Ruthenium carbonyl clusters containing PMe2(nap) and derived ligands (nap = 1-naphthyl): Generation of naphthalyne derivatives

Article abstract of DOI:10.1016/j.jorganchem.2004.09.085

Bis(dimethylphosphino)naphthalene, 1,8-(PMe₂)₂C ₁₀H₆ (dmpn), reacts readily with Ru₃(CO) ₁₂ or Ru₃(μ-dppm)(CO)₁₀ with replacement of one of the PMe₂ groups

Full text of DOI:10.1016/j.jorganchem.2004.09.085

Journal of Organometallic Chemistry 690 (2005) 784–791
www.elsevier.com/locate/jorganchem
Ruthenium carbonyl clusters containing PMe2(nap) and derived
ligands (nap = 1-naphthyl): generation of naphthalyne derivatives
a,
a
b
Michael I. Bruce *, Paul A. Humphrey , Reinhard Schmutzler ,
c
Brian W. Skelton , Allan H. White
c
a
Department of Chemistry, University of Adelaide, Adelaide, SA 5005, Australia
Institut fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t Carolo-Wilhelmina, 38023 Braunschweig, Germany
b
c
Department of Chemistry, University of Western Australia, Crawley, WA 6009, Australia
Received 19 August 2004; accepted 29 September 2004
Available online 10 December 2004
Dedicated to Professor Michael Veith on the occasion of his 60th birthday
Abstract
Bis(dimethylphosphino)naphthalene, 1,8-(PMe2)2C10H6 (dmpn), reacts readily with Ru3(CO)12 or Ru3(l-dppm)(CO)10 with
replacement of one of the PMe2 groups by H to give Ru3(CO)12 ꢀ n{PMe2(nap)}n (n = 1 2, 2 3) or Ru3(l-dppm)(CO)9{PMe2(nap)}
4; the complex Ru3(CO)10(dmpn) 1 is obtained only in small amount. Thermolysis of 2 or 4 gives Ru3(l-H)2{l3-PMe2(C10H5)}(l-
dppm)n(CO)8-2n (n = 0 5, 1 6, respectively) containing l3-naphthalyne groups.
ꢀ 2004 Elsevier B.V. All rights reserved.
1. Introduction
(dmpn) with ruthenium clusters. These results are pre-
sented in this paper.
The formation and subsequent chemistry of metal
carbonyl clusters containing Group 15 ligands continues
to excite interest, both from a synthetic point of view
and because of their possible involvement in catalytic
processes [1]. We have recently described the complexes
formed in reactions between triruthenium and trios-
mium cluster carbonyls and 1,8-bis(diphenylphosph-
ino)naphthalene, 1,8-(PPh2)2C10H6 (dppn), from which
products formed by C–H and C–P bond cleavage in
both the Ph and C10 rings were isolated [2,3]. A cluster
containing an unaltered dppn ligand was not detected
with Ru3(CO)12. In a move to restrict subsequent reac-
tions to the C10 ring, we have also studied similar chem-
istry of the methyl analogue of dppn, 1,8-(PMe2)2C10H6
2. Results and discussion
The reaction between Ru3(CO)12 and dmpn was car-
ried out in thf at r.t. Addition of trimethylamine oxide
(ONMe3, tmno) to activate the carbonyl resulted in a ra-
pid colour change to deep red, after which t.l.c. showed
the presence of four components. Separation by pre-
parative t.l.c. on silica gel afforded recovered Ru3(CO)12
(15%), together with three phosphine-substituted cluster
complexes identified as Ru3(CO)10(dmpn) (1) and Ru3-
(CO)12 ꢀ n{PMe2(nap)}n [n = 1 (2), 2 (3)] by elemental
analyses, spectroscopic methods and for 1 and 3, sin-
gle-crystal X-ray structure determinations.
Complex 1, which was isolated in only 6% yield, gave
an IR m(CO) spectrum containing only terminal CO
bands, while the 1H NMR spectrum contained a charac-
teristic virtual triplet at d 1.88 for the A part of an
*
Corresponding author. Fax: +618 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.09.085

M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 784–791
785
A6XX0A06 spin system resulting from the two PMe2
groups; multiplets between d 7.59 and 8.01 were as-
signed to the C10H6 portion of the dmpn ligand. The
electrospray mass spectrum (ES-MS) was obtained from
a methanol solution containing NaOMe as an ionisation
aid and contained ions at m/z 856 and 828, assigned to
[M + Na ꢀ nCO]+ (n = 0, 1).
and J(HH) 1.2 Hz. In the light of the crystal structure,
these can be assigned to H atoms bridging the Ru(1)–
Ru(2, 3) vectors, which are the longest Ru–Ru separa-
tions. The Me resonances are a doublets at d 1.96 and
2.01, and the C10H5 give five multiplets between d 7.43
and 8.07. The negative ion ES-MS spectrum contains
Mꢀ and [M + OMe]ꢀ at m/z 717 and 748, respectively.
