Diphenylvinylphosphine (DPVP) complexes containing the (η5-MeC5H4)Ru(II) moiety: Synthesis, characterization and reactions

Article abstract of DOI:10.1039/b210492j

The complex [(η⁵-MeC₅H₄)Ru(DPVP)₂(CH₃ CN)]PF₆ (4) (DPVP = Ph₂PCH=CH₂) loses CH₃CN under vacuum to produce the phosphaallyl complex [(η⁵-MeC₅H₄)Ru(η¹-DPVP)( η³-DPVP)]PF₆ (6) and reacts with Me₃SiC≡CH and PhC≡CH in CH₂Cl₂-CH₃OH solutions to form the methoxymethylcarbene [(η⁵-MeC₅H₄)(DPVP)₂Ru=C(OCH ₃)(CH₃)]PF₆ (7) and the carbonyl complex [(η⁵-MeC₅H₄)Ru(DPVP)₂(CO)]PF ₆ (8), respectively. In contrast [(η⁵-MeC₅H₄)Ru(DPVP)(CO)(CH₃CN)] PF₆ (15) does not lose CH₃CN to form a phosphaallyl complex. The structures of the complexes described herein have been deduced from elemental analyses, infrared spectroscopy, ¹H, ¹³C{¹H}, ¹H NOE, where appropriate by ³¹P{¹H} NMR spectroscopy and in eight cases by X-ray crystallography.

Full text of DOI:10.1039/b210492j

View Article Online / Journal Homepage / Table of Contents for this issue
Diphenylvinylphosphine (DPVP) complexes containing the
(ꢀ5-MeC5H4)Ru(II) moiety: synthesis, characterization and
reactions†
Dorota Duraczyn´ska and John H. Nelson*
Department of Chemistry/216, University of Nevada – Reno, Reno, Nevada 89557-0020, USA
Received 24th October 2002, Accepted 27th November 2002
First published as an Advance Article on the web 13th January 2003
The complex [(η5-MeC H )Ru(DPVP) (CH CN)]PF (4) (DPVP = Ph PCH᎐CH ) loses CH CN under vacuum
᎐
5
4
2
3
6
2
2
3
5
1
3
᎐
to produce the phosphaallyl complex [(η -MeC H )Ru(η -DPVP)(η -DPVP)]PF (6) and reacts with Me SiC᎐CH
᎐
5
4
6
3
5
᎐
and PhC᎐CH in CH Cl –CH OH solutions to form the methoxymethylcarbene [(η -MeC H )(DPVP) Ru᎐
᎐
᎐
2
2
3
5
4
2
C(OCH3)(CH3)]PF6 (7) and the carbonyl complex [(η5-MeC5H4)Ru(DPVP)2(CO)]PF6 (8), respectively. In contrast
[(η5-MeC5H4)Ru(DPVP)(CO)(CH3CN)]PF6 (15) does not lose CH3CN to form a phosphaallyl complex. The
structures of the complexes described herein have been deduced from elemental analyses, infrared spectroscopy, 1H,
13C{1H}, 1H NOE, where appropriate by 31P{1H} NMR spectroscopy and in eight cases by X-ray crystallography.
4 and 6 are very different. For 4 two resonances at δ 39.95 (s, 2P,
Introduction
η1-DPVP) and Ϫ145.00 (sept., 1J(PF) = 712 Hz, 1P, PF6Ϫ) were
observed. For 6 three resonances at δ 42.38 (d, 2J(PP) = 45.0 Hz,
We have previously reported the synthesis and characterization
of the only examples of ruthenium() complexes that contain
diphenylvinylphosphine (DPVP) bound to the metal as a
neutral four-electron donor phosphaallyl ligand. These
complexes, [(η5-C5H5)Ru(η3-DPVP)(η1-DPVP)]PF6 (A)1 and
[(η5-C5Me5)Ru(η3-DPVP)(η1-DPVP)]PF6 (B)2 are among a
growing number of ruthenium complexes that contain hybrid
hemilabile ligands.3 Complexes of hemilabile ligands are of
current interest because of their potential applications in
molecular activation, homogeneous catalysis, functional
materials, and small molecule sensing.
Synthesis of A entailed removing coordinated CH3CN
from the precursor [(η5-C5H5)Ru(DPVP)2(CH3CN)]PF6 by
thermolysis under vacuum at 70–75 ЊC for 7 days. We reasoned
that because the major stabilizing interaction in A is back
donation from ruthenium into the π* orbital of the vinyl group,
2
1P, η1-DPVP), 24.12 (d, J(PP) = 45.0 Hz, 1P, η3-DPVP) and
Ϫ145.00 (sept., 1J(PF) = 713 Hz, 1P, PF6Ϫ) were observed.
These data are similar to those reported for A1 (δ 42.3, 24.2;
2
2J(PP) = 43.9 Hz) and B2 (δ 44.8, 14.3; J(PP) = 48.5 Hz).
It is interesting to note that while there is no clear trend in
2
δ
31P among these three complexes, J(PP) increases of about
1 Hz for each additional CH3 group added to the Cp ring. The
1H NMR experiments illustrated in Fig. 1 were used to first
make chemical shift assignments and then from the NOE
experiment to assign the structure of 6. The effects of phos-
phorus decoupling upon the line shapes of the vinyl proton
resonances clearly established which phosphorus resonance was
due to the η1-DPVP and η3-DPVP ligands. This is most evident
in the proton resonances of the η1-DPVP ligand which occur at
δ 4.65, 5.09 and 5.61. Irradiation of the phosphorus resonance
at δ 42.38 removes phosphorus coupling from these three
resonances while irradiation of the phosphorus resonance at
δ 24.12 does not. In contrast, all three protons of the η3-DPVP
ligand are coupled to both phosphorus nuclei.
Ϫ
the significantly better donor C5Me5 would cause B to be
more easily formed and more stable than A. And in fact,
we found that CH3CN was removed from [(η5-C5Me5)Ru-
(DPVP)2(CH3CN)]PF6 on a rotary evaporator at ≈40 ЊC in
15 minutes.2 Complexes A and B are novel compounds that can
be considered to be latent stabilized coordinatively unsaturated
species since the vinyl group is readily displaced by a variety
of two-electron donor ligands.1,2 We describe herein the
synthesis, characterization, and reactions of an additional
A 13C APT experiment established that the carbon resonance
at δ 46.37 was due to a CH2 group and that at δ 36.67 was due to
a CH group of the phosphaallyl moiety. An HMQC experiment
established that the CH2 carbon resonance correlated with
the proton resonances at δ 2.51 and 3.66 and the CH carbon
resonance correlated with the proton resonance at δ 3.57.
Hence, one of the two CH2 protons (HcЈ) resonates at δ 2.51.
The η3-DPVP ligand is bound to ruthenium in the exo
orientation in A1 and B2 in both the solution and solid states.
The NOEs observed between the MeC5H4 – CH3 protons and
protons HaЈ and HbЈ (Fig. 1) of the η3-DPVP ligand establish
that these protons are proximate in space and that 6 also has the
exo geometry in solution. Since 6, like A1 and B2 is not dynamic
in solution over the Ϫ90 to ϩ60 ЊC temperature range in
CDCl3, it is most likely that 6 has the exo geometry in the
solid state as well. The NOE observed between the CH3 and Hα
protons of the MeC5H4 ring allows assignment of the Hα and
Hβ proton resonances. All aspects of the 1H NMR spectral data
for the η3-DPVP protons of 6 are comparable to those of A1
and B2, and Table 1 summarizes selected 1H NMR data for the
three compounds.
example of
a
phosphaallyl complex [(η5-MeC5H4)Ru-
(η3-DPVP)(η1-DPVP)]PF6 (6).
Results and discussion
[(η5-MeC5H4)Ru(η3-DPVP)(η1-DPVP)]PF6 (6) was prepared by
the sequence of reactions illustrated in Scheme 1. The first three
reactions are modeled after those employed in the syntheses of
Ϫ
Ϫ
the C5H5 analogs.4 Because the donor ability of MeC5H4
should lie between those of C5H5 and Me5C5Ϫ, we expected
that it would be easier to remove CH3CN from 4 than from A
and more difficult than from B. To our surprise, removal of
CH3CN from 4 was even more difficult than from A (10 days at
86–92 ЊC under vacuum vs. 7 days at 70–75 ЊC under vacuum).
Compounds 1–6 were characterized by elemental analyses,
cyclic voltammetry, 1H, 13C{1H}, and where appropriate
31P{1H} NMR spectroscopy. The structure of 6 was deduced
from NMR spectroscopic data. The 31P{1H} NMR spectra of
Ϫ
Compounds 4, 5, and 6 all undergo quasireversible one-
electron oxidations with E1/2 values of 0.80, 0.90 and 0.89 V vs.
Fc/Fcϩ, respectively. It is somewhat surprising that 5 is not the
easiest of the three compounds to oxidize as it possesses the
† Dedicated to the late Professor Noel McAuliffe.
