Phosphaallyl complexes of Ru(II) derived from dicyclohexylvinylphosphine (DCVP)

Article abstract of DOI:10.1039/b413446j

The complexes [(η⁵-RC₅H₄)Ru(CH ₃CN)₃]PF₆ (R = H, CH₃) react with DCVP (DCVP = Cy₂PCH=CH₂) at room temperature to produce the phosphaallyl complexes [(η⁵-C₅H ₅)Ru(η¹-DCVP)(η³-DCVP)]PF₆ (1) and [(η⁵-MeC₅H₄) Ru(η ¹-DCVP)(η³-DCVP)]PF₆ (2). Both compounds react with a variety of two-electron donor ligands displacing the coordinated vinyl moiety. In contrast, we failed to prepare the phosphaallyl complexes [(η⁵-C₅Me₅)Ru(η¹-DCVP) (η³-DCVP)]PF₆, [(η⁵-MeC ₅H₄)Ru(CO)(η³-DCVP)]PF₆ and [(η⁵-C₅Me₅)Ru(CO)(η ³-DPVP)]PF₆ (DPVP = Ph₂PCH= CH₂). The compounds [(η⁵-MeC₅H₄)Ru(CO)(CH ₃CN)(DPVP)]PF₆, and [(η⁵-C ₅Me₅)Ru(CO)(CH₃CN)(DPVP)]PF₆ (12) react with DMPP (3,4-dimethyl-1-phenylphosphole) to undergo [4 + 2] Diels-Alder cycloaddition reactions at elevated temperature. Attempts at ruthenium catalyzed hydration of phenylacetylene produced neither acetophenone nor phenylacetaldehyde but rather dimers and trimers of phenylacetylene. The structures of the complexes described herein have been deduced from elemental analyses, infrared spectroscopy, ¹H, ¹³C{¹H}, ³¹P{¹H} NMR spectroscopy and in several cases by X-ray crystallography.

Full text of DOI:10.1039/b413446j

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F U L L P A P E R
Phosphaallyl complexes of Ru(II) derived from
dicyclohexylvinylphosphine (DCVP)
Dorota Duraczyn´ska and John H. Nelson*
Department of Chemistry/216, University of Nevada-Reno, Reno, Nevada, 89557-0020, USA
Received 31st August 2004, Accepted 29th October 2004
First published as an Advance Article on the web 24th November 2004
5
=
The complexes [(g -RC5H4)Ru(CH3CN)3]PF6 (R = H, CH3) react with DCVP (DCVP = Cy2PCH CH2) at room
5
1
3
5
temperature to produce the phosphaallyl complexes [(g -C5H5)Ru(g -DCVP)(g -DCVP)]PF6 (1) and [(g -MeC5H4)
Ru(g -DCVP)(g -DCVP)]PF6 (2). Both compounds react with a variety of two-electron donor ligands displacing the
coordinated vinyl moiety. In contrast, we failed to prepare the phosphaallyl complexes [(g -C5Me5)Ru(g -DCVP)
1
3
5
1
3
5
3
5
3
=
(g -DCVP)]PF6, [(g -MeC5H4)Ru(CO)(g -DCVP)]PF6 and [(g -C5Me5)Ru(CO)(g -DPVP)]PF6 (DPVP = Ph2PCH
5
5
CH2).The compounds [(g -MeC5H4)Ru(CO)(CH3CN)(DPVP)]PF6 and [(g -C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6
(12) react with DMPP (3,4-dimethyl-1-phenylphosphole) to undergo [4 + 2] Diels–Alder cycloaddition reactions at
elevated temperature. Attempts at ruthenium catalyzed hydration of phenylacetylene produced neither acetophenone
nor phenylacetaldehyde but rather dimers and trimers of phenylacetylene. The structures of the complexes described
1
1
herein have been deduced from elemental analyses, infrared spectroscopy, 1H, 13C{ H}, 31P{ H} NMR spectroscopy
and in several cases by X-ray crystallography.