Similar treatment of 4 afforded the dppm analogue of
5 as orange crystals in 86% yield, as confirmed by an X-
The major product was 2, which was shown to be a
complex containing PMe2(nap) as the Group 15 ligand.
Isolated in 16% yield, this orange-red derivative has an
IR m(CO) pattern in the terminal region similar to those
of many other Ru3(CO)11(L) complexes [4]. In this case,
the Me resonance in the 1H NMR spectrum was a simple
doublet at d 2.13 showing a 8.4 Hz coupling to 31P. In the
negative ion ES-MS (solution in MeOH/NaOMe), ions
at m/z 832, 804 and 776 were assigned to
[M + OMe ꢀ nCO]ꢀ (n = 0–2). A single-crystal X-ray
structure determination showed that 3 was Ru3-
(CO)10{PMe2(nap)}2, which had a terminal m(CO) spec-
trum and a doublet similar to that of 2 at d 2.04 [J(HP)
8.4 Hz]. The ES-MS spectrum, obtained from solutions
containing NaOMe, contained both [M + Na]+ and
[M + OMe]ꢀ, at m/z 984 and 992, respectively.
1
ray structure determination. The H NMR spectrum of
the product, Ru3(l-H)2{l3-PMe2(C10H5)}(l-dppm)-
(CO)6 (6) shows the presence of two isomers in solution
in 85/15 ratio. The major isomer gives Ru–H signals at d
ꢀ17.94 and ꢀ15.53, while the minor component gives
Ru–H resonances at d ꢀ19.08 and ꢀ15.06, all with mul-
tiplet structure. Four P–Me doublets are found at d 1.60,
1.91 (major) and 1.71, 1.97 (minor). These data are con-
sistent with differentiation of the two P–Me groups in
each isomer as a result of the presence of the dppm li-
gand and the two isomers can be formulated at 6a and
6b. The ES-MS spectra obtained in the presence of
NaOMe, contain [M + Na]+ and [M ꢀ H]ꢀ at m/z
1068 and 1044, respectively.
We were not able to avoid the ready loss of the PMe2
fragment from dmpn in these reactions, which seems to
occurs more rapidly than substitution of CO in
Ru3(CO)12. The fate of this PMe2 group remains un-
known, although intractable materials in the t.l.c. plate
may have resulted from further reactions of a complex
such as {Ru(l-PMe2)(CO)3}2.
Only one complex was isolated from the reaction be-
tween dmpn and Ru3(l-dppm)(CO)10, carried out under
similar conditions to the reaction with the parent car-
bonyl. Dark red crystals of Ru3(l-dppm)(CO)9{PMe2-
(nap)} (4) were obtained in 45% yield. The IR spectrum
contained a relatively simple m(CO) pattern, while the 1H
NMR spectrum contained a doublet at d 2.04 [J(HP) 8.4
Hz], together with the CH2 resonance at d 4.21 and phe-
nyl proton multiplets between d 7.34 and 8.45. The ES-
MS contained several ions formed by loss of CO or
PMe2(nap) ligands in addition to M+ at m/z 1129. The
molecular structure was confirmed by an X-ray
determination.
The high reactivity of the dmpn ligand suggested that
thermolysis of complexes 2 and 4 might result in further
degradation of the Group 15 ligand. Accordingly, heat-
ing a solution of 2 in thf overnight and separation of
the products by preparative t.l.c. gave a major orange
fraction which contained the hydrido cluster Ru3(l-
H)2{l3-PMe2(C10H5)}(CO)8 (5), isolated in 64% yield.
The spectroscopic properties were consistent with the
molecular structure, determined from an X-ray study.
In addition to a terminal m(CO) spectrum, the 1H NMR
spectrum contained resonances at d ꢀ19.09 and ꢀ16.02
assigned to cluster-bonded H atoms, which showed dou-
ble doublets with J(HP) 32.1 and 9.9 Hz, respectively,
2.1. Molecular structures
The X-ray structures of 1 and 3–6 were determined,
projections of single molecules of each being given in
Figs. 1–5 and selected bond parameters being listed in
Table 1. All molecules are based on a closed Ru3 cluster
to which the Group 15 ligands and only terminal CO
groups are attached and all have 48-electron counts.
In 1, chelation of the dmpn ligand is similar to that
found in the dppn analogue 4, with Ru–P distances of
2
˚
2.2920, 2.2966(7) A , somewhat shorter than the Ru–P
˚
separations found in 3 [2.3461, 2.3438(7) A] and 4
˚
[2.349(3) PMe2(nap); 2.329, 2.330(3) A (dppm)]. These
Ru–P separations are similar to those found in many
complexes containing monodentate PR3 ligands and /
or dppm ligands listed in the Cambridge Data Base
˚
[5]. The P(1)ꢁ ꢁ ꢁP(2) separation in 1 is 3.1409(9) A (see
Table 2).
