
147.6(10)a
143.6(5)
Interline and interplane angles
C(1)–C(2)/Ru(1)–Ru(2)
C(1)–C(2)/Ru(3)–Ru(2)–Ru(1)
89.75(3)
17.94(3)
88.7(2)
20.21(2)
89.1(2)
19.45(2)
89.94(3)
18.08(2)
89.38(3)
17.36(3)
a
Due to positional disorder.
yield: 59.0%, 29.5 mg, yellow solid. IR
m(CO): 2058(s), 2000(vs),
4.4.3. [Ru3(CO)7(
(3c)
1-Ethynyl-2,4,5-trimethylbenzene
[Ru3(CO)7( -dppe)( -H){l3
2-(\)-C„CC6H2-2,4,5-(CH3)3}] (3c);
l-dppe)(l-H){l3-g
2-(\)-C„CC6H2-2,4,5-(CH3)3}]
1944(m), 1925(w) cmꢀ1. HR–MS (ESI–TOF); [M + CO + H2O]+ for
(C44H35O9P2Ru3) Calc. 1074.8892, found +1074.8898 amu. Anal.
Calc. for C43H34O7P2Ru3 (1027.89): C, 50.25; H, 3.33. Found: C,
49.49; H, 3.26%.
(7.40 mg,
0.051 mmol).
l
l
-g
yield: 62.0%, 31.0 mg, yellow solid. IR
m(CO): 2056(vs), 1992(vs),
Table 5
Crystal data and structure refinement parameters for compounds 2b-d and 3b.
Compound
2b
2c
2d
3b
Empirical formula
Formula weight
Crystal colour and shape
Crystal system
Crystal size (mm3)
Space group
C
19H10O9Ru3
C20H12O9Ru3
699.51
yellow plate
triclinic
C21H14O9Ru3
713.53
yellow prism
tetragonal
0.35 Â 0.29 Â 0.5
I 41/a
C44H34Cl3O7P2Ru3
1146.21
yellow prism
triclinic
685.5
red prism
monoclinic
0.25 Â 0.18 Â 0.16
C21/c
0.20 Â 0.10 Â 0.10
0.35 Â 0.21 Â 0.12
ꢀ
ꢀ
P1
P1
Unit cell dimensions
a (Å)
b (Å)
33.888(7)
7.7431(15)
17.453(4)
90.00
90.28(3)
90.00
4579.53(17)
8
1.988
9.7611(3)
14.6946(5)
17.5227(6)
80.826(3)
83.974(3)
73.633(3)
2375.89(14)
4
19.907(3)
19.907(3)
25.504(5)
90
90
90
10107(3)
16
1.876
9.5868(2)
12.5022(2)
20.2746(4)
81.7340(10)
82.4580(10)
74.5610(10)
2306.97(8)
2
c (Å)
a
(°)
b (°)
c
(°)
V, (Å3)
Z
Dcalcd, (Mg mꢀ3
)
1.956
1.928
1.650
1.260
l
, (mmꢀ1
)
1.998
1.815
T (K)
k (Mo K) (Å)
Scan type
2h range (°)
Index ranges
293(2)
0.71073
293(2)
0.71073
293(2)
0.71073
293(2)
0.71073
x
ꢀ /
x
ꢀ /
x
ꢀ /
x ꢀ /
3.19–27.53
2.92–27.00
2.89–28.88
2.50–27.49
(hmin/hmax, kmin/kmax, lmin/lmax)
Reflections collected
ꢀ27/43, ꢀ10/9, ꢀ20/22
11847
ꢀ12/12, ꢀ18/18, ꢀ22/22
50279
ꢀ25/25, ꢀ26/22, ꢀ32/32
61484
ꢀ12/11, ꢀ16/15, ꢀ26/26
34554
Independent reflections
Observed reflections
5073 (Rint = 0.0505)
10367 (Rint = 0.0293)
5908 (Rint = 0.1979)
10218 (Rint = 0.0675)
6732 (F > 2r(F))
2734(F > 2
r(F))
8454 (F > 2r(F))
4171 (F > 2
r(F))
Parameters/restrains
280/0
591/0
374/363
479/0
R final; R all data
Rw final, Rw all data
0.0741, 0.0998
0.1488, 0.1278a
0.993
0.679/ꢀ0.732
0.0244, 0.0502
0.0375, 0.0559b
1.109
0.454/ꢀ0.618
0.0479, 0.0851
0.0873, 0.0992c
1.112
0.561/ꢀ0.871
0.0665, 0.1369
0.1184, 0.1738d
1.034
1.096/ꢀ1.146
Goodness of fit (GOF) (all data)
Max, min peaks (e Åꢀ3
)
Where P ¼
r
ðF2o þ 2F2c Þ=3.
2
r2ðF2oÞ þ ð0:0541PÞ .
a
wꢀ1
wꢀ1
wꢀ1
wꢀ1
¼
¼
¼
¼
2
r2ðF2oÞ þ ð0:0244PÞ þ 02314P.
b
c
2
r2ðF2oÞ þ ð0:0295PÞ þ 12:6554P.