Introduction
Hemilabile ligands contain at least two different types of chemi-
cal functionalities bound to metal centers.1 One of these
functionalities is substitutionally labile and “opens” during
reactions, and the other group remains firmly bound to the
metal. The presence of such ligands may enhance selectivity,
influence reactivity, stabilize reactive intermediates and promote
transformations that would not otherwise occur.1,2 Complexes
of hemilabile ligands are of current interest because of their
potential applications in molecular activation, homogeneous
catalysis, functional materials, and small molecular sensing. We
Scheme 2 New phosphaallyl complexes containing DCVP.
5
5
5
have previously reported the synthesis and characterization of
the only examples of ruthenium(II) complexes having diphenyl-
vinylphosphine (DPVP) bound to the metal as a neutral,
plexes [(g -MeC5H4)Ru(CO)(CH3CN)(DPVP)]PF6 and [(g -
C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6 (12) react with DMPP
(3,4-dimethyl-1-phenylphosphole) to undergo [4 + 2] Diels–
Alder cycloadditions. Five new ruthenium compounds were
tested as catalysts for the hydration of phenylacetylene but
neither ketone nor aldehyde was obtained.
5
four-electron hemilabile phosphaallyl ligand; [(g -C5H5)Ru-
1
3
5
1
3
(g -DPVP)(g -DPVP)]PF6 (A),3 [(g -C5Me5)Ru(g -DPVP)(g -
DPVP)]PF6 (B)4 and [(g -MeC5H4)Ru(g -DPVP)-(g -DPVP)]-
PF6 (C)5 (Scheme 1). We were interested in discerning whether
similar phosphaallyl complexes with other olefinic phosphines
such as dicyclohexylvinylphosphine (DCVP) could be prepared
and if so in ascertaining their comparative stabilities. Accord-
5
1
3
Results and discussion
Synthesis and characterization of phosphaallyl complexes
5
5
1
3
5
ingly, we prepared DCVP analogs of A and C namely; [(g -
C5H5)Ru(g -DCVP)(g -DCVP)]PF6 (1) and [(g -MeC5H4)-
[(g -C5H5)Ru(g -DCVP)(g -DCVP)]PF6 (1) and [(g -MeC5H4)-
1
3
5
1
3
Ru(g -DCVP)(g -DCVP)]PF6 (2) were prepared similarly to
their DPVP analogs. The preparation of both A and C en-
1
3
Ru(g -DCVP)(g -DCVP)]PF6 (2) (Scheme 2), and probed their
hemilabile character. As expected, the metal-bound vinyl group
may be displaced by a variety of two-electron donor ligands such
as CO, PhNC, HC≡CPh and HC≡CSiMe3. Attempted prepa-
ration of a DCVP analog of B failed. Instead, the unexpected
product 9 [(C6H11)2P(l-CH2CH2)2P(C6H11)2]PF6 was isolated
and fully characterized. We failed also in attempts to prepare
5
tailed removing coordinated CH3CN from their precursors [(g -
RC5H4)Ru(CH3CN)3]PF6 (R = H, CH3) by thermolysis under
vacuum for several days at elevated temperature.3,5 On the
other hand, the syntheses of 1 and 2 did not require this step.
Both phosphaallyl compounds were formed easily by simple
5
addition of DCVP to [(g -RC5H4)Ru(CH3CN)3]PF6 (R = H,
5
3
the carbonyl phosphaallyl complexes [(g -MeC5H4)Ru(CO)(g -
CH3), as shown in Scheme 3, and by stirring overnight at room
temperature. This relative ease of formation may be attributed, in
part, to the higher electron-donating ability of the bulky DCVP
as compared to DPVP. Compounds 1 and 2 were characterized
5
3
DCVP)]PF6 and [(g -C5Me5)Ru(CO)(g -DPVP)]PF6. The com-
1
1
by elemental analyses, cyclic voltammetry, 1H, 13C{ H}, 31P{ H}
NMR spectroscopy, IR spectroscopy and X-ray crystallography.
