Some reactions of the ruthenium allenylidene complex [Ru(C=C=CPh2)(PPh3)2Cp][PF6] with nucleophiles

Article abstract of DOI:10.1016/S0022-328X(98)00526-9

Reactions between [Ru(C=C=CPh₂)(PPh₃)₂Cp][PF₆] and nucleophilic reagents LiMe, NaOMe, KCN and KC₅H₅ have given the neutral substituted alkynyl-ruthenium complexes Ru{CCCPh₂(Nu)}(

Full text of DOI:10.1016/S0022-328X(98)00526-9

Journal of Organometallic Chemistry 572 (1999) 3–10
Some reactions of the ruthenium allenylidene complex
[Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6] with nucleophiles
Michael I. Bruce *, Paul J. Low, Edward R.T. Tiekink
Department of Chemistry, Uni6ersity of Adelaide, Adelaide, SA 5005, Australia
Received 22 October 1997
Abstract
Reactions between [Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6] and nucleophilic reagents LiMe, NaOMe, KCN and KC5H5 have given the
neutral substituted alkynyl–ruthenium complexes Ru{CꢁCCPh2(Nu)}(PPh3)2Cp. The molecular structures of complexes with
Nu=OMe, CN and C5H5 have been determined. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; Allenylidene; Alkynyl; X-ray structures
1. Introduction
arene)]+ [11] or M(CO)5 (M=Cr or W) derivatives
[12,13] or at Ck in [RuL2Cp]+ [14] and trans-[Ru-
Cl(dppm)2]+ complexes [15]. In order to examine some
features of these reactions in more detail, we began a
study of the reactions of [Ru(ꢀCꢀCꢀCPh2)(PPh3)2Cp]+
and related complexes. However, while this project was
under way, closely related chemistry involving the
[Ru(CO)(PPri3)Cp]+ [16] and Ru(L)(L%)(p5-C9H7) (L=
L%=PPh3; L=CO, L%=PPh3, PPri3; LL%=dppm,
dppe) systems was reported [17–19]. Our results include
structural investigations of some of the products and
these are described below.
There is presently an increasing interest in the chem-
istry of transition metal complexes containing unsatu-
rated carbene ligands [1–3]. While the chemistry of
vinylidene complexes has been extensively developed,
that of the next member, allenylidene, is only now
receiving attention [4,5]. The first examples of these
complexes of Group 6 and 7 metals were reported as
long ago as 1976 [6,7] and the synthesis of
[Ru(ꢀCꢀCꢀCPh2)(PMe3)2Cp][PF6] by dehydration of an
intermediate hydroxyvinylidene complex obtained from
HCꢁCCR2(OH) was first demonstrated by Selegue in
1982 [8].
The reactivity of the allenylidene ligand has been
explored by several groups. Addition of electrophiles to
Ci in Mn(ꢀCꢀCꢀCR2)(CO)2Cp affords cationic carbyne
complexes, [Mn(ꢁCCH=CR2)(CO)2Cp]+ [9]; similar
chemistry is found with neutral ruthenium complexes
[10]. In contrast, addition of nucleophiles occurs at
either Ch or Ck. These reactions appear to depend on
the steric bulk of the other ligands present on the metal
centre, since alcohols add to Ch in [RuCl(PR3)(p6-
2. Results and discussion
Theoretical studies have indicated that the highly
unsaturated three-carbon allenylidene ligand would
show an alternation in electronic character of the car-
bon atoms, C(1) and C(3) being electron-deficient and
therefore subject to nucleophilic attack, and C(2) being
electron-rich and attracting electrophilic reagents [20],
entirely consistent with the chemistry summarised
above. The electron-deficient nature of the C(1) and
C(3) carbons in the unsaturated carbene ligand may
also be derived from consideration of the simple reso-
* Corresponding author. Tel.: +61
3034358.
8 3035939; fax: +61 8
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00526-9

4
M.I. Bruce et al. / Journal of Organometallic Chemistry 572 (1999) 3–10
nance structures shown below. Addition of nucleophiles
to C(3) would be preferred on steric grounds, bulky
ligands (such as PPh3) serving to protect C(1). Similar
results have been found for related vinylidene com-
plexes, but in this case, small nucleophiles (H− [21],
MeOH [22]) are able to react with C(1), while protona-
tion at C(2) to give carbyne complexes has been found
for several other vinylidene complexes [23].
[M+]ꢀC1ꢀC2ꢀC3R2v[M]–+C1ꢀC2ꢀC3R2v[M]–C1ꢁC2–+C3R2
We have looked at some reactions of the complex
[Ru(CꢀCꢀCPh2)(PPh3)2Cp] [PF6] (1). This compound
was obtained in 80% yield by reaction of
RuCl(PPh3)2Cp with HCꢁCCPh2(OH) in MeOH in the
presence of NH4PF6. The deep red crystalline solid was
identified by microanalysis and from its spectra, which
closely resembled (where appropriate) those found for
[Ru(ꢀCꢀCꢀCPh2)(PMe3)2Cp][PF6] [8]. In the IR spec-
trum, there is a strong w(CCC) absorption at 1934
cm−1, and the characteristic low-field 13C resonance for
C(1) is at l 293.79, showing a 19 Hz coupling to the
two 31P nuclei. Atoms C(2) and C(3) give rise to two
singlets at l 209.44 and 159.60, respectively, while the
Cp carbons are at l 93.55. The FAB mass spectrum
contains M+ at m/z 881, which fragments by loss of
PPh3, Cp and C3Ph2 groups.