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
449

View Article Online
Scheme 1
set of better electron donor ligands. An explanation may lie in
the structures of these compounds. Complexes 4 and 5 were
characterized by X-ray crystallography. Views of the structures
of the cations are shown in Figs. 2 and 3, respectively. Selected
bond distances and angles are given in the figure captions. Both
complexes are three-legged piano stools with distorted octa-
hedral structures. The three DPVP ligands in 5 are arranged
with approximate C3 symmetry minimizing interligand steric
interactions. A comparison of the metrical parameters for the
two compounds indicates that 5 is somewhat more sterically
encumbered than 4. This is evidenced by the slightly longer
average Ru–P distances (2.356 vs. 2.315 Å) and Ru–C distances
(2.238 vs. 2.212 Å) for 5 than 4, respectively. Also, because of
the small steric size of CH3CN the P(1)–Ru(1)–P(2) angle
(96.89(6)Њ) in 4 is larger than the average P–Ru–P angle
(94.92(14)Њ) in 5. Despite the steric crowding evidenced in 5, it
is formed by reaction of 3 with only two moles of DPVP per
mole of 3.
Scheme 2
a quasireversible one-electron oxidation at 0.89 V vs. Fc/Fcϩ,
similar to 4–6.
The structure of 7 was confirmed by X-ray crystallography
(Fig. 4). The complex is a three-legged piano stool with a dis-
One of the reasons for preparing compounds 4 and 6 was
to use them as precursors to vinylidene5 and allenylidene5
complexes that might be catalysts for the additions of nucleo-
torted octahedral geometry. The Ru᎐C (carbene) bond length
᎐
(1.921(10) Å) is on the low end of the range (1.90–2.02 Å)
typically found for such complexes.7–9 The Ru–P distances
(2.311(3), 2.314(3) Å) and average Ru–C distance (2.262(13) Å)
are in their expected ranges.7–9 The dihedral angle measured
between the C(MeC5H4)centroid–Ru–C(carbene) and CH3–
C(carbene)–OCH3 planes, 29.6Њ, is small,7–10 suggesting that this
is the preferred geometry7 and that the barrier to rotation about
6
᎐
philes to terminal alkynes. Reaction of 4 with Me SiC᎐CH in
᎐
3
CH2Cl2–CH3OH solution gave the methoxymethylcarbene
complex 7 (Scheme 2) by nucleophilic attack of CH3OH on
a vinylidene intermediate.7 The formation of 7 was deduced by
13C{1H} NMR spectroscopy. In particular, the carbene carbon
2
resonance is a triplet at δ 306.84 with J(PC) = 12.3 Hz as
1
typically found for such complexes.8 The other H, 13C{1H},
the Ru᎐C bond might be of the order of 6–12 kcal molϪ1 10
.
᎐
and 31P{1H} NMR data (see Experimental section) are fully
consistent with the assigned structure. The complex undergoes
Variable temperature 1H, 31P{1H} and 13C{1H} NMR studies in
acetone-d6 show that for this complex there is free rotation
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
450

View Article Online
1
1
Fig. 1 Expansions of the 499.826 MHz H NMR spectra for compound 6 (from bottom to top): normal spectrum; H{31P} decoupling of the
vinylphosphine phosphorus; 1H{31P} decoupling of the phosphaallyl phosphorus; 1H NOE difference spectrum with excitation of the MeC5H4–CH3
resonance.
Fig. 2 Structural drawing of the cation of 4 showing the atom
numbering scheme (40% probability ellipsoids). Hydrogen atoms have
been omitted for clarity. Selected bond distances (Å) and angles (Њ):
Ru(1)–P(1), 2.3161(16); Ru(1)–P(2), 2.3142(17); Ru(1)–N(1), 2.040(5);
N(1)–C(35), 1.135(7); Ru(1)–C(average), 2.212(6); P(1)–Ru(1)–P(2),
96.89(6); P(1)–Ru(1)–N(1), 88.11(14); P(2)–Ru(1)–N(1), 91.72(15).
Fig. 3 Structural drawing of the cation of 5 showing the atom
numbering scheme (20% probability ellipsoids). Hydrogen atoms have
been omitted for clarity. Selected bond distances (Å) and angles (Њ):
Ru(1)–P(1), 2.359(4); Ru(1)–P(2), 2.347(4); Ru(1)–P(3), 2.362(4);
Ru(1)–C(average), 2.238(15); P(1)–Ru(1)–P(2), 94.33(13); P(1)–Ru(1)–
P(3), 95.021(14); P(2)–Ru(1)–P(3), 95.41(13).
about the Ru᎐C bond between ϩ50 and Ϫ90 ЊC. Experi-
᎐
mentally, few ruthenium carbene complexes exhibit hindered
rotation.7
Complex 4 reacts with PhC᎐CH and adventitious H O to
previously described mechanism.11 Complex 8 exhibits νCO at
1983 cmϪ1. For [(η5-C5H5)Ru(DPVP)2(CO)]PF6 (9)1 and [(η5-
Me5C5)Ru(DPVP)2(CO)]PF6 (10)2 νCO was observed at 1982
᎐
᎐
2
produce the carbonyl complex 8 (Scheme 2) by nucleophilic
attack of H2O on a vinylidene intermediate according to a
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
451

View Article Online
Table 1 Selected 1H NMR data of A, B and 6 for the η3- and η1-DPVP ligandsa
η3-DPVP
HaЈ
4.08
η1-DPVP
HbЈ
4.06
HcЈ
2.41
m
21.94
10.52
Ha
Hb
5.61
ddd
37.57
Hc
5.12
ddd
18.33
A
B
6
δ
4.54
ddd
Multiplicity
3J(PH)
3J(PH)
3J(aЈbЈ)c
3J(aЈcЈ)
2J(bЈcЈ)
m
m
15.03b
10.52
8.65
6.1
22.24
4.51
8.65
3J(PH)
25.24b
3J(ab)
3J(ac)
2J(bc)
12.32
18.33
12.32
0.90
6.1
2.96
18.33
0.90
2.96
δ
3.12
m
3.20
m
34.86
1.80
10.37
2.62
m
16.23
6.31
4.25
ddd
5.35
ddd
36.06
5.03
ddd
17.43
Multiplicity
3J(PH)
3J(PH)
3J(aЈbЈ)
3J(aЈcЈ)
2J(bЈcЈ)
13.22b
2.10
10.37
0.62
3J(PH)
26.15b
3J(ab)
3J(ac)
2J(bc)
12.32
17.43
12.32
0.60
0.62
9.91
17.43
0.60
9.91
δ
3.57
m
3.66
m
24.5
1.0
2.51
m
10.0
15.0
4.65
ddd
5.61
ddd
37.50
5.09
ddd
18.00
Multiplicity
3J(PH)
3J(PH)
3J(aЈbЈ)
3J(aЈcЈ)
2J(bЈcЈ)
18.5b
1.5
3J(PH)
25.00b
9.0
9.5
9.0
3J(ab)
3J(ac)
2J(bc)
12.30
18.00
12.30
<0.2
9.5
2.0
18.00
<0.2
2.0
a NMR spectra measured in CDCl3, chemical shifts in ppm downfield from Me4Si, coupling constants in Hz. b 2J(PH). c J(HH) coupling where the
symbols aЈ, bЈ, cЈ, and a, b, c represent HaЈ, HbЈ, HcЈ, Ha, Hb, Hc, respectively.
Fig. 4 Structural drawing of the cation of 7 showing the atom
numbering scheme (10% probability ellipsoids). Hydrogen atoms have
Fig. 5 Structural drawing of the cation of 8ؒCH2Cl2 showing the atom
been omitted for clarity. Selected bond lengths (Å) and angles (Њ):
numbering scheme (10% probability ellipsoids). Hydrogen atoms have
Ru(1)–P(1), 2.314(3); Ru(1)–P(2), 2.311(3); Ru(1)–C(35), 1.921(10);
been omitted for clarity. Selected bond lengths (Å) and angles (Њ):
Ru(1)–P(1), 2.332(4); Ru(1)–P(2), 2.320(4); Ru(1)–C(35), 1.87(2);
Ru(1)–C(average), 2.262(11); P(1)–Ru(1)–P(2), 96.86(11); P(1)–Ru(1)–
C(35), 92.81(3); P(2)–Ru(1)–C(35), 88.2(3); C(36)–C(35)–O(1), 113.0
C(35)–O(1), 1.172(19); Ru(1)–C(average), 2.247(16); P(1)–Ru–P(2),
(9).