With one exception, the CO groups are terminally
bonded to their Ru atoms, with the expected differences
in Ru–C distances for axial [1.920–1.969(3) for 1, 1.927–
1.940(3) for 3, 1.92–1.95(1) A for 4] and equatorial
[1.902–1.913(3) for 1, 1.872–1.923(3) for 3, 1.89–
˚
1.92(1) A for 4] groups (with respect to the Ru3 plane)
[cf. Ru3(CO)12, where average values are Ru–CO(ax)
˚
1.942(5), Ru–CO(eq) 1.921(5) A] [7]. The exception is
˚
CO(31) in 1, which is bent towards Ru(1) [R(1,3)–
˚
C(31) 1.900, 2.501(3) A; Ru(1,3)–C(31)–O(31) 123.6ꢁ,
152.4(2)ꢁ. This bending is the result of a twist about
the Ru–Ru vectors, which in the parent carbonyl would
results in a change from D3d to D3 symmetry, and brings
CO(31) closer to a bridging position. However, there is

786
M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 784–791
CO(34)
CO(33)
Ru(3)
CO(31)
212
CO(32)
CO(21)
CO(12)
107
P(2)
106
105
CO(24)
Ru(1)
Ru(2)
108
211
101
CO(22)
104a
104
108a
CO(11)
111
P(1)
102
CO(23)
103
121
Fig. 1. Projection of a molecule of Ru3(CO)10(dmpn) (1), perpendicular to the Ru3 plane.
Fig. 2. Projection of a molecule of Ru3(CO)10{PMe2(nap)}2 (3), perpendicular to the Ru3 plane.
no m(CO) absorption in the l-CO region, the lowest fre-
quency band being at 1930 cmꢀ1. This feature of the
structure of complexes Ru3(CO)12 ꢀ n(PR3)n has been
noted on previous occasions [6]. The torsion angles
OC(n1)–Ru(n)–Ru(n + 1)–CO((n + 1)0) are ꢀ40.1ꢁ,
ꢀ43.2ꢁ and ꢀ40.2(1)ꢁ [in 1, containing the chelating
dmpn ligand on Ru(1)], but considerably less for the
di- and tri-substituted complexes [27.7ꢁ, 28.2ꢁ, 25.3(1)ꢁ
for 3, 23.8ꢁ, 23.5ꢁ, 25.9(4)ꢁ for 4].
age Ru–Ru separations in Ru3(CO)12 [2.8515,
˚
˚
2.860(1) A; the shortest bond is bridged by dppm] [8].
2.8595(4) A] [7] and Ru3(l-dppm)(CO)10 [2.834–
The differences result from steric interactions of the
Group 15 ligand substituents with the CO groups, which
result in the previously reported cis elongation of the
Ru–Ru vector. An interesting crystal packing is found
in 3, inversion-related naphthyl groups at either end of
each molecule packing in sheets about x = 0, 0.5.
The molecular structures of 5 and 6 are closely re-
lated, two CO groups on adjacent Ru atoms in the for-
mer being replaced by the bridging dppm ligand in 6.
The Ru3 cluster supports two bridging H atoms and
the Group 15 ligand, which is best described as a
The Ru–Ru separations in 1, 3 and 4 range between
2.8365(4) and 2.8918(3) (for 1), 2.8430 and 2.8810(3)
˚
(for 3) and 2.864 and 2.873(1) A (for 4), values which
are similar to those found for other analogous com-
plexes and which may also be compared with the aver-

M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 784–791
787
312
307
CO(33)
306
305
308
311
P(3)
CO(32)
322
321
304
303
301
Ru(3)
CO(31)
CO(32)
302
312
P(3)
311
CO(31)
222
Ru(3)
CO(11)
Ru(1)
CO(22)
CO(13)
106
105
CO(11)
Ru(1)
107
108
221 CO(21)
CO(23)
212
Ru(2)
P(2)
211
CO(21)
P(2)
CO(12)
P(1)
CO(12)
112
108a
101
112
104a
226
111
104
P(1)
0
103
212
102
211
111
CO(22)
122
Fig. 5. Projection of a molecule of Ru3(l-H)2{l3-PMe2(C10H5)}(l-
dppm)(CO)6 (6), perpendicular to the Ru3 plane.