Given the steric protection of C(1) afforded by the
Cp and PPh3 ligands, it was expected that nucleophilic
attack would be directed toward C(3). This was confi-
rmed in the reactions between 1 and several carbon-,
oxygen- and nitrogen-based nucleophiles which gave
functionalised alkynyl–ruthenium complexes contain-
ing the nucleophile attached to C(3). Thus, treatment of
1 with the LiMe, NaOMe and KCN gave the neutral
acetylide complexes Ru(CꢁCCPh2R)(PPh3)2Cp [R=Me
(2), OMe (3), CN (4)]. Similarly, treatment of 1 with
cyclopentadiene in the presence of KOtBu gave
Ru{CꢁCCPh2(C5H5)}(PPh3)2Cp (5):
Fig. 1. Molecular structure and crystallographic numbering scheme
employed for 3.
is notable that the alkynyl–C5H5 group is retained by
major ions in the spectrum of 5 under ES-MS condi-
tions. Other ions typically associated with the
Ru(PPh3)2Cp group were also present.
Single crystal X-ray structure determinations was
carried out on each of the complexes 3–5 (Figs. 1–3,
respectively); significant interatomic parameters are col-
lected in Table 1. The structural features of the
Ru(PPh3)2Cp fragment are unremarkable, with Ru–P
[Ru+]ꢀCꢀCꢀCPh2“[Ru]–CꢁC–CPh2(Nu),
where [Ru]=Ru(PPh3)2Cp
and Nu=Me (2), OMe (3), CN (4), C5H5 (5).
Complexes 2–5 were characterised by microanalysis
and from their spectra. In the IR spectra, w(CꢁC) bands
are found in the range 2065–2095 cm−1. The two
acetylenic carbons could be distinguished from one
another by the coupling to 31P (JCP ca. 20 Hz) shown
by C(1). The chemical shifts of both carbons were
between l 95 and 116. The mass spectra of these
complexes, obtained using either FAB or ES tech-
niques, were consistent with the proposed structures,
containing M+ ions which fragmented by loss of the
nucleophile (except for 5), alkynyl and PPh3 groups; it
Fig. 2. Molecular structure and crystallographic numbering scheme
employed for 4.

M.I. Bruce et al. / Journal of Organometallic Chemistry 572 (1999) 3–10
5
with the mean deviation of atoms C(41)–C(45) from
˚
their least-squares plane being 0.005 A.
These reactions provide an alternative synthesis of
ruthenium complexes containing functionalised alkynyl
groups which would be difficult to obtain via the more
conventional
1-alkyne/vinylidene/alkynyl
complex
transformations. In principle the reaction can be ex-
tended significantly by use of substituents other than Ph
(such as CF3, substituted aryl) on C(3) and as has
already been reported by others, replacement of Cp by
C5Me5 [14] or indenyl [19]. In turn, this should extend
the inventory of similar complexes which have been
shown to have non-linear optical properties [30].
A labile cationic complex (6) was obtained as a
lemon yellow solid when 1 was dissolved in neat
NHMe2. Subjecting this solid to dynamic vacuum re-
sulted in a slow change in colour to deep red, and 1 was
recovered quantitatively. Similarly, solutions of 6 were
deep red, and only 1 could be detected spectroscopi-
cally. On the basis of the IR spectrum (w(CꢁC) 2065,
w(PF) 843 cm−1), and by comparison with the forma-
Fig. 3. Molecular structure and crystallographic numbering scheme
employed for 5.
tion of 2–5, complex
6
is formulated as
˚
[Ru{CꢁCCPh2(NHMe2)}(PPh3)2Cp][PF6]:
[Ru+]ꢀCꢀCꢀCPh2[Ru]–CꢁC–CR2(N+HMe2)
[Ru]=Ru(PPh3)2Cp
distances between 2.289(2) and 2.308(1) A, Ru–C(Cp)
˚
separations between 2.207(4) and 2.251(4) A (av. 2.231
A). For the alkynyl group, Ru–C(1) lies between
2.002(4) and 2.033(8) A, the C(1)–C(2) triple bond is
1.200(9)–1.204(4) A and the C(2)–C(3) separations be-
˚
˚
˚
Table 1
˚
˚
tween 1.479(4) and 1.484(9) A. All these distances are
Selected bond lengths (A) and angles (°) for complexes 3–5
comparable with those previously found in compounds
of this type, such as Ru(CꢁCPh)(L2)Cp [L2=(PPh3)2
[24,25], dppe [25] and a series of more highly substi-
tuted arylacetylide complexes recently studied in con-
nection with their non-linear optical properties [26–29].