95.76(13); P(1)–Ru(1)–C(35), 88.8(5); P(2)–Ru(1)–C(35), 91.9(5).
and 1969 cmϪ1, respectively. The 31P{1H} NMR resonances for
and
[(η5-Me C )(DPVP) Ru᎐C᎐C(Ph)H]PF ,
respectively
the DPVP ligands in 8, 9, and 10 occur at δ 36.60, 36.22 and
35.3, respectively. The carbonyl carbon resonances in the
13C{1H} NMR spectra of all three complexes is a triplet at
δ 201.60, 202.68 and 204.25, with 2J(PP) = 17.3, 17.34 and 17.2
Hz, respectively. Both 8 (Fig. 5) and 91 have been characterized
by X-ray crystallography. Both complexes are three-legged
piano stools with distorted octahedral geometries. The metrical
parameters for the two complexes are very similar. For 9 the
Ru–P distances are 2.320(2) and 2.324(2) Å, the average Ru–C
distance is 2.235(7) Å, and the Ru–CO, and C–O distances are
1.867(6) and 1.124(8) Å, respectively.1
᎐ ᎐
5
5
2
6
under conditions similar to those used for the syntheses of
7 and 8. This suggests that the Cα is less electrophilic in these
vinylidene complexes than in the MeC5H4 analogs that are
intermediates in the formation of 7 and 8. Despite the
᎐
formation of 8 by hydration of PhC᎐CH, 4 is not a good
᎐
catalyst for this hydration.
We have previously shown1 that [(η5-C5H5)Ru(CO)(η3-
DPVP)]PF6 has the endo geometry in contrast to A, B, and 6 all
of which have the exo geometry. Since this suggested that the
ancillary ligands could control the geometry of the η3-phos-
phaallyl ligand we set out to prepare [(η5-MeC5H4)Ru(CO)(η3-
DPVP)]PF6 by the reactions illustrated in Scheme 3. Complex
11 exists in solution as an equilibrium mixture of cis and trans,
12
2
᎐
᎐
᎐
Complex B reacts with Me SiC᎐CH and PhC᎐CH to form
᎐
3
the vinylidene complexes [(η5-Me C )(DPVP) Ru᎐C᎐CH ]PF
᎐ ᎐
6
5
5
2
2
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
452

View Article Online
CH3CN and AgPF6. All complexes, except for 15 which is a low
melting waxy solid, are air stable crystalline solids. They were
characterized by elemental analyses, infrared spectroscopy, 1H,
13C{1H}, and for 14 and 15 by 31P{1H} NMR spectroscopy (see
Experimental section). All spectroscopic data are consistent
with the assigned structures and are unexceptional. Com-
pounds 12, 13, and 14 were also characterized by X-ray crystal-
lography. Structures are shown in Figs. 7 and 8. Compounds 12
Fig. 7 Structural drawing of 12 showing the atom labelling scheme
(30% probability ellipsoids). Hydrogen atoms have an arbitrary radius
of 0.1 Å. Compound 13 is isostructural with 12. Selected bond
distances (Å) and angles (Њ): (12) Ru(1)–Br(1), 2.5349(16); Ru(1)–C(7),
1.885(6); Ru(1)–C(8), 1.881(6); C(7)–O(1), 1.127(7); C(8)–O(2),
1.131(8); Ru(1)–C(average), 2.232(6); C(7)–Ru(1)–Br(1), 92.64(19);
C(7)–Ru(1)–C(8), 90.4(3); C(8)–Ru(1)–Br(1), 88.8(2). (13) Ru(1)–I(1),
2.7030(11); Ru(1)–C(7), 1.874(8); Ru(1)–C(8), 1.882(9); C(7)–O(1),
1.133(10); C(8)–O(2), 1.138(11); Ru(1)–C(average), 2.240(9); C(7)–
Ru(1)–I(1), 91.6(3); C(7)–Ru(1)–C(8), 90.6(4); C(8)–Ru(1)–I(1), 88.2(3).
Scheme 3
Fig. 8 Structural drawing of 14 showing the atom labelling scheme
(30% probability ellipsoids). Hydrogen atoms have been omitted for
clarity. Selected bond distances (Å) and angles (Њ): Ru(1)–P(1), 2.292(2);
Ru(1)–Br(1), 2.5434(15); Ru(1)–C(21), 1.902(15); Ru(1)–C(average),
2.219(12); C(21)–O(1), 1.005(13); P(1)–Ru(1)–Br(1), 89.39(8); P(1)–
Ru(1)–C(21), 91.3(3); Br(1)–Ru(1)–C(21), 92.5(4).
Fig. 6 Structural drawing of 11 showing the atom numbering scheme
(30% probability ellipsoids). Hydrogen atoms have been omitted for
clarity. Selected bond lengths (Å) and angles (Њ): Ru(1)–C(7), 1.857(3);
Ru(1)–C(8), 2.056(3); Ru(1)–Ru(1A), 2.7437(7); Ru(1)–C(average),
2.272(3); C(7)–O(1), 1.145(4); C(8)–O(2), 1.170(3); Ru(1)–C(8)–
Ru(1A), 84.26(10); C(7)–Ru(1)–C(8), 92.19(12); C(8)–Ru(1)–C(8a),
95.74(10).
and 13 are isostructural and for both the CH3 and halide are
eclipsed. Except for the Ru–X distances, the bond distances in
the two compounds differ very little. All three compounds are
three-legged piano stools with distorted octahedral structures.
The Ru–Br distances in 12 and 14 are essentially the same.
Neither 14 nor 15 could be converted to phosphaallyl com-
plexes by removal of bromide from 14 or CH3CN from 15.
We have recently described the syntheses of tethered phos-
phinopropylcyclopentadiene18 and phosphinopropylarene19
compounds by hydroalkylation of coordinated DPVP. In an
effort to extend the scope of the hydroalkylation reaction to the
MeC5H4 ring system we reacted complex 14 with KOBut in
refluxing acetonitrile and with the radical initiator azobisiso-
butyronitrile (AIBN) in refluxing benzene. Both reactions failed
carbonyl bridged and nonbridged isomers.13–15 Its solid state
structure (Fig. 6) has not previously been reported. As can be
seen in Fig. 6 it has the centrosymmetric trans structure in the
solid state. The two compounds [(η5-C5H5)M(CO)2]2 (M = Fe,
Ru) also have centrosymmetric trans structures in the solid
state.16 There is very little difference in the metrical parameters
of 11 and its C5H5 analog.
Compound 13 has been previously prepared17 by oxidation
of 11 with CH3I. In our hands this procedure worked very
poorly, whereas oxidation of 11 with I2 to form 13 and with Br2
to form 12 proceeded in good yield (see Scheme 3). Compound
14 was prepared by [(η5-C5H5)Fe(CO)2]2 catalyzed17 ligand sub-
stitution of 12. Complex 15 was prepared by reaction of 14 with
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
453

View Article Online
to produce a tethered phosphinopropylcyclopentadienide com-
plex. Decomposition occurred instead. With the weaker base,
K2CO3, starting material was recovered.
TlCl was removed by filtration through Celite, and the filtrate
evaporated. The dark-brown compound was dried under
vacuum to give 0.30 g of pure product in 51% yield.
Method b. A 100 mL, three-neck round-bottom flask was
charged with 2.5 mL (0.025 mol) of freshly cracked methyl-
cyclopentadiene (MeC5H5) and 80 mL of freshly distilled
hexane. The whole was purged with nitrogen for 30 min, and
then cooled in ice. 20 mL (0.05 mol) of 2.5 M n-BuLi was added
dropwise and the mixture was stirred for 2 hours, giving a
yellowish precipitate. LiMeC5H4 was isolated by filtration using
a Schlenk line (LiMeC5H4-air sensitive) and immediately
transferred to another round-bottom flask containing 4 g
Concluding remarks
We have synthesized and characterized nine new ruthenium
complexesincludingthenewphosphaallylcomplex[(η5-MeC5H4)-
Ru(η3-DPVP)(η1-DPVP)]PF6 (6). It like its C5H5 (A) and
C5Me5 (B) analogs contains the η3-phosphaallyl ligand bound
to ruthenium in the exo orientation. For all three phosphaallyl
complexes the exo isomer does not interconvert with the endo
isomer in solution. We have compared the reactivity of 4 with
that of its Me5C5 analog toward terminal alkynes, and have
shown that the Ru᎐C carbon of the vinylidenes derived from 4
22
(8 mmol) [(C6H6)RuCl2]2 suspended in 300 mL freshly dis-
tilled acetonitrile. The whole mixture was stirred at ambient
temperature overnight. The resulting precipitate of LiCl was
removed by filtration through Celite, and the filtrate evap-
orated. The dark-brown compound was dried under vacuum to
give 1.34 g of pure product in 29% yield.
᎐
α
is much more electrophilic than those derived from the Me5C5
analog. Attempted syntheses of the carbonylphosphaallyl
complex [(η5-MeC5H4)Ru(η3-DPVP)(CO)]PF6 and a tethered
phosphinopropylcyclopentadienide complex failed.
Anal. calc. for C12H13ClRu: C, 49.07; H, 4.46. Found: C,
1
49.12; H, 4.29%. H NMR (acetone-d6): δ 6.36 (s, 6H, C6H6),
5.58 (m, 2H, Hβ), 5.43 (m, 2H, Hα), 2.11 (s, 3H, CH3). 13C{1H}
NMR (CD3CN): δ 100.70 (Ci), 87.34 (C6H6), 82.57 (Cβ), 80.70
(Cα), 13.92 (CH3).