Fig. 3. Projection of a molecule of Ru3(l-dppm)(CO)9{PMe3(nap)}
(4), perpendicular to the Ru3 plane.
in 6] are unexceptional and are similar to those found
˚
for the dppm ligand in 6 [2.298, 2.358(3) A]. The C10
group is attached to the P atom by a single bond
[1.82(1)] and to the cluster by atoms C(107, 108), which
form two Ru–C r bonds with Ru(1,3) [Ru(1)–C(108)
2.073(1), 2.088(9); Ru(3)–C(107) 2.093(1), 2.08(1) A;
values for 5, 6, respectively] and a p bond to Ru(2)
[Ru(2)–C(107, 108) 2.359(1), 2.276(1) for 5, 2.340(8),
CO(33)
˚
CO(31)
CO(32)
˚
2.242(7) A for 6]. The C(107)–C(108) bonds are
Ru(3)
˚
1.395(2), 1.38(1) A, respectively. These values may be
compared with those found for Ru3(l3-C2H2)(l-
˚
CO)(CO)9 [2.048, 2.122(7) and 2.213, 2.246(7) A] [9],
106
105
107
CO(12)
from which it is evident that conventional l3-alkyne–
Ru3 interactions are present in 5 and 6, the C10H6 group
being a rare example of naphthalyne stabilised by
attachment to an Ru3 cluster. Analogous complexes
containing benzyne have been known for decades [10]
and, indeed, Cullen and coworkers have previously de-
scribed complexes containing naphthalyne isolated from
reactions of M3(CO)12 (M = Ru, Os) and E(nap)3
(E = P, As), including a direct analogue of 5, obtained
in 50% yield by heating Ru3(CO)12 with P(nap)3 in
refluxing cyclohexane for 24 h [11].
Ru(1)
108
CO(23)
CO(11)
CO(21)
Ru(2)
108a
104a
P(1)
101
104
CO(22)
102
111
103
112
The locations of the two l-H ligands can be deduced
from the structural and spectroscopic results. Conven-
tionally, the presence of a l-H atom is revealed by a
lengthening of the M–M vector. In the present cases,
Fig. 4. Projection of a molecule of Ru3(l-H)2{l3-PMe2(C10H5)}(CO)8
(5), perpendicular to the Ru3 plane.
˚
both Ru(1)–Ru(3) vectors [3.0459(2), 3.049(1) A] are
considerably longer than the other two [range
˚
2.7319(2)–2.877(1) A], suggesting that both H atoms
are bridging this vector. However, in 5, two Ru–H
dimethylphosphino-naphthalyne attached by the P atom
and a conventional l3-alkyne interaction from C(107)–
˚
C(108). The Ru–P distances [2.3211(4) in 5, 2.301(3) A

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M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 784–791
Table 1
˚
Selected bond distances (A) and angles (ꢁ)
Compound
1
3
4
5
6
Bond distances
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(1)–P(1)
2.8918(3)
2.8524(3)
2.8365(4)
2.2920(6)
2.2966(7)
2.8430(3)
2.8697(3)
2.8810(3)
2.3461(7)
2.864(1)
2.871(1)
2.873(1)
2.329(3)
2.8656(2)
3.0459(2)
2.7319(2)
2.3211(4)
2.877(1)
3.049(1)
2.739(1)
2.301(3)
Ru(1)–P(2)
Ru(2)–P(2)
Ru(3)–P(3)
2.3438(7)
2.330(3)
2.349(3)
2.298(3)
2.358(3)
2.088(9)
2.340(7)
2.242(8)
2.08(1)
Ru(1)–C(108)
Ru(2)–C(107)
Ru(2)–C(108)
Ru(3)–C(107)
Ru(1)–CO(ax)
Ru(1)–CO(eq)
Ru(2)–CO(ax)
Ru(2)–CO(eq)
Ru(3)–CO(ax)
Ru(3)–CO(eq)
P(1)–C(101)
2.073(1)
2.359(1)
2.276(1)
2.093(1)
1.920, 1.939(3)
1.936, 1.928(3)
1.878(3)
1.95, 1.94(1)
1.92(1)
1.940(2)
1.882(2)
1.925(10)
1.864(9)
1.954, 1.935(3)
1.908, 1.913(3)
1.940, 1.969(3)
1.902, 1.911(3)
1.832(3)
1.927, 1.934(3)
1.888(3)
1.92, 1.94(1)
1.89(1)
1.887(2)
1.939, 1.893(1)
1.968(2)
1.875, 1.901(10)
1.940, 1.933(3)
1.923, 1.911(3)
1.824(3)
1.94, 1.92(1)
1.90(1)
1.86(1)
1.897, 1.908(2)
1.825(1)
1.850, 1.882(9)
1.819(11)
P(2)–C(201)
P(1)–C(111, 121)
P(2)–C(211, 212)
1.846(2) [C(108)]
1.820, 1.820(3)
1.817, 1.830(3)
1.837(3)
1.825, 1.823(3)
1.832, 1.820(3)
1.84(1)
1.84, 1.84(1)
1.83, 1.83(1)
1.79, 1.80(1)
1.84, 1.82(1)
˚
For 4: For C(n01) read C(0) and for C(n12) read C(n21); P(3)–C(301, 311, 312) are 1.85, 1.83, 1.82(1) A, P(1)–C(0)–P(2) 116.1(5)ꢁ.