As expected, angles at Ru are largest for those sub-
tended by the bulky PPh3 ligands [100.61(5)–
104.51(7)°]; the C(1)–Ru–P angles are between 88.7(1)
and 90.5(1)°. The phenyl rings of the CꢁCCPh2R and
PPh3 ligands are disposed in such a way as to minimise
any steric interactions. The most significant feature of
these structures is the deviation from linearity of the
Ru–C(1)–C(2) and C(1)–C(2)–C(3) angles, which lie
between 171.2(6) and 177.3(3)°. The largest deviations
from linearity are found in 5 (values of 171.1(7) and
174.0(8)°, respectively). This is most likely a result of
the increased steric interaction between the C5H5 sub-
stituent on C(3) and the bulky PPh3 ligand, such that
the C3 chain is orientated away from the P(1)Ph3
ligand. The substituents show no unusual features, with
C(3)–O(4) (in 3) and C(3)–C(4) (in 4) distances of
3
4
5
˚
Bond lengths (A)
Ru–P(1)
Ru–P(2)
Ru–C(1)
2.294(1)
2.276(1)
2.013(3)
1.204(4)
1.479(4)
1.542(4)
1.535(5)
1.448(3)
1.416(5)
2.308(1)
2.276(1)
2.002(4)
1.201(5)
1.482(5)
1.546(5)
1.556(5)
2.289(2)
2.299(2)
2.033(8)
1.200(9)
1.484(9)
1.541(9)
1.55(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(21)
C(3)–C(31)
C(3)–O(4)
O(4)–C(5)
C(3)–C(4)
C(4)–N(5)
C(3)–C(41)
C(41)–C(42)
C(42)–C(43)
C(43)–C(44)
C(44)–C(45)
C(45)–C(41)
1.491(6)
1.134(5)
1.531(9)
1.49(1)
1.51(1)
1.42(1)
1.46(1)
1.334(9)
Bond angles (°)
P(1)–Ru–P(2)
101.96(3)
89.09(9)
88.7(1)
174.8(3)
177.3(3)
111.1(3)
109.1(3)
111.3(3)
100.61(5)
90.5(1)
88.8(1)
173.7(3)
175.0(4)
109.8(3)
111.4(3)
104.51(7)
90.3(2)
89.2(2)
171.2(6)
174.0(8)
108.8(6)
111.5(6)
P(1)–Ru–C(1)
P(2)–Ru–C(1)
Ru–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(21)
C(2)–C(3)–C(31)
C(2)–C(3)–O(4)
C(2)–C(3)–C(4)
C(2)–C(3)–C(41)
C(3)–C(4)–N(5)
˚
1.448(3) and 1.491(6) A, respectively. The C(5)–N(5)
˚
separation is 1.134(5) A. For the uncomplexed C5H5
ring in 5, the expected bond length alternation around
the ring is found, with CꢀC double bonds localised
106.8(3)
179.0(5)
108.5(6)
˚
between C(41)–C(45) (1.334(9) A) and C(43)–C(44)
˚
˚
(1.42(1) A). The ring itself is planar to 90.007(8) A,

6
M.I. Bruce et al. / Journal of Organometallic Chemistry 572 (1999) 3–10
20 cm) coated with silica gel (Merck 60 GF254, 0.5 mm
As anticipated from earlier studies, addition of the
thick).
nucleophile to 1 has occurred at C(3), the sterically
least encumbered site. Of interest is the addition of
cyclopentadienide to give the unusual cyclopentadi-
enyldiphenylmethyl-substituted alkynyl ligand in 5. In
principle, further deprotonation of this group and sub-
sequent reactions with metal substrates could lead to
novel heterometallic systems.
Complex 3 reacted rapidly with traces of acid to give
1. It is highly likely that addition of H+ occurs at C(2)
of 3 and the resulting methoxyvinylidene complex then
rapidly eliminates methanol to give 1, in a reaction
which is closely related to the dehydration of the hy-
droxyvinylidene which affords 1.
4.2. Instrumental conditions
IR: Perkin Elmer 1700X FT-IR. NMR: Spectra of
CDCl3 solutions were recorded on Bruker ACP300 (1H
at 300.13 MHz, 13C at 75.47 MHz) or Varian Gemini
200 (1H at 199.98 MHz, 13C at 50.29 MHz) spectrome-
ters. FAB mass spectra: VG ZAB 2HF spectrometer,
using 3-nitrobenzyl alcohol as matrix, exciting gas Ar,
FAB gun voltage 7.5 kV, current 1 mA, accelerating
potential 7 kV. ES mass spectra: VG Platform II.
Solutions in acetonitrile:water (1:1), injected via a 10 ml
injection loop. Nitrogen was used as the drying and
nebulising gas.
4.3. Reagents
Cyclopentadiene (Fluka) was distilled prior to use.
Dimethylamine (Aldrich), KCN (BDH) and KOtBu
(Fluka) were used as received. The compounds
RuCl(PPh3)2Cp [31] and HCꢁCCPh2(OH) [32] were
prepared by literature methods.
Alternatively, an equilibrium of the type
(1)+MeO− X (3)+PF6−
4.4. Preparation of [Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6] (1)
may be set up, as proposed for the trans-RuCl(dppm)2]
system [15].
A mixture of RuCl(PPh3)2Cp (1.0 g, 1.38 mmol),
HCꢁCCPh2OH (300 mg, 1.4 mmol) and NH4PF6 (225
mg, 1.38 mmol) was stirred in MeOH (100 ml)
overnight. The resulting deep red solution was filtered
and the solvent removed. The deep red residue was
extracted with the minimum volume of CH2Cl2 and
filtered into an excess of rapidly stirred Et2O. The
precipitate was collected, washed with a small volume
of cold Et2O, and dried. The filtrate was evaporated
and worked up as before to give a second crop of
[Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6] (1) (total yield 1.14 g,
80%). Anal. Found: C 65.34, H 4.30. C56H45P3F6Ru
calc.: C 65.50, H 4.39%. IR (CH2Cl2): w(CꢀCꢀC) 1934s,
3. Conclusion
The
allenylidene
ligand
in
the
complex
[Ru(CꢀCꢀCPh2)(PPh3)2Cp]PF6 (1) reacts with oxygen-,
nitrogen- and carbon-based nucleophiles to give neutral
alkynyl derivatives in which the nucleophile has added
to the exposed C(3) atom. These reactions allow func-
tionalisation of the C3 ligand and, as shown by others,
allow further examples of unusual unstaurated ligands
to be made. In the present case, the introduction of the
cyclopentadienyl group may allow addition of other
metal fragments and the synthesis of novel heterometal-
lic systems.
w(PF) 840m cm−1 1H-NMR: l 7.75–7.05 (40H, m,
.