1
The 31P{ H} NMR spectra of 1 and 2 show two doublets
corresponding to the two inequivalent phosphine groups at
1
3
41.80 ppm (g -DCVP) and 26.10 ppm (g -DCVP) with 2J(PP) =
1
3
37.3 Hz for 1, and 38.49 ppm (g -DCVP) and 23.86 ppm (g -
DCVP) with 2J(PP) = 37.5 Hz for 2. The 31P{ H} spectrum of
1
2 also shows two additional doublet resonances at 38.56 and
23.28 ppm with 2J(PP) = 37.6 Hz. Those signals are attributed
Scheme 1 Phosphaallyl complexes containing DPVP.
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3 T h i s j o u r n a l i s
9 2
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 5
©

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3
1
Table 1 Selected 1H NMR data of 1 and 2 for the g - and the g -DCVP ligands
3
1
g -DCVP
g -DCVP
ꢀ
ꢀ
ꢀ
Ha
Hb
Hc
Ha
Hb
Hc
1a
d
3.91
apptdd
10.8c
1.5d
8.8
10.8
3.30
ddd
33.5
1.57
dddd
13.5
8.5e
5.81
ddd
5.64
dd
13.5
5.97
dd
30.0
Multiplicity
3J(PH)
3J(PH)
3J(aꢀbꢀ)f
3J(aꢀcꢀ)
2J(bꢀcꢀ)
d
Multiplicity
3J(PH)
3J(PH)
3J(aꢀbꢀ)
3J(aꢀcꢀ)
2J(bꢀcꢀ)
3J(PH)
20.5c
8.8
3J(ab)
3J(ac)
2J(bc)
18.5
13.0
18.5
10.8
1.5
2.2–1.0
m
13.0
1.5
2b
3.20
appdtd
9.0c
2.84
ddd
33.0
5.81
ddd
5.98
dd
30.0
5.67
dd
13.5
3J(PH)
21.0c
2.0d
9.0
10.5
9.0
2.0
3J(ab)
3J(ac)
2J(bc)
13.0
18.8
13.0
18.8
a NMR spectra measured in CDCl3, chemical shifts in ppm downfield from Me4Si, coupling constants in Hz. b NMR spectra measured in CD2Cl2.
c
5
f
ꢀ
ꢀ
ꢀ
2J(PH). d 4J(PH). e J(PH). J(HH) coupling where the symbols a , b , c and a, b, c represent Ha , Hb , Hc , Ha, Hb, Hc, respectively.
ꢀ
ꢀ
ꢀ
to the presence of the endo isomer of 2. The relative ratio of
the exo and endo isomers was estimated as 7 : 1. The 1H NMR
1
spectrum of 1 shows three multiplets corresponding to the g -
DCVP hydrogens at 5.97, 5.81 and 5.64 ppm for Hc, Ha and
3
Hb protons, respectively. The g -DCVP phosphallyl hydrogens
ꢀ
ꢀ
ꢀ
resonate at 3.91, 3.30 and 1.57 ppm for Ha , Hb , and Hc , and
appear as complex muliplets. Similarly, the 1H NMR spectrum
of 2 shows three multiplets at 5.98, 5.81 and 5.67 ppm for Hb,
Ha, and Hc, respectively. The phosphaallyl hydrogens resonate at
ꢀ
ꢀ
ꢀ
3.20, 2.84 and 2.2–1.0 for Ha , Hb and Hc . Table 1 summarizes
Scheme 3
1
selected H NMR data for 1 and 2 (major isomer). For 1 and
the major isomer of 2 the g -DCVP ligand is bound in the exo
3
orientation both in solution and in the solid state, as confirmed
by 1D-NOE spectroscopy and X-ray crystallography. Views of
the geometries of the cations of 1 and 2 are shown in Figs. 1 and
2, respectively. The analyses reveal that both compounds have a
5
distorted octahedral geometry about ruthenium, the g -RC5H4
(R = H, CH3) moiety occupies three coordination sites, with
1
3
one g -DCVP and one g -DCVP completing the coordination
sphere. The greater steric bulk of DCVP as compared to DPVP
influences the bond distances and the bond angles. The C(14)–
P(1)–P(8) angle (see Fig. 1) should be larger for 1 than for A, and
the P(1)–C(6)–C(7) angle smaller for 1. This trend is observed,
the C(14)–P(1)–C(8) angle for 1 has a value of 113.23(22)◦
compared to◦107.5(2)◦ for A.3 The P(1)–C(6)–C(7) angle for
1 (117.33(17) ) is smaller than that for A (119.1(3)◦).3 Changes
in bond distances should also be observed. The Ru(1)–P(1),