Experimental
Reagents and physical measurements
All chemicals were reagent grade and were used as received
form commercial sources (Aldrich, Fisher Scientific, Acros
Organics, GFS Chemicals, Strem Chemicals) or synthesized as
described below. All syntheses were conducted under a nitrogen
atmosphere. [(C6H6)RuCl2]2 was synthesized by the literature
procedure.20 Acetonitrile was distilled from CaH2 prior to use.
Melting points were obtained using a Mel-Temp melting point
apparatus and are uncorrected. 1H NMR spectra were recorded
at 499.8 MHz on a Varian Unity Plus 500 FT-NMR spectro-
meter and at 300 MHz on a General Electric GN 300 FT-NMR
spectrometer. 13C{1H} NMR spectra were recorded at 125.7
MHz on a Varian Unity Plus 500 FT-NMR spectrometer and
at 75 MHz on a General Electric 300 FT-NMR spectrometer.
31P{1H} NMR spectra were recorded at 202.3 MHz on a Varian
Unity Plus 500 FT-NMR spectrometer and at 121.65 MHz on
a General Electric 300 FT-NMR spectrometer. Proton and
carbon chemical shifts were referenced to residual solvent
resonances; phosphorus chemical shifts were referenced to an
external 85% aqueous solution of H3PO4. All shifts to low field,
high frequency are positive. NOE experiments were performed
with the pulse sequence reported by Shaka and co-workers.21
IR spectra were recorded on a Perkin-Elmer Spectrum BX
spectrometer. Cyclic voltammograms were obtained at 25 ЊC in
freshly distilled CH2Cl2 containing 0.1 M tetrabutylammonium
hexafluorophosphate using a BAS CV50-W voltammetric
analyzer. A three-electrode system was used. The working elec-
trode was glassy carbon, the auxiliary electrode was a platinum
wire and the reference electrode was Ag/AgCl (aqueous) separ-
ated from the cell by a Luggin capillary. The Fc/Fcϩ couple
occurred at 508 mV22 under the same conditions. Elemental
analyses were performed by Galbraith Laboratories, Knoxville,
TN.
[(ꢀ5-MeC5H4)Ru(ꢀ6-C6H6)]PF6 (2). Method a. 0.25 g (0.9
mmol) of [(η5-MeC5H4)Ru(η6-C6H6)]Cl (1) was dissolved in 30
mL distilled water, and the green–brown solution was filtered
into a round-bottom flask. To this solution 0.5 g (3 mmol)
of NaPF6 was added. A precipitate of [(η5-MeC5H4)Ru-
(η6-C6H6)]PF6 was immediately obtained. This compound was
isolated by filtration, and dried in vacuum; 0.11 g of pure white
solid was obtained in 32% yield.
Method b. An adaptation of the procedure of Trost and
Older23 was used. 50 mL of absolute ethanol was purged with
nitrogen for 30 min. 1.95 g (14 mmol) of K2CO3 followed by
22
1.18 g (2.4 mmol) of [(C6H6)RuCl2]2 and 4.2 mL (0.042 mol)
of freshly cracked methylcyclopentadiene (MeC5H5) were
added. The resulting heterogeneous brown mixture was heated
to 60 ЊC with rapid stirring and kept at this temperature over-
night. The reaction mixture was cooled to room temperature
and filtered through Celite. The brown filtrate was concentrated
to about 20 mL, and then 1.61 g (9.8 mmol) of NH4PF6in 16
mL of water was added. The immediate formation of a brown
precipitate was observed. The remaining ethanol was removed
leaving a dark brown compound, which was dissolved in a
minimum amount of acetone and passed through a short
alumina column. The resulting yellow solution was concen-
trated, and an excess of ether was added; a white compound
was formed immediately. The mixture was left in the freezer
overnight. The white compound was separated by filtration,
washed with ether and dried under vacuum for 4 hours. 0.45 g
(24%) of pure compound was obtained.
Mp: 288–290 ЊC (decomp.). Anal. calc. for C12H13F6PRu:
C, 35.74; H, 3.25. Found: C, 35.61; H, 3.16%. 1H NMR
(acetone-d6): δ 6.28 (s, 6H, C6H6), 5.52 (m, 2H, Hβ), 5.38 (m,
2H, Hα), 2.08 (s, 3H, CH3). 13C{1H} NMR (acetone-d6):
δ 100.75 (Ci), 87.37 (C6H6), 82.51 (Cβ), 80.62 (Cα), 13.71 (CH3).
31P{1H} NMR (acetone-d6): δ Ϫ142.06 (sept., 1J(PF) = 706 Hz).
Syntheses
[(ꢀ5-MeC5H4)Ru(ꢀ6-C6H6)]Cl (1). Method a. A 100 mL,
three-neck round-bottom flask was charged with 30 mL of
absolute ethanol and purged with nitrogen for 30 min. Then 0.5
mL (5.0 mmol) of freshly cracked methylcyclopentadiene
(MeC5H5) and 3.5 g (0.014 mol) of thallium ethoxide were
added. The whole was stirred at ambient temperature for
30 min, giving a yellowish compound. TlMeC5H4 was isolated
by filtration using a Schlenk line (TlMeC5H4-air sensitive)
and immediately transferred to another round-bottom flask
containing 0.5 g (1 mmol) of [(C6H6)RuCl2]2 22 suspended in 30
mL freshly distilled acetonitrile. The whole mixture was stirred
at ambient temperature overnight. The resulting precipitate of
[(ꢀ5-MeC5H4)Ru(CH3CN)3]PF6 (3). A solution containing
0.45 g (1.12 mmol) of [(η5-MeC5H4)Ru(η6-C6H6)]PF6 (2) in 150
mL of freshly distilled acetonitrile (yellowish solution) was
irradiated in a quartz vessel with a medium pressure Hg lamp
for 24 h. The solvent was removed from the golden-yellow
solution on a rotary evaporator and the yellow solid residue was
dried under vacuum. 0.45 g (90%) of pure compound was
obtained. Mp: 67–70 ЊC. 1H NMR (acetone-d6): δ 4.23 (m, 2H,
Hβ), 3.99 (m, 2H, Hα), 2.45 (s, 9H, CH3CN), 1.70 (s, 3H, CH3).
13C{1H} NMR (acetone-d6): δ 126.16 (CN), 87.00 (Ci), 70.93
(Cβ), 64.55 (Cα), 12.66 (CH3), 3.06 (CH3CN). 31P{1H} NMR
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
454

View Article Online
2
(acetone-d6): δ Ϫ142.3 (sept., 1J(PF) = 705 Hz). IR (CN region,
Nujol, cmϪ1): 2324, 2283. IR (PF6 region, acetone film, cmϪ1):
842.
Hz, 1P, PF6Ϫ). 13C{1H} NMR (CDCl3): δ 135.11 (d, J(PC) =
11.3 Hz, Co), 134.45 (dd, 1J(PC) = 48.0 Hz, 3J(PC) = 2.6 Hz, Ci),
2
2
133.00 (d, J(PC) = 12.6 Hz, Co), 132.57 (d, J(PC) = 11.3 Hz,
2Co), 132.41 (d, 4J(PC) = 2.4 Hz, Cp), 131.79 (d, 4J(PC) = 2.1 Hz,
[(ꢀ5-MeC5H4)Ru(CH3CN)(DPVP)2]PF6 (4) and [(ꢀ5-MeC5-
H4)Ru(DPVP)3]PF6 (5). A 50 mL, three-neck round-bottom
flask was charged with 0.45 g (1 mmol) of [(η5-MeC5H4)-
Ru(CH3CN)3]PF6 (3) and 25 mL of freshly distilled acetonitrile.
The whole was purged with nitrogen for 30 min. Then 0.5 mL
Cp), 131.61 (d, J(PC) = 2.0 Hz, Cp), 131.51 (dd, J(PC) = 52.3
4
1
Hz, 3J(PC) = 4.0 Hz, Ci), 130.57 (CβCp), 129.78 (d, 1J(PC) = 43.5
3
3
Hz, Cα), 129.59 (d, J(PC) = 12.2 Hz, Cm), 129.42 (d, J(PC) =
11.9 Hz, Cm), 128.76 (d, 3J(PC) = 10.4 Hz, Cm), 128.54 (d,
1
3
3J(PC) = 10.2 Hz, Cm), 125.34 (dd, J(PC) = 52.7 Hz, J(PC) =
5.0 Hz, Ci), 102.68 (CiMeCp), 86.46 (CβMeCp), 85.09 (d, J(PC)
= 4.9 Hz, CαMeCp), 84.88 (CαMeCp), 83.31 (CβMeCp), 46.37
(d, 2J(PC) = 4.8 Hz, CβЈ), 36.67 (d, 1J(PC) = 32.2 Hz, CαЈ), 11.06
(CH3).