Ph), 5.12 (5H, s, Cp). 13C-NMR: l 293.79 [t, JCP=19
Hz, C(1)], 209.44 [s, C(2)], 159.60 [s, C(3)], 143.50–
128.32 (m, Ph), 93.55 (s, Cp). 31P-NMR: l 43.82 (s,
PPh3). FAB MS (m/z): 881 [M]+, 619 [M−PPh3]+,
553 [M−PPh3−Cp]+, 429 [Ru(PPh3)(C5H5)]+.
4. Experimental
4.5. Reactions of Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6](1)
4.1. General reaction conditions
4.5.1. With LiMe ·LiBr
All reactions were carried out under nitrogen using
standard Schlenk techniques. Solvents were dried, dis-
tilled and degassed before use. Light petroleum refers to
a fraction of b.p. 60–80°C. Elemental analyses were by
the Canadian Microanalytical Service, Delta, BC.
Preparative TLC was carried out on glass plates (20×
A solution of [Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6] (150
mg, 0.19 mmol) in THF (15 ml) was treated with
MeLi·LiBr (one drop of a 1.5 M solution in Et2O) and
was then stirred for 15 min. During this time the
solution changed colour from red to green brown. The
solvent was removed, the residue extracted with CH2Cl2

M.I. Bruce et al. / Journal of Organometallic Chemistry 572 (1999) 3–10
7
Table 2
Crystallographic data for complexes 3–5
Compound
3
4
5
Formula
C57H48OP2Ru
912.0
Triclinic
P
11.765(7)
19.73(1)
10.93(1)
94.01(6)
117.37(5)
86.84(5)
2246(2)
2
C57H45NP2Ru
907.0
Triclinic
P
11.601(6)
19.166(8)
11.255(8)
94.97(5)
117.43(4)
85.94(4)
2211(2)
2
C
946.1
Triclinic
P
13.896(3)
14.820(4)
12.172(3)
91.33(3)
110.21(1)
89.54(2)
2352(1)
2
61H50P2Ru
Formula weight
Crystal system
Space group
˚
a (A)
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
V (A )
Z
Crystal size (mm3)
0.11×0.24×0.24
1.348
944
0.11×0.18×0.29
1.362
936
0.08×0.11×0.24
1.336
980
Dcalc. (g cm−3
F(000)
)
No. of data collected
2qmax (°)
8344
50.0
8736
55.0
6463
45.0
No. of unique data
No. of reflections with I]3.0|(I)
R
7925
6078
0.034
8239
5672
0.038
6160
3291
0.045
Rw
0.036
0.51
0.038
0.45
0.039
0.35
−3
˚
Residual zmax (e A
)
4.5.3. With KCN
and the extracts filtered through a pad of Celite. The
yellow solution was diluted with MeOH and concen-
trated to give a pale yellow powder, which was crys-
tallised (CH2Cl2/MeOH) to give Ru(CꢁCCMePh2)
(PPh3)2Cp (2) (yield: 70 mg, 54%). Anal. Found: C
76.39, H 5.36. C57H49P2Ru calc.: C 76.33, H 5.47%. IR
A solution of [Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6] (150
mg, 0.146 mmol) in dry THF (15 ml), was treated with
KCN (10 mg, 0.15 mmol) and heated at reflux point for
12 h. The solution changed colour from deep red to
yellow. The solvent was removed and the yellow residue
was extracted with CH2Cl2 (2×5 ml). The filtered
extracts were diluted with MeOH (5 ml) and concen-
trated to ca. 5 ml. The precipitate was washed with
MeOH, dried and recrystallised (CH2Cl2/MeOH) to
give Ru{CꢁCC(CN)Ph2}(PPh3)2Cp (4) (yield: 108 mg,
81%). Anal. Found: C 71.79, H 4.73. C57H45NP2Ru
calc.: C 75.50, H 4.97%. IR (nujol): w(CꢁC) 2083s
1
(nujol): w(CꢁC) 2090m cm−1. H-NMR: l 7.63–6.98
(40H, m, Ph), 4.29 (5H, s, Cp), 1.89 (3H, s, Me).
13C-NMR: l 139.41–125.05 (m, Ph), 95.50 [t, JCP
=
23.4Hz, C(1)], 93.51 [s, C(2)], 85.02 (s, Cp), 47.16 [s,
C(3)], 31.73 (s, Me). FAB MS (m/z): 896 M+, 881
[M−Me]+, 691 [Ru(PPh3)2(C5H5)]+, 633 [M−
PPh3]+,
619
[M−Me–PPh3]+,
429
1
cm−1. H-NMR: l 7.64–7.04 (40H, m, Ph), 4.34, (5H,
[Ru(PPh3)(C5H5)]+.
s, Cp). 13C-NMR: l 142.82–127.09 (m, Ph), 121.63 (s,
CN), 110.66 [t, JCP=23.93 Hz, C(1)], 103.25 [s, C(2)],
85.25 (s, Cp), 50.83 [s, C(3)]. FAB MS (m/z): 907 M+,
691 [Ru(PPh3)2(C5H5)]+, 644 [M−PPh3]+, 455
[Ru(CN)(PPh3)Cp]+, 429 [Ru(PPh3)(C5H5)]+.