Ru(1)–C(6) and Ru(1)–C(7) bond distances for 1 are expected
to be shorter than those for A. But this trend is not observed
here. The Ru(1)–P(1) and Ru(1)–C(7) bond distances for 1 are
Fig. 1 Structural drawing of the cation of 1 showing the atom
numbering scheme (40% probability ellipsoids). Hydrogen atoms have
˚
been omitted for clarity. Selected bond lengths (A) and angles
(◦): Ru(1)–P(1), 2.2977(7); Ru(1)–P(2), 2.3450(6); P(1)–C(6), 1.772(3);
P(2)–C(20), 1.829(2); Ru(1)–C(average), 2.228(3); P(1)–Ru(1)–P(2),
99.58(2); P(1)–Ru(1)–C(6), 46.61(7); P(2)–C(20)–C(21), 128.5(2).
˚
˚
longer than analogous bonds for A, 2.2977(7) A and 2.253(2) A
˚
˚
for 1 vs. 2.276(1) A and 2.244(4) A for A. The Ru(1)–C(6) bond
˚
distance is almost identical for both compounds, 2.171(2) A for
1 and 2.176(3) A for A. Unfortunately, we cannot compare these
˚
The addition of CD3CN to compound 1 produces an equi-
5
values for compounds 2 and C because the X-ray structure of C
librium mixture of 1 and [(g -C5H5)Ru(DCVP)2(CD3CN)]PF6
has not been reported.5
(Scheme 4). This equilibrium is evidenced by the two doublet
1
Compound 1 undergoes quasireversible one-electron oxida-
tion with an E1/2 value of 0.395 V.
31P{ H} resonances for 1 diminishing in intensity as a singlet res-
5
onance for [(g -C5H5)Ru (DCVP)2(CD3CN)]PF6 slowly appears.
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3
9 3

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5
= = =
[(g -C5Me5)(DPVP)2Ru C C CPh2]PF6 via spontaneous de-
hydration of an intermediate vinylidene6 complex with no
competing reaction of DPVP with the allenylidene ligand.8
The formation of this compound was confirmed by NMR
spectroscopy of the product mixture (near complete conversion
was achieved). But when we reacted compounds 1 and 2 with
1,1-diphenylpropargyl alcohol neither an allenylidene nor a
vinylidene complex was obtained. The resulting purple reaction
mixture was recrystallized from CH2Cl2/hexane and colorless
crystals of phosphonium salt 3 were isolated (Scheme 5).
Compound 3 was fully characterized by elemental analysis,
1H, 13C{ H}, and 31P{ H} NMR spectroscopy, and X-ray
1
1
crystallography. The 31P{ H} NMR spectrum shows a singlet
1
resonance at 64.1 ppm for the cationic phosphorus and a septet
−
resonance at −145.00 ppm for the PF6 group. Fig. 3 shows the
geometry of cation 3. Compound 3 was most likely formed by
nucleophilic attack of DCVP on Ca of a vinylidene intermediate.
1
31P{ H} NMR spectroscopy of the crude reaction mixtures
1
showed that the major phosphorus containing species is 3. H
NMR spectroscpopy of the crude reaction mixtures showed that
essentially all of the compounds 1 and 2 disappeared. Following
separation of 3, a brown gummy residue that defied purification
and identification remained. The identity of the final ruthenium
product/s of these reactions is unknown.
Fig. 2 Structural drawing of the cation of 2 showing the atom
numbering scheme (40% probability ellipsoids). Hydrogen atoms have
˚
been omitted for clarity. Selected bond lengths (A) and angles
(◦): Ru(1)–P(1), 2.316(2); Ru(1)–P(2), 2.359(2); P(1)–C(8), 1.785(8);
P(2)–C(21), 1.825(7); Ru(1)–C(average), 2.220(8); P(1)–Ru(1)–P(2),
99.41(7); P(1)–Ru(1)–C(8), 46.8(2); P(2)–C(21)–C(22), 128.4(7).