(2.5 mmol) of DPVP (Ph PCH᎐CH ) was added, and the
᎐
2
2
mixture was stirred at room temperature overnight. Solvent was
evaporated leaving a brown solid. This solid was dissolved
in CH2Cl2 and passed through a silica gel column packed with
hexane and eluted with CH2Cl2. Recrystallization from
CH2Cl2–hexane gave 0.61 g (77% yield) of yellow crystalline 4.
Mp: 155–160 ЊC. Anal. calc. for C36H36F6NP3Ru: C, 54.69; H,
4.59. Found: C, 54.67; H, 4.81%. 1H NMR (CDCl3): δ 7.70 (m,
2H, Ho), 7.52 (m, 2H, Hp), 7.45 (m, 4H, Hm), 7.36 (m, 2H, Hp),
7.30 (m, 6H, Ho,m), 6.98 (m, 4H, Ho), 5.82 (m, 4H, HaHb), 5.11
(m, 2H, Hc), 4.40 (s, 2H, HβЈ), 3.99 (s, 4H, HαЈ), 2.42 (s, 3H,
CH3CN), 2.01 (d, J(PH) = 1.0 Hz, 3H, CH3). 31P{1H} NMR
[(ꢀ5-MeC H )(DPVP) Ru᎐C(OCH )(CH )]PF (7). A 50 mL,
three-neck round-bottom flask was charged with 0.40 g
(0.5 mmol) of [(η5-MeC5H4)Ru(CH3CN)(DPVP)2]PF6 (4)
and 30 mL of a 1 : 1 CH2Cl2–MeOH mixture. The whole was
purged with nitrogen for 30 min. Then 0.25 mL (1.8 mmol) of
HC᎐CSiMe was added, and the mixture was heated at reflux
᎐
5
4
2
3
3
6
᎐
᎐
3
for 3 days (color turned dark). The solution was placed in a
freezer and the formation of a yellow precipitate was observed.
This precipitate was separated by filtration and analyzed. It
appeared to be starting material (0.014 g). Solvent from the
filtrate was evaporated and the residue was recrystallized from
CH2Cl2–hexane to give 0.12 g of pure product in 29% yield.
Mp: 221–225 ЊC. Anal. calc. for C37H39F6OP3Ru: C, 55.02; H,
4.89. Found: C, 54.93; H, 5.10%. 1H NMR (CDCl3): δ 7.52 (m,
2H, Hp), 7.45 (m, 4H, Hm), 7.36 (m, 2H, Hp), 7.29 (m, 4H, Hm),
7.18 (m, 4H, Ho), 6.96 (m, 4H, Ho), 6.14 (m, |2J(PH) ϩ 4J(PH)| =
24.5 Hz, 3J(HaHc) = 18.0 Hz, 3J(HaHb) = 12.3 Hz, 2H, Ha), 5.78
(m, |3J(PH) ϩ 5J(PH)| = 36.0 Hz, 3J(HaHb) = 12.3 Hz, 2H, Hb),
4.89 (m, |3J(PH) ϩ 5J(PH)| = 18.0 Hz, 3J(HaHc) = 18.0 Hz, 2H,
1
(CDCl3): δ 39.95 (s, 2P, DPVP), Ϫ145.00 (sept., J(PF) = 712
Hz, 1P, PF6Ϫ). 13C{1H} NMR (CDCl3):24 δ 135.36 (m, |1J(PC) ϩ
4
3J(PC)| = 46.9 Hz, Ci), 133.87 (T, |2J(PC) ϩ J(PC)| = 11.3 Hz,
3
Co), 133.01 (m, |1J(PC) ϩ J(PC)| = 50.5 Hz, Ci), 132.29 (T,
|2J(PC) ϩ 4J(PC)| = 10.1 Hz, Co), 131.83 (m, |1J(PC) ϩ 3J(PC)| =
81.7 Hz, Cα), 130.81 (s, Cp), 130.15 (s, Cp), 128.96 (s, Cβ), 128.55
(T, |3J(PC) ϩ 5J(PC)| = 9.8 Hz, Cm), 128.40 (T, |3J(PC) ϩ 5J(PC)|
= 9.8 Hz, Cm), 126.98 (s, CH3CN), 107.12 (s, CiCp), 82.64 (s,
CβCp), 80.30 (s, CαCp), 12.48 (s, CH3), 4.61 (s, CH3CN). E1/2
=
0.80 V vs. Fc/Fcϩ.
When an excess of DPVP (for example a 1 : 3 molar ratio) is
used, only [(η5-MeC5H4)Ru(DPVP)3]PF6 (5) is obtained in 65%
yield. Mp: 188–189 ЊC. Anal. calc. for C48H46F6P4Ru: C, 59.94;
Hc), 4.73 (m, |3J(HH) ϩ J(HH)| = 3.5 Hz, 2H, Hβ), 4.68 (m,
4
1
H, 4.82. Found: C, 59.78; H, 4.63%. H NMR (acetone-d6):
|3J(HH) ϩ 4J(HH)| = 3.5 Hz, 2H, Hα), 3.73 (s, 3H, OCH3), 3.01
(s, 3H, CH3), 1.60 (s, 3H, CH3). 31P{1H} NMR (CDCl3): δ 45.17
δ 7.44 (m, 6H, Hp), 7.32 (m, 12H, Hm), 7.15 (m, 6H, Ho), 7.15
(m, 3J(HaHc) = 18.0 Hz, 3J(HaHb) = 12.0 Hz, 3H, Ha), 6.08 (m,
(s, 2P), Ϫ145.00 (sept., J(PF) = 713 Hz, 1P, PF6Ϫ). 13C{1H}
1
2
2
3J(HaHb) = 12.0 Hz, J(HbHc) = 1.2 Hz, 3H, Hb), 5.17 ([AB]2,
NMR (CDCl ): δ 306.84 (t, J(PC) = 12.3 Hz, Ru᎐C), 134.50
᎐
3
|3J(HH) ϩ 4J(HH)| = 4.0 Hz, 2H, HβCp), 4.81 ([AB]2, |3J(HH) ϩ
(AXXЈ, 5L, J(PP) = 34.5 Hz, J(PC) = 48.5 Hz, J(PC) = 2.3
2
1
3
4J(HH)| = 4.0 Hz, 2H, HαCp), 4.86 (m, J(HaHc) = 18.0 Hz,
Hz, Ci), 133.73 (T, |2J(PC) ϩ J(PC)| = 10.9 Hz, Co), 133.39
3
4
2J(HbHc) = 1.2 Hz, 3H, Hc), 1.60 (s, 3H, CH3). 31P{1H} NMR
(AXXЈ, 5L, J(PP) = 34.5 Hz, J(PC) = 42.7 Hz, J(PC) = 2.0
2
1
3
1
4
(acetone-d6): δ 29.28 (s, 3P, DPVP), Ϫ145.96 (sept., J(PF) =
Hz, Cα), 132.80 (T, |2J(PC) ϩ J(PC)| = 9.7 Hz, Co), 132.62
707 Hz, 1P, PF6Ϫ). 13C{1H} NMR (acetone-d6): δ 136.44 (m, Ci),
(AXXЈ, 5L, J(PP) = 34.5 Hz, J(PC) = 46.1 Hz, J(PC) = 2.2
Hz, Ci), 130.89 (s, Cp), 130.27 (s, Cp), 128.48 (T, |3J(PC) ϩ
2
1
3
4
135.41 (m, Cα), 134.58 (D, |2J(PC) ϩ J(PC)| = 6.5 Hz, Co),
134.55 (D, |2J(PC) ϩ 4J(PC)| = 6.5 Hz, Co), 131.23 (s, Cp), 130.91
5J(PC)| = 9.9 Hz, Cm), 128.23 (T, |3J(PC) ϩ J(PC)| = 9.7 Hz,
5
5
(s, Cβ), 129.12 (D, |3J(PC) ϩ J(PC)| = 6.3 Hz, Cm), 129.10 (D,
Cm), 127.72 (s, Cβ), 110.42 (s, CqCp), 89.95 (s, CαЈ), 89.57 (s, CβЈ),
61.26 (s, OCH3), 45.25 (s, CH3), 12.43 (s, CH3). E1/2 = 0.89 V vs.
Fc/Fcϩ.
|3J(PC) ϩ 5J(PC)| = 7.0 Hz, Cm), 104.08 (s, CiCp), 86.92
(q, J(PC) = 1.1 Hz, CβCp), 85.18 (q, J(PC) = 1.4 Hz, CαCp),
13.29 (s, CH3). E1/2 = 0.90 V vs. Fc/Fcϩ.