For 5: C(107)–C(108) 1.395(2), Ru(1)–H(1,2) 1.64, 1.65(3); Ru(2)–H(1) 1.79(2); Ru(3)–H(2) 1.83(3) A.
˚
For 6: For C(212) read C(221); Ru(2)–C(107, 108) 2.340, 2.242(7); C(107)–C(108) 1.376(11); P(3)–C(311, 321) 1.849, 1.824(9), C(0)–P(2,3) 1.837,
˚
1.847(9) A; P(2)–C(0)–P(3) 112.0(5)ꢁ.
Table 2
Crystal data and refinement details
Compound
1
3
4
5
6
Formula
C
831.56
24H18O10P2Ru3
C34H26O10P2Ru3
959.75
C46H35O9P3Ru3
1127.93
C20H13O8P2Ru3
715.50
C43H35O6P3Ru3
1043.90
Molecular weight
Crystal system
Space group
Monoclinic
P21/c
Monoclinic
P21/c
Monoclinic
P21/c
Monoclinic
P21/c
Monoclinic
P21/n
Unit cell dimensions
˚
a (A)
˚
11.047(1)
19.343(2)
13.130(1)
101.064(3)
2753
26.336(1)
8.3240(5)
15.9908(9)
99.262(1)
3459
17.114(4)
12.277(3)
21.649(5)
104.336(5)
4407
14.9034(8)
10.6819(6)
14.4156(8)
96.079(1)
2282
16.702(3)
12.181(2)
20.907(4)
110.459(3)
3985
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
Z
4
2.006
1.79
4
1.842
1.44
4
1.179
1.18
4
2.082
2.07
4
1.736
1.29
Dc (g cmꢀ3
)
l (cmꢀ1
)
Crystal size (mm)
Tmin/max
0.28 · 0.08 · 0.06
0.80
75
0.18 · 0.16 · 0.03
0.81
75
0.08 · 0.08 · 0.04
0.90
50
0.21 · 0.18 · 0.10
0.84
75
0.15 · 0.08 · 0.06
0.85
53
2hmax (ꢁ)
Ntot
56679
69290
39524
44914
36717
N (Rint
No
)
14394 (0.037)
10932
0.038
18117 (0.060)
12520
0.045
7644 (0.090)
5539
0.063
11963 (0.021)
16623
0.022
8108 (0.085)
5372
0.061
R
Rw (nw)
0.044 (3)
0.051 (7)
0.083 (30)
0.035 (6)
0.073 (20)
resonances are found, showing significantly different
coupling to the P nucleus. For 6, two isomeric forms
are indicated, but in each, there are two Ru–H reso-
nances with different J(HP). These data taken together
suggest that one H bridges Ru(1)–Ru(3) while the sec-
ond bridges Ru(1)–Ru(2). In the analogous molecule

M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 784–791
789
Ru3(l-H)2{l3-PPh2(C10H5)}(CO)9, the H atoms are
3. Experimental
shown to bridge the two longest Ru–Ru vectors; the lon-
gest separation links the two Ru atoms which are r-
bonded to the C10 system.
3.1. General experimental conditions
In conclusion, we have shown a remarkably high
reactivity for the bis(phosphine) dmpn which is mani-
fested by extremely facile cleavage of one P–C10 bond
with loss of the PMe2 group. Equally facile addition
of H to this position is found with formation of the
PMe2(nap) ligand found in 3 and 4. Alternatively, fur-
ther loss of H (from the 2-nap C–H bond) occurs to give
5 or 6, which are rare examples of complexes containing
a naphthalyne group. These results contrast with those
found in similar reactions of dppn, which are character-
ised by facile C–H or C–P bond cleavages giving altered
ligands, such as PPh2(C10H6)PPh(C6H4), PPh(C10H6)-
PPh2 or P(C10H6)PPh2 (C10H6 = 1,8-naphthalenediyl),
which are retained on the clusters [2].
All reactions were carried out under dry, high purity
argon using standard Schlenk techniques. Common sol-
vents were dried, distilled under argon and degassed be-
fore use.
3.2. Instrumentation
Infrared spectra were obtained on a Bruker IFS28
FT-IR spectrometer. Spectra in CH2Cl2 were obtained
using a 0.5 mm path-length solution cell with NaCl win-
dows. NMR spectra were recorded on Bruker
AM300WB (1H at 300.13 MHz) or 600 Unity Nova
(1H at 599.92 MHz) instruments. Samples were dis-
solved in CDCl3, unless otherwise stated, contained in
5 mm sample tubes. Chemical shifts are given in ppm
relative to internal tetramethylsilane. ES mass spectra:
A VG Platform 2 instrument was used, solutions in
MeOH being directly infused into the instrument.
Chemical aids to ionisation were used as required [12].