4.5.2. With NaOMe
Addition of NaOMe (1
M in methanol) to
[Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6] (150 mg, 0.15 mmol) in
MeOH (10 ml) resulted in a rapid colour change from
deep red to yellow. After 5 min, the precipitate was
filtered and recrystallised (CH2Cl2/MeOH) to yield yel-
low crystals of Ru{CꢁCCPh2(OMe)}(PPh3)2Cp (3)
(yield: 120 mg, 88%). Anal. Found: C 74.98, H 5.22.
C57H48OP2Ru calc.: C 75.08, H 5.27%. IR (nujol):
4.5.4. With cyclopentadiene in the presence of KOBut
To a solution of [Ru(CꢀCꢀCPh2)(PPh3)2Cp][PF6]
(200 mg, 0.19 mmol) in THF (15 ml), cyclopentadiene
(250 mg, 3.8 mmol) and KOBut (50 mg, 0.45 mmol)
were added. The solution immediately turned green–
yellow. Solvent was removed and the residue purified
by column chromatography on Al2O3. Elution with 4:1
light petroleum:acetone gave a bright yellow band,
which yielded Ru{CꢁCCPh2(C5H5)}(PPh3)2Cp (5) (130
mg, 70%) after crystallisation (CH2Cl2/MeOH). Anal.
Found: C 77.17, H 5.75. C61H50P2Ru calc.: C 77.46, H
1
w(CꢁC) 2070m cm−1. H-NMR: l 7.62–7.01 (40H, m,
Ph), 4.35 (5H, s, Cp), 3.34 (3H, s, OMe). 13C-NMR: l
147.27–126.87 (m, Ph), 110.51 [s, C(2)], 107.52 [t,
J
CP=24 Hz, C(1)], 85.25 (s, Cp), 82.36 [s, C(3)], 51.51
(s, OMe). ES MS (m/z): 912 M+, 881 [M−OMe]+,
732 [M+NCMe−C2C(OMe)Ph2]+.

8
M.I. Bruce et al. / Journal of Organometallic Chemistry 572 (1999) 3–10
Table 3
Table 3 (continued)
Fractional atomic coordinates for complexes 3–5
Atom
x
y
z
Atom
x
y
z
Complex 4
Ru
P(1)
P(2)
N(5)
C(1)
C(2)
C(3)
C(4)
Complex 3
Ru
P(1)
P(2)
O(4)
C(1)
C(2)
C(3)
C(5)
0.16649(3)
0.37064(9)
0.20868(10)
0.2669(4)
0.1279(3)
0.0941(3)
0.0551(4)
0.1753(4)
−0.20810(2)
−0.16753(5)
−0.32592(5)
−0.1779(3)
−0.2120(2)
−0.2106(2)
−0.2023(2)
−0.1879(2)
−0.1953(3)
−0.1292(3)
−0.1110(2)
−0.1660(3)
−0.2173(2)
−0.2708(2)
−0.3145(3)
−0.3772(3)
−0.3961(3)
−0.3526(3)
−0.2901(2)
−0.1380(2)
−0.1091(3)
−0.0493(3)
−0.0200(3)
−0.0501(3)
−0.1091(3)
−0.1611(2)
−0.1010(2)
−0.0994(3)
−0.1565(3)
−0.2162(3)
−0.2187(2)
−0.2057(2)
−0.2118(2)
−0.2373(2)
−0.2551(2)
−0.2464(2)
−0.2223(2)
−0.0768(2)
−0.0463(2)
0.0221(2)
−0.47418(3)
−0.33204(9)
−0.46848(10)
0.1010(4)
−0.3189(4)
−0.2326(4)
−0.1238(4)
0.0036(4)
−0.16441(2)
−0.35939(7)
−0.20862(8)
−0.1616(2)
−0.1237(3)
−0.0923(3)
−0.0526(3)
−0.2279(4)
0.0337(4)
−0.0468(4)
−0.1299(4)
−0.1007(4)
0.0003(4)
0.0448(3)
0.1013(4)
0.1860(4)
0.2128(4)
0.1585(4)
0.0755(4)
0.0022(3)
0.1271(4)
0.21911(1)
0.17393(4)
0.33273(4)
0.1938(1)
0.2187(2)
0.2145(2)
0.2057(2)
0.1336(2)
0.2151(3)
0.2374(2)
0.1846(2)
0.1305(2)
0.1486(2)
0.1460(2)
0.1150(2)
0.0597(2)
0.0359(2)
0.0667(2)
0.1221(2)
0.2726(2)
0.2883(2)
0.3494(3)
0.3956(2)
0.3808(2)
0.3192(2)
0.0862(2)
0.0590(2)
−0.0061(2)
−0.0439(2)
−0.0179(2)
0.0471(2)
0.2081(2)
0.2287(2)
0.2484(2)
0.2496(2)
0.2296(2)
0.2081(2)
0.1635(2)
0.1043(2)
0.0995(2)
0.1549(3)
0.2138(2)
0.2187(2)
0.3776(2)
0.3628(2)
0.3928(2)
0.4363(3)
0.4499(3)
0.4213(2)
0.3685(2)
0.3856(2)
0.4095(2)
0.4159(2)
0.3983(2)
0.3750(2)
0.3757(2)
0.4461(2)
0.4778(2)
0.4398(2)
0.3708(2)
0.3391(2)
0.49724(3)
0.35123(8)
0.47601(8)
0.0023(2)
0.3373(3)