Scheme 4
The equilibrium constants in CD3CN were evaluated as a
1
Scheme 5
function of temperature by 1H and 31P{ H} NMR spectroscopy
and were determined to be 4.3 × 10−2 and 2.9 × 10−2 at 273 K
and 303 K, respectively. Similarly the equilibrium constant for
the addition of CH3CN to A in CDCl3 was found to be 4.8 × 102
at 303 K.3 Thus, even in CD3CN solution this equilibrium for 1
lies mostly on the left side. On the other hand, the equilibrium
constant for the addition of CD3CN to complex 2 was too
small to measure by NMR spectroscopy. Thus, acetronitrile
dissociates from 1 and 2 much more readily than from A.
Reactions of phosphaallyl complexes
One of the reasons for preparing compounds 1 and 2 was
to use them as precursors to vinylidene6 and allenylidene6
complexes that might be catalysts for the addition of nu-
cleophiles to terminal alkynes.7 The reactions of propargyl
alcohols HC≡CC(OH)R2 with ruthenium complexes represent
simple and convenient routes for the preparation of vinylidene
and allenylidene complexes.6 For example, treatment of com-
plex B with propargyl alcohol (HC≡CCH2(OH)) in chloro-
5
Fig. 3 Structural drawing of the cation of 3 showing the atom
form resulted in the formation of the vinylidene species [(g -
4
numbering scheme (50% probability ellipsoids). Included hydrogen
=
C5Me5)Ru(DPVP)2{C C(H)(CH2OH)}]PF6. Refluxing a so-
˚
˚
atoms have an arbitrary radius of 0.1 A. Selected bond lengths (A)
and angles (◦): P(1)–C(1), 1.807(3); P(1)–C(7), 1.811(3); C(17)–O(1),
1.442(4); C(1)–P(1)–C(7), 110.26(14); C(24)–C(17)–O(1), 110.6(2).
lution of this vinylidene compound in methanol over a period of
several days resulted in the unexpected precipitation of the rose-
5
=
colored solid [(g -C5Me5)Ru(DPVP)2{C C(CH2)2PPh2C H2}]-
[PF6]2.
Compound 2 reacts with PhC≡CH, HC≡CSiMe3, CO and
PhNC (Scheme 6) at the metal center displacing the coordinated
vinyl moiety. This is evidenced by the disappearance of the two
doublet resonances and appearance of a singlet resonance in
This compound containes a heterocyclic, disubstituted vinyli-
ꢀ
ꢀ
=
dene (C CR∼R ), where R∼R is a P,P-diphenyltrihydrophos-
pholonium ring. Formation of this unexpected product most
probably resulted from the nucleophilic attack of DPVP on
the Cc carbon of an allenylidene intermediate. On the other
hand, the reaction of B with 1,1-diphenylpropargyl alco-
hol (HC≡CC(OH)Ph2) gave the diphenylallenylidene complex
1
the 31P{ H} spectra of the reaction mixtures. Compounds 4
1
1
were characterized by elemental analyses, 1H, 13C{ H}, 31P{ H}
NMR spectroscopy and IR spectroscopy. The product of the
reaction of 2 with PhC≡CH and adventitious water, the carbonyl
9 4
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3

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and IR spectroscopy. Their structures were deduced from NMR
1
and IR spectroscopies. For 7 the 13C{ H} NMR spectrum shows
a triplet resonance for the N≡C group at 164.41 ppm with
1
2J(PC) = 20.2 Hz while the 31P{ H} NMR spectrum shows
a singlet resonance at 39.70 ppm indicative of two equivalent
DCVP groups. The absence of the CH3 group on the C5H5 ring
in this compound allows free rotation about the Ru–C bond.