Elemental analyses were performed at CMAS, Mel-
bourne, Australia.
Ru3(CO)4
Ru2(CO)4
Ph2
P1
101
108
2 Ru1
(OC)
P2
Ph2
3.3. Reagents
The ligand dmpn [13], Ru3(CO)12 [14] and Ru3(l-
dppm)(CO)10 [15] were made by the cited literature
methods. ONMe3 (tmno) was sublimed before use.
(1)
Ru1(CO)3{P1Me2(nap)}
3.4. Reaction of Ru3(CO)12 with dmpn
(OC)4Ru3
Ru2(CO)3(L)
To a solution of Ru3(CO)12 (106 mg, 0.166 mmol) in
thf (20 ml) was added a solution of dmpn (40 mg, 0.161
mmol) in thf (4 ml); tmno (30 mg, 0.40 mmol) was then
added as solid producing a colour change to deep red.
After stirring for 1 h and evaporation to dryness, pre-
parative t.l.c. (acetone–hexane 1/3) separated four major
(2) L = CO
(3) L = P2Me2(nap)
(CO)3
Ru2
P2Ph2
P1Ph2
(nap)Me2P3
bands. Band
1 (red, Rf = 0.42) contained Ru3-
Ru3
(CO)10(dmpn) (1) (7.6 mg, 6%), obtained as red crystals
from CH2Cl2/MeOH. Anal. Found: C, 34.72; H, 2.19%.
Calc. (C24H18O10P2Ru3): C, 34.67; H, 2.18%; M, 833. IR
(CH2Cl2): m(CO) 2073m, 2023vs, 1994vs (br), 1963m,
(OC)3
Ru1
(CO)3
(4)
1930 (sh) cmꢀ1
.
1H NMR (CDCl3): d 1.88 [vt,
J(PH) = 9.0 Hz, 12H, 4 · Me], 7.59–7.62, 7.85–7.88,
7.99–8.01 (3 · 2H, 3 · m, 6H, nap). ES-MS (positive
ion, MeOH + NaOMe, m/z): 856, [M + Na]+; 828,
[M + Na ꢀ CO]+. Band 2 (orange, Rf = 0.44) contained
Ru3(CO)10{PMe2(nap)}2 (3) (2.6 mg, 2%), obtained as
red crystals from CH2Cl2/MeOH. Anal. Found: C,
42.47; H, 2.81%. Calc (C34H26O10P2Ru3): C, 42.55; H,
2.73%; M, 961. IR (CH2Cl2): m(CO) 2070w, 2015vs,
101
101
107
Me2P1
Me2P1
(OC)2Ru1
108
107
108
H
H
(OC)2Ru1
Ru3(CO)2
P3Ph2
Ru3(CO)3
H
H
Ru2
(OC)2
Ru2
(CO)3
Ph2P2
1993 (sh), 1991vs, 1988vs, 1970 (sh), 1957 (sh) cmꢀ1
1H NMR (CDCl3): d 2.04 [d, J(HP) 8.4 Hz, 12H,
.
(5)
(6)

790
M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 784–791
4 · Me], 7.45–7.47, 7.51–7.57, 7.62–7.65, 7.90–7.92,
8.34–8.35 (5 · m, 14H, nap). EI-MS (positive ion,
MeOH, m/z): 961, M+; (positive ion, MeOH + NaOMe):
984, [M + Na]+; (negative ion, MeOH + NaOMe): 992
[M + OMe]ꢀ. Band 3 (orange, Rf = 0.60) contained
Ru3(CO)11{PMe2(nap)} (2) (20.4 mg, 16%) obtained as
an orange-red powder from CH2Cl2/MeOH. Anal.
Found: C, 34.60; H, 1.67%. Calc. (C23H13O11PRu3): C,
34.55; H, 1.64%; M, 801. IR (CH2Cl2): m(CO) 2095w,
1.96 [d, J(HP) 10.2 Hz, 3H, Me], 2.01 [d, J(HP) 9.6
Hz, 3H, Me], 7.43–7.45, 7.51–7.53, 7.74–7.77, 7.81–
7.83, 8.06–8.07 (m, 5H, C10H5). EI-MS (negative ion
MeOH + NaOMe, m/z): 748, [M + OMe]ꢀ; 717, Mꢀ.