0.2466(3)
0.1361(3)
−0.0125(4)
0.6649(5)
0.7235(4)
0.7033(4)
0.6327(4)
0.6082(4)
0.1627(3)
0.2856(4)
0.3064(5)
0.2021(5)
0.0794(5)
0.0587(4)
0.1250(3)
0.2123(5)
0.2073(6)
0.1148(6)
0.0272(5)
0.0326(4)
0.2845(3)
0.2989(4)
0.2452(5)
0.1781(5)
0.1606(4)
0.2133(4)
0.1867(3)
0.0997(3)
−0.0318(3)
−0.0774(4)
0.0067(4)
0.1376(4)
0.4430(3)
0.5079(4)
0.5905(4)
0.6086(4)
0.5463(4)
0.4637(4)
0.5465(4)
0.4897(4)
0.5451(5)
0.6598(5)
0.7194(5)
0.6632(4)
0.3072(3)
0.2195(4)
0.0912(4)
0.0477(4)
0.1326(4)
0.2614(4)
0.5753(3)
0.5703(4)
0.6436(4)
0.7181(4)
0.7234(4)
0.6511(4)
C(11)
C(12)
C(13)
C(14)
C(15)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
C(71)
C(72)
C(73)
C(74)
C(75)
C(76)
C(81)
C(82)
C(83)
C(84)
C(85)
C(86)
C(91)
C(92)
C(93)
C(94)
C(95)
C(96)
−0.0370(4)
0.0044(4)
0.1054(4)
0.1298(4)
0.0411(5)
−0.0035(4)
0.0589(5)
0.0051(7)
−0.1101(7)
−0.1741(5)
−0.1218(4)
−0.0401(4)
−0.0604(4)
−0.1401(5)
−0.2024(5)
−0.1875(5)
−0.1062(5)
0.4635(3)
0.4529(4)
0.5089(5)
0.5779(5)
0.5902(4)
0.5323(4)
0.4879(3)
0.6214(4)
0.7047(4)
0.6570(4)
0.5259(4)
0.4421(3)
0.3672(4)
0.2540(4)
0.2530(5)
0.3647(6)
0.4789(5)
0.4801(4)
0.2882(4)
0.3200(5)
0.3763(5)
0.4048(5)
0.3763(5)
0.3174(4)
0.0530(4)
−0.0367(4)
−0.1554(5)
−0.1886(5)
−0.1025(6)
0.0171(5)
0.3050(4)
0.2524(4)
0.3300(6)
0.4610(6)
0.5157(4)
0.4388(4)
−0.6320(5)
−0.5678(4)
−0.5893(4)
−0.6696(4)
−0.6940(4)
−0.1163(4)
−0.0142(5)
−0.0151(7)
−0.1192(7)
−0.2202(6)
−0.2200(5)
−0.1423(4)
−0.0374(5)
−0.0536(6)
−0.1742(7)
−0.2807(6)
−0.2645(5)
−0.4250(3)
−0.4911(4)
−0.5760(5)
−0.5941(5)
−0.5292(4)
−0.4462(4)
−0.1747(4)
−0.1323(4)
−0.0082(4)
0.0752(4)
C(11)
C(12)
C(13)
C(14)
C(15)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
C(71)
C(72)
C(73)
C(74)
C(75)
C(76)
C(81)
C(82)
C(83)
C(84)
C(85)
C(86)
C(91)
C(92)
C(93)
C(94)
C(95)
C(96)
0.1751(4)
0.0992(6)
−0.0252(6)
−0.0739(4)
−0.3477(3)
−0.2314(4)
−0.2230(5)
−0.3302(6)
−0.4465(5)
−0.4559(4)
−0.4758(3)
−0.4286(3)
−0.5109(3)
−0.6411(4)
−0.6891(3)
−0.6078(3)
−0.4541(3)
−0.4462(3)
−0.5059(4)
−0.5743(4)
−0.5840(4)
−0.5241(3)
−0.0560(3)
0.0275(4)
0.0370(4)
−0.0871(4)
−0.2639(4)
−0.2676(4)
−0.2137(5)
−0.1540(5)
−0.1466(4)
−0.2009(4)
−0.5666(4)
−0.5647(4)
−0.6430(5)
−0.7200(5)
−0.7218(5)
−0.6449(4)
−0.5457(4)
−0.4970(5)
−0.5536(6)
−0.6624(6)
−0.7132(6)
−0.6558(5)
−0.3073(4)
−0.2237(4)
−0.0990(5)
−0.0545(5)
−0.1341(5)
−0.2601(4)
0.0591(2)
0.0285(2)
−0.0391(2)
−0.3674(2)
−0.4391(2)
−0.4698(3)
−0.4296(3)
−0.3583(3)
−0.3281(2)
−0.3723(2)
−0.3566(2)
−0.3880(3)
−0.4350(3)
−0.4500(3)
−0.4194(3)
−0.3654(2)
−0.3799(2)
−0.4047(2)
−0.4154(2)
−0.4012(2)
−0.3761(2)
0.1460(4)
0.1844(4)
0.1049(5)
−0.0139(4)
−0.3086(3)
−0.2600(4)
−0.3412(5)
−0.4712(5)
−0.5206(4)
−0.4396(3)
−0.2857(3)
−0.3110(4)
−0.3710(4)
−0.4086(4)
−0.3855(4)
−0.3239(3)

M.I. Bruce et al. / Journal of Organometallic Chemistry 572 (1999) 3–10
9
Table 3 (continued)
5.29%. IR (nujol): w(CꢁC) 2095m, w(CꢀC) 1652br
1
cm−1. H-NMR: l 7.48–6.98 (40H, m, Ph), 6.41, 6.27
Atom
x
y
z
(both 2H, both dd, 3JHH=5 Hz, 4JHH=1 Hz,
CHꢀCH), 5.87 (1H, s, CH), 4.35 (5H, s, Cp). 13C-
NMR: l 157.41, 154.31, 148.93, 148.14, 136.6 (5×s,