2
r2ðF2oÞ þ ð0:0893PÞ þ 2:9746P.
d

182
M. Hernández-Sandoval et al. / Polyhedron 52 (2013) 170–182
1942(s), 1923(m) cmꢀ1
(C44H37O7P2Ru3) Calc. 1044.9139, found +1044.9153 amu. Anal.
Calc. for C44H36O7P2Ru3 (1041.92): C, 50.72; H, 3.48. Found: C,
49.99; H, 3.21%.
.
HR–MS (ESI–TOF); [M+H]+ for
dered over two equally populated positions; the occupancies of the
disordered fragments were fixed at 0.5. A semi-empirical absorp-
tion correction method (SADABS) [27] was applied in all cases. All
structures were resolved by direct methods, completed by subse-
quent difference Fourier synthesis, and refined by full-matrix
least-squares procedures using the SHELX-97 package [27]. All crys-
tallographic programs were used under WINGX program [28].
4.5. General procedure for the synthesis of compounds 4a–c
A mixture of [Ru3(CO)10(l-dfppe)] (50.0 mg, 0.0370 mmol) and
Acknowledgements
an excess of the corresponding alkyne HC„CR was refluxed in
20.0 mL of THF at 60 °C under N2 for 1 h. The solvent was removed
under reduced pressure, and the resulting residue was dissolved in
a minimal amount of chloroform and separated by means of tlc
chromatographic plates [eluent: hexane:CH2Cl2 (50:50 v/v)],
obtaining the compounds 4a–c in the second fraction of each reac-
tion. The first fraction corresponds to an unidentified compound.
We gratefully acknowledge funding from Consejo Nacional de
Ciencia y Tecnología CONACyT, Mexico, (Grants No. CB-106849)
and PROMEP, UAEHGO-PTC-258. M.H.S thanks CONACyT for her
scholarship. We also wish to thank Yolanda Marmolejo and Ana
Lilia Carrasco for their technical assistance to get the elemental
analysis of all compounds. Angelica Cerón, Viridiana Juárez and
Abril Munguía are gratefully acknowledged for their lab assistance.
4.5.1. [Ru3(CO)7(
1-Ethynyltoluene (16.0
-H){l3
2-(\)-C„C C6H4-4-CH3}] (4a); yield: 63.0%, 31.5 mg,
l
-dfppe)(
l
-H){l3
-
g
2-(\)-C„C C6H4-4-CH3}] (4a)
-dfppe)
lL, 0.126 mmol). [Ru3(CO)7(
l
Appendix A. Supplementary data
(l
-g
yellow solid. IR
m(CO): 2078(s), 2021(vs), 1997(h), 1976(m),
1951(w) cmꢀ1. HR–MS (ESI–TOF); [M+H]+ for (C42H13F20O7P2Ru3)
CCDC 847452, 866510, 847463 and 847451 contain the supple-
mentary crystallographic data for 2b–d and 3b, respectively. These
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk.
Calc. 1376.6942, found +1376.6950 amu. Anal. Calc. for
C42H12O7F20P2Ru3 (1373.67): C, 36.72; H, 0.88. Found: C, 36.25;
H, 0.85%.
4.5.2. [Ru3(CO)7(
(4b)
l-dfppe)(l-H){l3-g
2-(\)-C„C C6H3-2,5-(CH3)2}]
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.poly.2012.10.013.
1-Ethynyl-2,5-dimethylbenzene (15.0
(CO)7( -dfppe)( -H)(l3 C6H3-2,5-(CH3)2}]
2-(\)-C„C
yield: 65.0%, 32.5 mg, yellow solid. IR (CO): 2073(s), 2014(vs),
lL, 0.105 mmol). [Ru3
l
l
-g
(4b);
References
m
1993(sh), 1971(m), 1945(w) cmꢀ1. HR–MS (ESI–TOF); [M+H]+ for
(C43H13F20O7P2Ru3) Calc. 1388.6953, found +1388.6984 amu. Anal.
Calc. for C43H14O7F20P2Ru3 (1387.69): C, 37.22; H, 1.02. Found: C,
37.46; H, 1.12%.
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2-(\)-C„CC6H2-2,4,5-(CH3)3}] (4c);
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38.96; H, 1.45%.
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Mounts (MiTeGen company) www.mitegen.com. Data collection,
determination of unit cell, and integration of frames of all com-
pounds were carried out using the suite COLLECT software [24] and
HKL Scalepack [25]. X-ray diffraction data of 2c were collected on
an Oxford Diffraction CCD Gemini diffractometer with graphite-
monochromated Mo K
a radiation. Data were integrated, scaled,
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hydrides in all models were located in their corresponding Fourier
maps, and their coordinates and thermal parameters were refined
isotropically. The position of the remaining hydrogen atoms the
C-bound H-atoms were introduced in calculated positions and
refined on their parent atoms. The tert-butyl group in 2d is disor-
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