3.7. Pyrolysis of Ru3(CO)9(l-ppm){PMe2(nap)} (4)
A solution of Ru3(l-dppm)(CO)9{PMe2(nap)} (43
mg, 0.038 mmol) in thf (12 ml) was heated at reflux
point overnight then evaporated to dryness (rotary
evaporator). Preparative TLC (acetone–hexane 1/2)
showed one major orange band (Rf = 0.50) which was
extracted and crystallised (CH2Cl2/MeOH) to give
Ru3(l-H)2(l3-PMe2C10H5)(l-dppm)(CO)6 (6) (34 mg,
86%) as orange crystals. Anal. Found: C, 49.37; H,
3.24%. Calc. (C43H35O6P3Ru3): C, 49.48; H, 3.38%; M,
1045. IR (CH2Cl2): m(CO) 2025w, 2000m, 1975vs, 1968
1
2043vs, 2026vs, 2011vs, 1984 (sh), 1954 (sh) cmꢀ1. H
NMR (CDCl3): d 2.13 [d, J(HP) 8.4 Hz, 6H, 2 · Me],
7.52–7.55, 7.57–7.64, 7.68–7.71, 7.98–7.99, 8.30–8.32
(m, 7H, nap). EI-MS (negative ion, MeOH + NaOMe,
m/z): 832, [M + OMe]ꢀ; 804, [M + OMe ꢀ CO]ꢀ, 776,
[M + OMe ꢀ 2CO]+. Band 4 (yellow, Rf = 0.92) (16.0
mg, 15%) was identified as Ru3(CO)12 by comparison
of its IR m(CO) spectrum with that of an authentic
sample.
(sh), 1940w, 1917w cmꢀ1
.
1H NMR (CD2Cl2): d
ꢀ19.08 (m, ꢂ0.15H, Ru–H), ꢀ17.94 (m, ꢂ0.85H, Ru–
H), ꢀ15.53 (m, ꢂ0.85H, Ru–H), –15.06 (m, ꢂ0.15H,
Ru–H), 1.60 [d, J(HP) 9.6 Hz, ꢂ0.85 · 3H, Me], 1.71
[d, J(HP) 9.6 Hz, ꢂ0.15 · 3H, Me], 1.91 [d, J(HP) 9.0
Hz, ꢂ0.85 · 3H, Me], 1.97 [d, J(HP) 9.6 Hz,
ꢂ0.15 · 3H, Me], 4.19 (m, 1H, CH2), 4.68 (m, 1H,
CH2), 6.55–8.25 (m, 25H, Ph + C10H5). EI-MS (positive
ion, MeOH + NaOMe, m/z): 1068, [M + Na]+; 1045,
M+; (negative ion, MeOH + NaOMe): 1044, [M ꢀ H]ꢀ.
3.5. Reaction of Ru3(CO)10(l-dppm) with dmpn
To a solution of Ru3(CO)10(l-dppm) (200 mg, 0.207
mmol) in CH2Cl2 (60 ml) was added a solution of dmpn
(65 mg, 0.26 mmol) in CH2Cl2 (5 ml). Tmno (38 mg,
0.40 mmol) was then added as solid producing a colour
change from orange-red to dark red. After stirring for 2
h and evaporation to dryness, preparative t.l.c. (ace-
tone–hexane 1/4) gave one major band (orange,
Rf = 0.55) which was extracted and crystallised
(CH2Cl2/MeOH) to give Ru3(l-dppm)(CO)9{PMe2-
(nap)} (4) (105 mg, 45%) as dark red crystals. Anal.
Found: C, 49.03; H, 3.08%. Calc. (C46H35O9P3Ru3): C,
48.99; H, 3.13%; M, 1129. IR (CH2Cl2): m(CO) 2050w,
3.8. Structure determinations
Full spheres of diffraction data to the indicated limits
were measured at ca. 153 K using a Bruker AXS CCD
area-detector instrument. Ntot reflections were merged
to N unique (Rint quoted) after ‘‘empirical’’/multiscan
absorption correction (proprietary software), No with
F > 4r(F) being used in the full matrix least squares
refinement. All data were measured using monochro-
1
1989vs, 1972vs, 1936w(br) cmꢀ1. H NMR (CD2Cl2): d
2.04 [d, J(HP) 8.4 Hz, 6H, 2 · Me], 4.21 [t, J(HP) 10.8
Hz, 2H, CH2], 7.34–7.39 (m, 20H, Ph), 7.48–7.51,
7.56–7.60, 7.65–7.68, 7.93–7.95, 8.43–8.45 (m, 7H,
nap). EI-MS (positive ion, MeOH + NaOMe, m/z):
1152, [M + Na]+; 1129, M+; (negative ion, MeOH +
NaOMe): 1128, [M ꢀ H]ꢀ; 940, [M ꢀ H ꢀ PMe2nap]ꢀ;
912, [M ꢀ H ꢀ PMe2nap ꢀ CO]ꢀ.