In the IR spectrum a strong band at 2096 cm−1 appears for
1
the N≡C group. The 13C{ H} NMR spectrum of the DPVP
analog of 7 also shows a triplet resonance for the N≡C group at
1
161.17 ppm with 2J(PC) = 21.01 Hz while the 31P{ H} spectrum
shows a singlet resonance at 40.55 ppm.3 For the DPVP analog
of 7 a strong N≡C band was reported at 2130 cm−1.3 Complex
8 exhibits a strong carbonyl band, mCO, at 1962 cm−1 while for
its DPVP analog this band occurs at 1982 cm−1.3 The carbonyl
1
carbon resonances for 8 and its DPVP analog in their 13C{ H}
2
spectra are triplets at 203.67 ppm with J(PC) = 17.6 Hz, and
2
1
202.683 Hz with J(PC) = 17.33 Hz, respectively. The 31P{ H}
spectra of 8 and its DPVP analog show singlet resonances at
37.94 and 36.223 ppm, respectively, corresponding to equivalent
phosphine groups. In general, the substitution reactions of 1 and
2 required higher temperatures and longer reaction times than
for their DPVP analogs.
5
1
3
The [(g -C5Me5)Ru(g -DPVP)(g -DPVP)]PF6 complex (B)
was prepared by treating an acetonitrile solution of [(g -
5
C5Me5)RuCl2]2 with excess Zn. After 2 hours of stirring at
room temperature, the excess Zn was removed and DPVP was
added. The stirring was continued for another 8 hours, and
then the resulting solution was treated with NaPF6 to produce
the desired product in 72% yield.4 We used the same procedure
in an attempt to prepare the DCVP analog of B but instead of
5
1
3
[(g -C5Me5)Ru(g -DCVP)(g -DCVP)]PF6, the unexpected prod-
Scheme 6
uct, 9 was isolated (Scheme 7). 31P{ H} NMR spectroscopy
1
showed two major resonances at 33.9 ppm, which we ten-
5
1
complex 4, most probably resulted from nucleophilic attack of
H2O on a vinylidene intermediate according to a previously
described mechanism.9 In this reaction PhC≡CH dimers were
also isolated and identified by GC/MS. Compound 4 was also
obtained when a 1,2-dichloroethane solution of 2 was bubbled
with CO for 5 days. Complex 4 exhibits mCO at 1966 cm−1
compared to mCO for its DPVP analog at 1983 cm−1.5 The
low magnitude of mCO for 4 is a manifestation of the greater
tatively attributed to [(g -C5Me5)Ru(g -DCVP)2(CH3CN)]PF6,
and 24.8 ppm attributed to 9. Over time the former resonance
disappeared as the latter augmented in intensity. Through
repeated attempts at fractional crystallization and column chro-
matography on silica gel we were not able to isolate and identify
the ruthenium containing material/s. Compound 9 was fully
characterized by elemental analysis, H, 13C{ H}, and 31P{ H}
NMR spectroscopy, IR spectroscopy and X-ray crystallography.
Fig. 4 shows the geometry of cation 9. The central ring, which
sits on a crystallographic center of symmentry, is in the chair
conformation. Each phosphorus ion has two cyclohexyl groups
attached, one of which is equatorial and the other axial. As
expected the C(1)–P(1)–C(7) angle is◦bigger for 9 than for its
phenyl analog, 117.11(14)◦ and 111(1) , respectively.10 The value
1
1
1
1
donor ability of DCVP compared to DPVP. The 31P{ H} NMR
resonances for 4 and its DPVP analog occur at 37.75 and
36.605 ppm, respectively. The carbonyl carbon resonance in
1
the 13C{ H} NMR spectra of both compounds is a triplet at
205.15 and 201.605 ppm with 2J(PC) = 17.1 Hz, and 17.35 Hz,
respectively.
Reaction of 2 with HC≡CSiMe3 in ClCH2CH2Cl–CH3OH
solution gave the reddish-brown vinylidene complex 5. The
formation of 5 was deduced from NMR and IR spectroscopy.