[(ꢀ5-MeC5H4)Ru(DPVP)2(CO)]PF6 (8). A 50 mL, three-neck
round-bottom flask was charged with 0.40 g (0.5 mmol) of
[(η5-MeC5H4)Ru(CH3CN)(DPVP)2]PF6 (4) and 30 mL of a 1 : 1
CH2Cl2–MeOH mixture. The whole was purged with nitrogen
for 30 min. Then 0.3 mL (2.7 mmol) of HC᎐CPh was added,
and the mixture was heated at reflux overnight (change of color
was noticed: yellow to orange to red). The solution was placed
in a freezer and the formation of a yellow precipitate was
observed. This precipitate was collected by filtration and
analyzed. It appeared to be starting material (0.017 g). Solvent
from the filtrate was evaporated and the residue was recrystal-
lized from CH2Cl2–MeOH–ether to give 0.10 g of pure product
in 26% yield. Mp: 95–98 ЊC. Anal. calc. for C35H33F6OP3Ru: C,
54.06; H, 4.28. Found: C, 53.95; H, 4.34%. 1H NMR (CDCl3):
δ 7.60 (m, 6H, Ho,p), 7.38 (m, 6H, Hm,p), 7.29 (m, 4H, Hm), 6.91
[(ꢀ5-MeC5H4)Ru(ꢀ1-DPVP)(ꢀ3-DPVP)]PF6 (6). 0.51 g (0.6
mmol) of [(η5-MeC5H4)Ru(CH3CN)(DPVP)2]PF6 (4) was
heated under vacuum at 86–92 ЊC for 10 days. Recrystallization
from CH2Cl2–MeOH–hexane gave 0.19 g (40%) of a yellow
product. Mp: 212–220 ЊC. Anal. calc. for C34H33F6P3Ru: C,
54.31; H, 4.74. Found: C, 54.01; H, 4.43%. 1H NMR (CDCl3):
δ 7.82 (m, 2H, Ho), 7.56 (m, 8H, Ho,m), 7.44 (m, 3H, Hp), 7.31
(m, 3H, Hm,p), 7.04 (m, 2H, Hm), 6.91 (m, 2H, Ho), 5.61 (dd,
᎐
᎐
3
3J(PH) = 37.5 Hz, J(HaHb) = 12.3 Hz, 1H, Hb), 5.60 (bs, 1H,
MeCpHβ), 5.09 (apparent t, 3J(PH) = 3J(HaHc) = 18.0 Hz,
1H, Hc), 4.81 (bs, 1H, MeCpHα), 4.65 (ddd, 2J(PH) = 25.0 Hz,
3J(HaHc) = 18.0 Hz, 3J(HaHb) = 12.3 Hz, 1H, Ha), 4.57 (bs, 1H,
MeCpHβ), 4.21 (bs, 1H, MeCpHα), 3.66 (ABMX, 3J(PH) = 24.5
3
2
3
Hz, J(HaЈHbЈ) = 9.0 Hz, J(HbЈHcЈ) = 2.0 Hz, J(PH) = 1.0 Hz,
1H, HbЈ), 3.57 (ABMX, 3J(PH) = 18.5 Hz, 3J(HaЈHcЈ) = 9.5 Hz,
3
3
(m, 4H, Ho), 5.93 (dd, J(HaHb) = 12.3 Hz, J(PH) = 39.5 Hz,
2H, Hb), 5.78 (ddd, 2J(PH) = 29.5 Hz,3J(HaHc) = 18.0 Hz,
3J(HaHb) = 12.3 Hz, 2H, Ha), 5.16 (apparent t, 3J(PH) =
3J(HaHc) = 18.0 Hz, 2H, Hc), 5.00 (s, 2H, Cpβ), 4.86 (s, 2H, Cpα),
2.01 (s, 3H, CH3). 31P{1H} NMR (CDCl3): δ 36.60 (s, 2P,
3J(HaЈHbЈ) = 9.0 Hz, J(PH) = 1.5 Hz, 1H, HaЈ), 2.51 (dddd,
3
3J(PH) = 15.0 Hz, 3J(PH) = 10.0 Hz, 3J(HaЈHcЈ) = 9.5 Hz,
2J(HbЈHcЈ) = 2.0 Hz, 1H, HcЈ), 1.45 (s, 3H, CH3). 31P{1H} NMR
(CDCl3): δ 42.38 (d, 2J(PP) = 45.0 Hz, 1P, η1-DPVP), 24.12 (d,
2J(PP) = 45.0 Hz, 1P, η3-DPVP), Ϫ145.00 (sept., J(PF) = 713
DPVP), Ϫ145.00 (sept., J(PF) = 713 Hz, 1P, PF6Ϫ). 13C{1H}
1
1
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
455

View Article Online
2
NMR (CDCl3): δ 201.60 (t, J(PC) = 17.3 Hz, CO), 134.08 (T,
brought to reflux under a nitrogen atmosphere. A tenth-molar
amount of the catalyst (17 mg) [(η5-C5H5)Fe(CO)2]2, was added
to the refluxing mixture. The reaction progress was monitored
by IR spectroscopy in the CO region. After 3 hours at reflux the
reaction was complete (band at 2057 cmϪ1 disappeared).
Solvent was removed leaving a brown, oily compound. This
compound was dissolved in CH2Cl2 and passed through a silica
gel column packed with hexane and eluted with CH2Cl2.
Recrystallization from CH2Cl2–hexane gave 1.17 g of pure
product in 53% yield. Mp: 130–131 ЊC. Anal. calc. for
C21H20BrOPRu: C, 50.41; H, 4.03; Br, 15.97. Found: C, 50.26;
H, 3.95; Br, 15.62%. 1H NMR (CDCl3): δ 7.06 (m, 4H, Hm), 6.89
(m, 6H, Ho,p), 6.26 (apparent td, J(PH) = J(HaHc) = 19.3 Hz,
3J(HaHb) = 11.8 Hz, 1H, Ha), 5.50 (dd, 3J(PH) = 39.5 Hz,
2J(HaHb) = 11.8 Hz, 1H, Hb), 5.01 (apparent t, 3J(PH) =
3J(HaHc) = 19.3 Hz, 1H, Hc), 4.26 (s, 1H, Cp), 4.12 (s, 1H, Cp),
4.06 (s, 1H, Cp), 3.90 (s, 1H, Cp), 1.43 (s, 3H, CH3). 31P{1H}
NMR (CDCl3): δ 42.14 (s). 13C{1H} NMR (CDCl3): δ 202.80
|2J(PC) ϩ 4J(PC)| = 11.7 Hz, Co), 133.75 (AXXЈ, 1J(PC) = 49.4
2
3
Hz, J(PP) = 30.7 Hz, J(PC)| = 5.1 Hz, Ci), 132. 04 (s, Cp),
131.91 (T, |2J(PC) ϩ J(PC)| = 10.3 Hz, Co), 130.96 (s, Cp),
4
130.77 (s, Cβ), 130.60 (D, |1J(PC) ϩ J(PC)| = 45.2 Hz, Cα),
3
130.09 (AXXЈ, 1J(PC) = 49.5 Hz, 2J(PP) = 30.7 Hz, 3J(PC) = 5.0
Hz, Ci), 129.26 (T, |3J(PC) ϩ 5J(PC)| = 10.8 Hz, Cm), 128.76 (T,
|3J(PC) ϩ J(PC)| = 10.6 Hz, Cm), 110. 34 (t, J(PC) = 2.0 Hz,
5
Cpq), 91.36 (s, Cpβ), 66.74 (s, Cpα), 13.19 (s, CH3). IR (CO
region, CH2Cl2, cmϪ1): 1983.
[(ꢀ5-MeC5H4)Ru(CO)2]2 (11). A 500 mL, three-neck round-
bottom flask was charged with 4.0 g (6.3 mmol) of Ru3(CO)12
and 280 mL freshly distilled heptane (2,2,4-trimethylpentane
may be used as well). This solution was then heated to
reflux under a nitrogen atmosphere. When all Ru3(CO)12 had
dissolved, 7.0 mL (0.070 mol) of freshly cracked methyl-
cyclopentadiene (MeC5H5) was added via syringe, and the
whole was heated at reflux for 2 days. The resulting orange–
brown solution was stirred magnetically at ambient temper-
ature for another 2 days. Solvent was removed, leaving a brown,
oily compound, which was washed with pentane. This com-
pound was dissolved in CH2Cl2 and passed through a silica gel
column wetted with hexane and eluted with CH2Cl2. Recrystal-
lization from CH2Cl2–hexane gave 3.11 g of orange crystals in
2
3
2
1
(d, J(PC) = 20.5 Hz, CO), 134.64 (d, J(PC) = 29.9 Hz, Ci),
1
1
134.61 (d, J(PC) = 45.5 Hz, Cα), 134.25 (d, J(PC) = 31.0 Hz,
Ci), 133.22 (d, J(PC) = 10.8 Hz, Co), 132.70 (d, J(PC) = 10.6
2
2
4
Hz, Co), 130.50 (s, Cβ), 130.25 (d, J(PC) = 2.4 Hz, Cp), 130.04
(d, 4J(PC) = 2.4 Hz, Cp), 128.20 (d, 3J(PC) = 8.8 Hz, Cm), 128.11
(d, 3J(PC) = 8.8 Hz, Cm), 110.10 (d, J(PC) = 2.0 Hz, CiЈ), 86.29
(d, J(PC) = 1.5 Hz, Cp), 84.10 (s, Cp), 80.97 (d, J(PC) = 5.7 Hz,
Cp), 79.65 (s, Cp), 13.31 (s, CH3). IR (CO region, CH2Cl2,
cmϪ1): 1955. E1/2 = 0.53 V vs. Fc/Fcϩ.