˚
matic Mo Ka radiation, k = 0.71073 A. Anisotropic
thermal parameter forms were refined for the non-
hydrogen atoms, (x, y, z, Uiso H being constrained at
)
estimated values. Conventional residuals R, Rw on |F|
are given [weights: (r2(F) + 0.000nwF2)ꢀ1]. Neutral atom
complex scattering factors were used; computation used
the XTAL 3.7 program system [16]. Pertinent results are
given in the Figure (which shows non-hydrogen atoms
with 50% probability amplitude displacement ellipsoids
3.6. Pyrolysis of Ru3(CO)11{PMe2(nap)} (2)
A solution of Ru3(CO)11{PMe2(nap)} (49 mg, 0.061
mmol) in thf (12 ml) was refluxed for 18 h then evapo-
rated to dryness. Preparative t.l.c. (acetone–hexane
1/2) gave a major band (orange, Rf = 0.72) which was
extracted and crystallised (CH2Cl2/MeOH) to give
Ru3(l-H)2(l3-PMe2C10H5)(CO)8 (5) (28 mg, 64%) as
orange-yellow crystals. Anal. Found: C, 33.69; H,
2.21%. Calc. (C20H13O8PRu3): C, 33.57; H, 1.83%; M,
717. IR (CH2Cl2): m(CO) 2079s, 2045vs, 2035s, 2004s,
˚
and hydrogen atoms with arbitrary radii of 0.1 A) and
Tables 1 and 2.
3.9. Variata
5. (x, y, z, Uiso)H were refined throughout.
6. The precision of the determination did not permit
confident location of the core hydrogens and these were
positioned according to the difference map and spectro-
scopic evidence.
1
1999 (sh), 1983m cmꢀ1. H NMR (CD2Cl2): d ꢀ19.09
[dd, J(HP) 32.1 Hz, J(HH) 1.2 Hz, 1H, Ru–H],
ꢀ16.02 [dd, J(HP) 9.9 Hz, J(HH) 1.2 Hz, 1H, Ru–H],

M.I. Bruce et al. / Journal of Organometallic Chemistry 690 (2005) 784–791
791
[2] M.I. Bruce, P.A. Humphrey, S. Okucu, R. Schmutzler, B.W.
Skelton, A.H. White, Inorg. Chim. Acta 357 (2004) 1805.
[3] M.I. Bruce, P.A. Humphrey, R. Schmutzler, B.W. Skelton, A.H.
White, J. Organomet. Chem. 689 (2004) 2415.
4. Supplementary material
Full details of the structure determinations (except
structure factors) have been deposited with the Cam-
bridge Crystallographic Data Centre as CCDC 246355–
246359 (complexes 1, 3–6, respectively). Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: +44 1223 336 033; e-mail: deposit@ccdc.
cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
[4] M.I. Bruce, M.J. Liddell, C.A. Hughes, B.W. Skelton, A.H.
White, J. Organomet. Chem. 347 (1988) 157.
[5] Cambridge Structural Database, Version 5.25, November 2003.
[6] M.I. Bruce, M.J. Liddell, O. bin Shawkataly, I.R. Bytheway,
B.W. Skelton, A.H. White, J. Organomet. Chem. 369 (1989)
217.
[7] M.R. Churchill, F.J. Hollander, J.P. Hutchinson, Inorg. Chem.
16 (1977) 2655.
[8] A.W. Coleman, D.F. Jones, P.H. Dixneuf, C. Brisson, J.-J.
Bonnet, G. Lavigne, Inorg. Chem. 23 (1984) 952.
[9] M.I. Bruce, B.W. Skelton, A.H. White, N.N. Zaitseva, J. Chem.
Soc., Dalton Trans. (1999) 1445.
Acknowledgements
[10] M.A. Bennett, H.P. Schwembein, Angew. Chem. 101 (1989) 0000;
Angew. Chem., Int. Ed. Engl. 28 (1989) 1349.
We thank the Australian Research Council for sup-
port and Prof. B.K. Nicholson (University of Waikato,
Hamilton, New Zealand), for obtaining the mass spectra
for us. Johnson Matthey plc, Reading, UK, is thanked
for a generous loan of RuCl3 Æ nH2O.
[11] W.R. Cullen, S.J. Rettig, T.C. Zheng, Organometallics 14 (1995)
1466.
[12] W. Henderson, J.S. McIndoe, B.K. Nicholson, P.J. Dyson, J.
Chem. Soc., Dalton Trans. (1998) 519.
[13] (a) A. Karacar, H. Thonnessen, P.G. Jones, R. Bartsch, R.
Schmutzler, Heteroatom Chem. 8 (1997) 539;
(b) T. Costa, H. Schmidbaur, Chem. Ber. 115 (1982) 1374.
[14] M.I. Bruce, C.M. Jensen, N.L. Jones, Inorg. Synth. 26 (1989)
259.
References
[15] M.I. Bruce, B.K. Nicholson, M.L. Williams, Inorg. Synth. 26
(1989) 276.
[1] A.J. Deeming, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, 7, Oxford, Perg-
amon, 1995, p. 683 (Chapter 12).
[16] S.R. Hall, D.J. du Boulay, R. Olthof-Hazekamp (Eds.), The XTAL
3.7 System, University of Western Australia, Perth, 2000.