C5H5), 148.93–125.2 (m, Ph), 115.47 [s, C(2)], 96.13 [t,
Complex 5
Ru
P(1)
P(2)
C(1)
0.16203(5)
0.3344(2)
0.1314(2)
0.1882(5)
0.1935(5)
0.1889(6)
0.0694(7)
0.0032(6)
0.0230(7)
0.1003(7)
0.1303(6)
0.0758(6)
0.0393(7)
−0.19478(4)
−0.1767(1)
−0.1288(1)
−0.3141(5)
−0.3890(5)
−0.4832(5)
−0.2640(5)
−0.2198(6)
−0.1258(6)
−0.1132(5)
−0.1991(6)
−0.5088(5)
−0.5513(6)
−0.5726(7)
−0.5531(8)
−0.5120(6)
−0.4874(6)
−0.4948(5)
−0.4221(5)
−0.4325(7)
−0.5168(8)
−0.5883(7)
−0.5787(5)
−0.5456(5)
−0.5378(6)
−0.6118(8)
−0.6567(6)
−0.6130(5)
−0.0712(5)
−0.0679(6)
0.0142(7)
0.16296(6)
0.2040(2)
0.3204(2)
0.2476(6)
0.2845(6)
0.3213(6)
J
CP=24.04Hz, C(1)], 85.11 (s, Cp), 43.01 [s, C(3)]. ES
C(2)
C(3)
MS (m/z): 946 [M+H]+, (with NaOMe) 968 [M+
Na]+.
C(11)
C(12)
C(13)
C(14)
C(15)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
C(71)
C(72)
C(73)
C(74)
C(75)
C(76)
C(81)
C(82)
C(83)
C(84)
C(85)
C(86)
C(91)
C(92)
C(93)
C(94)
C(95)
C(96)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
−0.0051(6)
0.0434(7)
0.0463(7)
−0.0004(7)
−0.0314(6)
0.2955(7)
0.3722(7)
0.3427(10)
0.237(1)
4.5.5. With NHMe2
Neat NHMe2 (ca. 2 ml) was condensed into a
schlenk flask containing [Ru(CꢀCꢀCPh2)(PPh3)2Cp]
[PF6] (100 mg, 0.097 mmol). The solid rapidly turned
yellow and dissolved to give a bright yellow solution.
Excess amine was allowed to evaporate to give a
lemon yellow solid that resulted was tentatively iden-
tified as [Ru{CꢁC–CPh2(NHMe2)}(PPh3)2Cp][PF6] (6)
(yield: 98 mg, 94%). Further attempts to dry the pow-
der in vacuo resulted in a gradual colour change of
the solid from yellow to deep red, and
[Ru(CꢀCꢀCPh2)(PPh3)2Cp]PF6 was recovered quantita-
tively. Similarly, when the solid was dissolved in a
range of solvents (acetone, CDCl3, CH2Cl2, THF,
MeOH), a red solution was obtained, from which only
[Ru(CꢀCꢀCPh2)(PPh3)2Cp]PF6 could be isolated in
high yield. Reproducible analyses could not be ob-
tained. Anal. Found: C 62.30, H 5.44, N 3.60.
C58H52NP3F6Ru calc.: C 64.98, H 4.86, N 1.31%. IR
−0.0619(9)
−0.1277(8)
−0.0971(7)
0.0038(7)
0.2522(6)
0.2789(6)
0.3377(7)
0.3706(8)
0.3443(7)
0.2866(7)
0.2346(6)
0.3435(7)
0.3603(8)
0.2646(9)
0.1911(6)
0.3599(6)
0.3624(7)
0.3690(8)
0.3732(8)
0.3705(7)
0.3649(6)
0.3911(6)
0.4885(7)
0.5308(7)
0.4749(8)
0.3792(7)
0.3376(6)
0.4362(6)
0.5239(7)
0.6020(6)
0.5930(7)
0.5086(7)
0.4288(6)
0.1250(6)
0.1395(6)
0.1324(6)
0.1088(7)
0.0956(7)
0.1035(7)
0.2059(6)
0.3021(7)
0.3619(7)
0.3264(9)
0.2330(9)
0.1709(7)
0.0010(6)
−0.0796(7)
−0.1784(8)
−0.1967(8)
−0.1183(9)
−0.0204(7)
0.1565(9)
0.1862(8)
0.4523(7)
0.5288(7)
0.6454(8)
0.6884(8)
0.6141(8)
0.4985(8)
0.2501(6)
0.2584(7)
0.1799(9)
0.1294(8)
0.1753(7)
0.1439(6)
0.0303(7)
−0.0207(8)
0.0426(9)
0.1534(8)
0.2052(6)
0.1277(6)
0.1247(7)
0.0667(7)
0.0100(7)
0.0136(7)
0.0727(6)
0.3480(6)
0.3858(7)
0.4896(8)
0.5584(7)
0.5238(7)
0.4190(7)
0.3275(7)
0.2424(6)
0.2446(7)
0.3324(9)
0.4195(8)
0.4185(7)
0.4745(6)
0.5194(7)
0.6355(9)
0.7094(8)
0.6694(8)
0.5521(8)
0.3093(6)
0.2854(8)
0.2720(10)
0.2817(10)
0.3016(9)
0.0927(6)
0.0904(6)
0.0099(5)
(nujol): w(CꢁC) 2065m, w(PF) 843s(br) cm−1
.