1
70% yield. Mp: 135–137 ЊC. H NMR (CDCl3): δ 5.18 ([AB]2,
|3J(HH) ϩ J(HH)| = 4.5 Hz, 4H, Hβ), 5.01 ([AB]2, |3J(HH) ϩ
4
4J(HH)| = 4.5 Hz, 4H, Hα), 2.02 (s, 6H, 2CH3). 13C{1H} NMR
(CDCl3): δ 222.87 (CO), 109.45 (Ci), 89.40 (Cβ), 88.57 (Cα),
12.85 (CH3). IR (CO region, CH2Cl2, cmϪ1): 2044, 1992, 1766,
1964 (sh).
[(ꢀ5-MeC5H4)Ru(DPVP)(CH3CN)(CO)]PF6 (15). A 250 mL,
three-neck round-bottom flask was charged with 2.05 g (4.1
mmol) of [(η5-MeC5H4)Ru(CO)(DPVP)(Br)] (14), and 100 mL
freshly distilled acetonitrile. The whole was stirred under a
nitrogen atmosphere for 30 min. The flask was wrapped with
aluminium foil and then 1.14 g (4.5 mmol) of AgPF6 was
added. The solution was heated at reflux overnight. AgBr was
separated by filtration through Celite and the solvent was
evaporated. The green–brown residue was dissolved in CH2Cl2
and passed through a silica gel column packed with hexane and
eluted with CH2Cl2. Solvent was removed in vacuo leaving 1.06
g (43% yield) of waxy product. Anal. calc. for C23H23NOF6-
[(ꢀ5-MeC5H4)Ru(CO)2(Br)] (12). A solution of 0.7 g (4.4
mmol) of bromine in 30 mL CH2Cl2 was added dropwise to a
solution of 2.03 g (4.3 mmol) of [(η5-MeC5H4)Ru(CO)2]2 (11) in
40 mL CH2Cl2 at Ϫ20 ЊC (CCl4 with dry ice) under a nitrogen
atmosphere. The dark red solution was then stirred for 2 hours
at ambient temperature. Solvent was removed. The brown
residue was dissolved in CH2Cl2 and passed through a silica gel
column wetted with hexane and eluted with CH2Cl2. Recrystal-
lization from CH2Cl2–hexane gave 1.52 g of pure product in
56% yield. Mp: 48–53 ЊC. Anal. calc. for C8H7BrO2Ru: C,
30.40; H, 2.23; Br, 25.28. Found: C, 30.24; H, 2.19; Br, 25.31%.
1H NMR (CDCl3): δ 5.11 ([AB]2, |3J(HH) ϩ 4J(HH)| = 4.0 Hz,
2H, Hβ), 5.09 ([AB]2, |3J(HH) ϩ 4J(HH)| = 4.0 Hz, 2H, Hα), 1.99
(s, 3H, CH3). 13C{1H} NMR (CDCl3): δ 195.75 (CO), 115.48 (s,
Ci), 83.93 (s, Cβ), 83.85 (s, Cα), 13.39 (s, CH3). IR (CO region,
CH2Cl2, cmϪ1): 2049, 1997.
1
P2Ru: C, 45.55; H, 3.82. Found: C, 45.49; H, 3.84%. H NMR
(CDCl3): δ 7.45 (m, 6H, Hm,p), 7.33 (m, 4H, Ho), 6.78 (ddd,
2J(PH) = 30.0 Hz, 3J(HaHc) = 18.0 Hz, 3J(HaHb) = 12.0 Hz, 1H,
3
3
Ha), 6.15 (dd, J(PH) = 41.5 Hz, J(HaHb) = 12.0 Hz, 1H, Hb),
5.40 (dd, 3J(PH) = 20.5 Hz, 3J(HaHc) = 18.0 Hz, 1H, Hc), 4.96 (s,
1H, Cp), 4.94 (s, 1H, Cp), 4.80 (s, 2H, Cp), 2.09 (s, 3H,
CH3CN), 1.87 (s, 3H, CpCH3). 13C{1H} NMR (CDCl3):
δ 200.02 (d, 2J(PC) = 18.2 Hz, CO), 132.81 (d, 2J(PC) = 11.3 Hz,
2
1
[(ꢀ5-MeC5H4)Ru(CO)2(I)] (13). A solution of 0.8 g (3.1 mmol)
of iodine in 30 mL CH2Cl2 was added dropwise to a solution of
1.48 g (3.1 mmol) of [(η5-MeC5H4)Ru(CO)2]2 (11) in 35 mL
CH2Cl2 at Ϫ20 ЊC (CCl4 with dry ice) under a nitrogen
atmosphere. The dark purple solution was then stirred for
2 hours at ambient temperature. Solvent was removed. The
brown residue was dissolved in CH2Cl2 and passed through a
silica gel column wetted with hexane and eluted with CH2Cl2.
The first fraction (purple) contained iodine, and the second
(orange) the product. Recrystallization from ether–hexane gave
1.97 g of pure product in 86% yield. Mp: 43–45 ЊC. Anal. calc.
for C8H7IO2Ru: C, 26.46; H, 1.94; I, 34.95. Found: C, 26.22; H,
Co), 132.14 (d, J(PC) = 10.6 Hz, Co), 132.03 (d, J(PC) = 46.0
1
Hz, Cα), 131.9 (s, Cβ), 131.49 (d, J(PC) = 52.4 Hz, Ci), 131.15
(d, 4J(PC) = 2.4 Hz, Cp), 130.95 (d, 4J(PC) = 2.5 Hz, Cp), 130.81
1
3
(d, J(PC) = 52.0 Hz, Ci), 128.88 (d, J(PC) = 10.4 Hz, Cm),
128.85 (d, 3J(PC) = 10.6 Hz, Cm), 127.98 (s, CH3CN), 111.84 (d,
J(PC) = 2.5 Hz, Cpq), 86.61 (s, Cp), 85.12 (s, Cp), 81.10 (s, Cp),
80.51 (d, J(PC) = 4.0 Hz, Cp), 12.48 (s, CpCH3), 3.16 (s,
CH3CN). IR (CO region, CH2Cl2, cmϪ1): 1988, IR (CN region,
CH2Cl2, cmϪ1): 2306.
X-Ray crystallographic studies
1.69; I, 35.02%. H NMR (CDCl3): δ 5.28 ([AB]2, |3J(HH) ϩ
1
Single crystals of 4, 5, 7, 8ؒCH2Cl2, 11, 12, 13, and 14 were
obtained as follows: slow diffusion of hexane into a CH2Cl2
solution (4, 11, 12, and 14), slow diffusion of ether into a
CH2Cl2 solution (7 and 8), slow diffusion of ether into a CHCl3
solution (5), and slow diffusion of hexane into an ether solution
(13). The crystals were mounted on glass fibers, coated with
epoxy, and placed on a Siemens P4 diffractometer. Intensity
data were taken in the ω mode with graphite monochromated
Mo-Kα radiation (λ = 0.71073 Å). Three check reflections,
monitored every 100 reflections, showed random (<2%)
4J(HH)| = 4.0 Hz, 2H, Hβ), 5.19 ([AB]2, |3J(HH) ϩ 4J(HH)| = 4.0
Hz, 2H, Hα), 2.24 (s, 3H, CH3). 13C{1H} NMR (CDCl3):
δ 195.61 (CO), 111.47 (Ci), 85.32 (Cβ), 85.01 (Cα), 14.54 (CH3).
IR (CO region, CH2Cl2, cmϪ1): 2044, 1994.
[(ꢀ5-MeC5H4)Ru(CO)(DPVP)(Br)] (14). A 100 mL, three-
neck round-bottom flask was charged with 1.4 g (4.4 mmol) of
[(η5-MeC5H4)Ru(CO)2(Br)] (12), 20 mL of benzene and 0.9 mL
(4.5 mmol) of DPVP (Ph PCH᎐CH ). This solution was then
᎐
2
2
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
456

View Article Online
Table 2 Crystallographic data
4
5
7
8ؒCH2Cl2
11
12
13
14
Empirical
formula
FW
Crystal system Monoclinic
Space group
a/Å
b/Å
c/Å
α/Њ
β/Њ
C36H36F6NP3Ru C48H47F6P4Ru C37H39F6OP3Ru C36H35Cl2F6OP3Ru C8H7O2Ru C8H7BrO2Ru C8H7IO2Ru C21H17BrOPRu
790.64
962.81
Monoclinic
P21/c
15.716(4)
13.605(2)
20.704(5)
90
97.081(19)
90
4392.9(17)
4
807.66
Tetragonal
P41212
13.6771(19)
13.6771(19)
39.271(8)
90
90
90
7346(2)
8
862.52
236.21
Monoclinic Triclinic
P21/c
8.0001(12)
11.9948(14) 7.662(3)
8.2434(14)
90
100.329(16) 93.86(5)
90
316.12
363.11
Triclinic
¯
P1
497.30
Monoclinic
P21/n
Triclinic
¯
¯
P21/n
P1
P1
13.5787(10)
13.166(4)
20.392(2)
90
97.630(8)
90
9.464(20)
10.951(4)
18.964(7)
90.68(4)
103.09(3)
101.30(3)
1874.1(11)
2
6.959(5)
7.0680(17) 9.665(2)
7.538(2) 14.513(4)
10.2386(14) 14.740(3)
92.931(18) 90
96.106(13) 104.747(18)
109.316(19) 90
509.7(2)
2
9.871(4)
91.84(3)
γ/Њ
112.85(4)
483.0(5)
2
V/Å3
3613.4(12)
4
778.2(2)
4
1999.4(8)
4
Z
dc/g cmϪ3
µ/mmϪ1
R1(F)/
wR2(F 2)a
1.453
0.624
0.0562/
0.1262
1.456
0.562
0.0859/
0.1913
1.461
0.617
0.0598/
0.1089
1.528
0.747
0.1040/
0.2298
2.016
1.954
0.0308/
0.0782
2.174
5.715
0.0446/
0.1085
2.366
4.525
0.0845/
0.2023
1.652
2.868
0.0605/
0.1504
2
2
½
a Final R indices have I > 2σ(I ). R1(F) = Σ(|Fo| Ϫ |Fc|)/Σ|Fo|; wR2(F 2) = [Σw(|Fo | Ϫ |Fc2|)2/Σw(|Fo |)2] .
4 T. P. Gill and K. R. Mann, Organometallics, 1982, 1, 485.
5 (a) M. I. Bruce, Chem. Rev., 1998, 98, 2797; (b) M. I. Bruce, Chem.
Rev., 1991, 91, 197.
6 (a) C. Bruneau and P. H. Dixneuf, Acc. Chem. Res., 1999, 32, 311; (b)
B. M. Trost, F. D. Toste and A. B. Pinkerton, Chem. Rev., 2001, 101,
2067; (c) V. Guerchais, Eur. J. Inorg. Chem., 2002, 783; (d )
V. Cadierno, M. P. Gamasa and J. Gimeno, Eur. J. Inorg. Chem.,
2001, 571.
variation during the data collections. The data were corrected
for Lorentz, polarization effects, and absorption (using an
empirical model derived from azimuthal data collections).
Crystals of 8 were of poor quality and did not diffract well. For
14 the vinyl group is disordered over two sites. Scattering
factors and corrections for anomalous dispersion were taken
from a standard source.25 Calculations were performed within
the Siemens SHELXTL Plus (version 5.10) software package
on a PC. The structures were solved by direct methods (4, 8,
and 11) or Patterson methods (5, 7, 12, 13, and 14). Anisotropic
thermal parameters were assigned to all non-hydrogen atoms.
Hydrogen atoms were refined at calculated positions with a
riding model in which the C–H vector was fixed at 0.96 Å. The
data were refined by the method of full matrix least-squares on
F 2. Final cycles of refinement converged to the R1(F) and
wR2(F 2) values given in Table 2, where wϪ1 = σ2(F) ϩ 0.001F 2.
CCDC reference numbers 195526–195533.
7 H. D. Hansen and J. H. Nelson, Organometallics, 2000, 19, 4740 and
references therein.
8 (a) H. Le Bozec, K. Ouzzine and P. H. Dixneuf, Organometallics,
1991, 10, 2768; (b) K. Ouzzine, H. Le Bozec and P. H. Dixneuf,
J. Organomet. Chem., 1986, 317, C25; (c) P. H. Dixneuf, Pure Appl.
Chem., 1989, 61, 1763; (d ) D. Pilette, K. Ouzzine, H. Le Bozec,
P. H. Dixneuf, C. E.F. Rickard and W. R. Roper, Organometallics,
1992, 11, 809.
9 (a) U. Schubert, in Transition Metal Carbene Complexes, Verlag
Chemie, Weinheim, Germany, 1983, p. 73; (b) C. Bianchini, D. Masi,
A. Romerosa, F. Zanobini and M. Peruzzini, Organometallics, 1999,
18, 2376; (c) K. E. Stockman, M. Sabat, M. G. Finn and
R. N. Grimes, J. Am. Chem. Soc., 1992, 114, 8733; (d ) G. Consiglio,
F. Morandini, G. F. Ciani and A. Sironi, Organometallics, 1986,
5, 1976.
See http://www.rsc.org/suppdata/dt/b2/b210492j/ for crystal-
lographic data in CIF or other electronic format.
10 (a) B. E. R. Schilling, R. Hoffmann and D. L. Lichtenberger, J. Am.
Chem. Soc., 1979, 101, 585; (b) N. M. Kostic and R. F. Fenske,
Organometallics, 1982, 1, 974; (c) N. M. Kostic and R. F. Fenske,
J. Am. Chem. Soc., 1982, 104, 3879; (d ) P. Hoffmann, in Transition
Metal Carbene Complexes, Verlag Chemie, Weinheim, Germany,
1983, p. 113.
Acknowledgements
We are grateful to the donors of the Petroleum Research Fund,
administered by the American Chemical Society, for financial
support.
11 See discussion and references cited in ref. 7.
12 H. D. Hansen and J. H. Nelson, Inorg. Chim. Acta, 2002, in press.
13 P. McArdle and A. R. Manning, J. Chem. Soc. A, 1970, 2128.
14 O. A. Gansow, A. R. Burke and W. D. Vernon, J. Am. Chem. Soc.,
1976, 98, 5817.
15 T. E. Bitterwolf, J. C. Linehan and J. E. Shade, Organometallics,
2001, 20, 775.
16 M = Fe: O. S. Mills, Acta Crystallogr., 1958, 11, 620; M = Ru:
O. S. Mills and J. P. Nice, J. Organomet. Chem., 1967, 9, 339.
17 M. S. Loonat, L. Carlton, J. C. A. Boeyens and N. J. Coville,
J. Chem. Soc., Dalton Trans., 1989, 2407.
18 L. P. Barthel-Rosa, V. J. Catalano, K. Maitra and J. H. Nelson,
Organometallics, 1996, 15, 3924.
19 K. Y. Ghebreyessus and J. H. Nelson, Organometallics, 2000, 19,
3387.
20 M. A. Bennett and A. K. Smith, J. Chem. Soc., Dalton Trans., 1974,
233.
21 K. Stott, J. Stonehouse, J. Keeler, T.-L. Hwang and A. Shaka, J. Am.
Chem. Soc., 1995, 117, 4199.
22 R. R. Gagné, C. A. Koval and G. C. Lisensky, Inorg. Chem., 1980,
19, 2854.
References
1 H.-L. Ji, J. H. Nelson, A. De Cian, J. Fischer, L. Solujic and
E. B. Milosavljevic, Organometallics, 1992, 11, 401.
2 L. P. Barthel-Rosa, K. Maitra, J. Fischer and J. H. Nelson,
Organometallics, 1997, 16, 1714.
3 (a) J. C. Jeffrey and T. B. Rauchfuss, Inorg. Chem., 1979, 18, 2658; (b)
M. Martin, O. Gevert and H. Werner, J. Chem. Soc., Dalton Trans.,
1996, 2275 and references therein; (c) H. Werner, A. Stark,
M. Schulz and J. Wolf, Organometallics, 1992, 11, 1126; (d ) M. A.
Esteruelas, A. M. Lopez, L. A. Oro, A. Perez, M. Schulz and
H. Werner, Organometallics, 1993, 12, 1823; (e) M. R. Mason and
J. G. Verkade, Organometallics, 1992, 11, 1514; ( f ) C. A. Sassano
and C. A. Mirkin, J. Am. Chem. Soc., 1995, 117, 11379; (g)
E. Lindner, M. Haustein, R. Fawzi, M. Steimann and P. Wegner,
Organometallics, 1994, 13, 5021; (h) T. Braun, P. Steinert and
H. Werner, J. Organomet. Chem., 1995, 488, 169; (i) G. W. Parshall
and S. D. Ittel, Homogeneous Catalysis: The Applications and
Chemistry of Catalysis by Soluble Transition Metal Complexes, 2nd
edn., Wiley Interscience, New York, 1992, pp. 70–72; (j) W. Keim,
Angew. Chem., Int. Ed. Engl., 1990, 29, 235; (k) J. Andrieu,
P. Braunstein, F. Naud, R. D. Adams and R. Layland, Bull. Soc.
Chem. Fr., 1996, 133, 669; (l ) P. Braunstein and F. Naud, Angew.
Chem., Int. Ed., 2001, 40, 680.
23 B. M. Trost and C. M. Older, Organometallics, 2002, 21, 2544.
24 See J. H. Nelson, Concepts Magn. Reson., 2002, 14, 19 for an
explanation of the 13C lineshapes.
25 International Tables for X-Ray Crystallography, D. Reidel, Boston,
MA, 1992, vol. C..
D a l t o n T r a n s . , 2 0 0 3 , 4 4 9 – 4 5 7
457