−0.2605(5)
−0.2484(5)
−0.3090(6)
−0.3823(5)
−0.3987(5)
−0.3373(5)
−0.1832(5)
−0.1294(5)
−0.1460(6)
−0.2151(6)
−0.2697(6)
−0.2516(5)
−0.0047(5)
0.0462(5)
4.6. Crystallography
Intensity data for yellow crystals of 3–5 were col-
lected at room temperature on a Rigaku AFC6R dif-
fractometer employing Mo–Kh radiation (u=0.71073
˚
A) and the ꢀ:2q scan technique. The data sets were
corrected for Lorentz and polarisation effects [33] as
well as for absorption employing an empirical proce-
dure [34]. Data that satisfied the I]3.0|(I) criterion
of observability were used in the subsequent analysis.
Crystal data and refinement details are given in Table
2.
0.1407(5)
0.1836(6)
0.1338(7)
0.0405(6)
The structures were each solved by direct methods
(3 and 5 [35], 4 [36]) and refined by a full-matrix
least-squares procedure based on F [33]. All non-H
atoms were refined with anisotropic displacement
parameters and H atoms were included in the models
−0.1471(5)
−0.1086(5)
−0.1152(6)
−0.1637(7)
−0.2010(7)
−0.1936(6)
−0.1618(6)
−0.1020(6)
−0.1292(9)
−0.2193(10)
−0.2821(7)
−0.2542(6)
˚
at their calculated positions (C–H 0.97 A). The refine-
ments were continued until convergence employing |
weights, i.e. 1/|2(F). Fractional atomic coordinates are
listed in Table 3, selected interatomic parameters are
collected in Table 1 and the crystallographic number-
ing schemes employed are shown in Figs. 1–3 which
were drawn with ORTEP [37].
0.3161(7)
.

10
M.I. Bruce et al. / Journal of Organometallic Chemistry 572 (1999) 3–10
[14] R. Le Lagadec, E. Roman, L. Toupet, U. Mu¨ller, P.H.
Dixneuf, Organometallics 13 (1994) 5030.
5. Supplementary material available
[15] D. Touchard, N. Pirio, P.H. Dixneuf, Organometallics 14
(1995) 4920.
A copy of the CIF and the observed and calculated
structure factors for each structure are available from
E.R.T. Tiekink (etiekink@chemistry. adelaide.edu.au).
[16] M.A. Esteruelas, A.V. Go´mez, F.J. Lahoz, A.M. Lo´pez, E.
On˜ate, L.A. Oro, Organometallics 15 (1996) 3423.
[17] V. Cadierno, M.P. Gamasa, J. Gimeno, J. Borge, S. Garc´ıa-
Granda, J. Chem. Soc. Chem. Commun. (1994) 2495.
[18] V. Cadierno, M.P. Gamasa, J. Gimeno, E. Lastra, J.
Organomet. Chem. 474 (1994) 27.
Acknowledgements
[19] V. Cadierno, M.P. Gamasa, J. Gimeno, et al., Organometallics
15 (1996) 2137.
[20] B.E.R. Schilling, R. Hoffmann, D.L. Lichtenberger, J. Am.
Chem. Soc. 101 (1979) 585.
[21] A. Davison, J.P. Selegue, J. Am. Chem. Soc. 102 (1980) 2455.
[22] M.I. Bruce, A.G. Swincer, Aust. J. Chem. 33 (1980) 1471.
[23] R.G. Beevor, M. Green, A.G. Orpen, I.G. Williams, J. Chem.
Soc. Dalton Trans. (1987) 1319.
We thank the Australian Research Council for sup-
port of this work and Johnson Matthey Technology,
Reading, UK, for a generous loan of RuCl3 ·nH2O.
P.J. Low was the holder of an Australian Post-Gradu-
ate Award.
[24] J.M. Wisner, T.J. Bartczak, J.A. Ibers, Inorg. Chim. Acta 100
(1985) 115.
[25] M.I. Bruce, M.G. Humphrey, M.R. Snow, E.R.T. Tiekink, J.
Organomet. Chem. 314 (1986) 213.
References
[1] M.I. Bruce, Chem. Rev. 91 (1991) 197.
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[3] H. Werner, J. Organomet. Chem. 475 (1994) 45.
[4] H. Le Bozec, P.H. Dixneuf, Izv. Akad. Nauk Russ. Ser. Khim.
5 (1995) 827.
[5] H. Werner, Chem. Commun. (1997) 903.
[6] (a) E.O. Fischer, H.-J. Kalder, A. Frank, F.H. Kohler, G.
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