13
1
=
The C{ H} NMR spectrum shows the characteristic Ru Ca
carbon resonance at 321.59 ppm, while the 31P{ H} NMR
1
spectrum shows a singlet resonance at 40.68 ppm corresponding
to two equivalent DCVP groups. The 1H NMR spectrum shows
the vinylidene hydrogens resonance as a singlet at 3.84 ppm. In
the IR spectrum a strong band at 1621 cm−1 appears, a region
typical for carbon–carbon double bonds.
Complex 2 reacts with PhNC in ClCH2CH2Cl solution to
afford compound 6. The structure of 6 was deduced from
1
NMR and IR data. The 13C{ H} NMR spectrum shows a
triplet resonance at 164.37 ppm for the N≡C group with
1
2J(PC) = 20.6 Hz. The 31P{ H} NMR spectrum shows two
singlet resonances at 39.56 and 39.27 ppm which indicates a
lack of symmetry in the molecule caused by hindered rotation
about the Ru–C bond. In the IR spectrum a strong band at
2091 cm−1 appears for the N≡C group.
Compound 1 reacts with PhNC and CO to afford 7 and 8,
respectively (Scheme 6). Both complexes were fully characterized
1
1
by elemental analyses, 1H, 13C{ H}, 31P{ H} NMR spectroscopy
Scheme 7
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3
9 5

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5
solution of [(g -C5Me5)Ru(CO)(Br)DPVP)] was treated with
AgOTf (AgOTf = silver trifuoromethanesulfonate) a mixture
5
3
of starting material and [(g -C5Me5)Ru(CO)(g -DPVP)]OTf
was formed.8 But these complexes have so far been in-
separable and the g -phosphaallyl compound has not been
3
characterized. We tried several different approaches in or-
der to obtain a pure compound. First, we treated an ace-
5
tonitrile solution of [(g -C5Me5)Ru(CO)(Br)(DPVP)]8 with
5
AgPF6 to substitute bromide with CH3CN. The isolated [(g -
C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6 (12) was then heated in a
◦
vacuum oven at 120 C for several days. But this reaction also
failed to produce the desired compound (Scheme 9). Complex 12
1
1
1
was characterized by elemental analysis, H, 13C{ H}, 31P{ H}
NMR spectroscopy, IR spectroscopy and X-ray crystallography.
A view of the geometry of the cation of 12 is shown in Fig. 5. It is
a three-legged piano stool with a distorted octahedral structure.
Because CH3CN could not be displaced by the vinyl group of
DCVP in 11 or its DPVP analogue we wondered if other ligands
would displace the CH3CN from these complexes.
Fig. 4 Structural drawing of 9 showing the atom numbering scheme
(40% probability ellipsoids). Hydrogen atoms have been omitted for
◦
˚
clarity. Selected bond lengths (A) and angles ( ): P(1)–C(13), 1.813(4);
P(1)–C(1), 1.810(4); C(13)–P(1)–C(7), 106.51(18); C(14)–C(13)–P(1),
115.1(2).
˚
of the P(1)–C(13) bond distance (1.813(4) A) is similar to the
10
˚
average P–C distance, 1.78(3) A for the phenyl analog.
5
3
We have previously shown3 that [(g -C5H5)Ru(CO)(g -
DPVP)]PF6 has the endo geometry in contrast to A, B, C
and 1 all of which have the exo geometry. As we mentioned
before the phosphaallyl complex 2 was obtained as a 7 : 1
mixture of exo and endo isomers. Since this suggested that
3
the ancillary ligands could control the geometry of the g -
phosphaallyl ligand we tried to prepare other examples of
such complexes. As we showed before attempts to prepare
5
3
[(g -MeC5H4)Ru(CO)(g -DPVP)]PF6 failed.5 We set out to
5
3
prepare [(g -MeC5H4)Ru(CO)(g -DCVP)]PF6 by removal of
bromide from 10 or CH3CN from 11 (Scheme 8). Neither of
these reactions were successful. Complexes 10 and 11 were
characterized by elemental analyses, cyclic voltammetry, 1H,
13C{ H}, and 31P{ H} NMR spectroscopy, IR spectroscopy
and X-ray crystallography. The crystals of 10 and 11 are
of poor quality but confirmed the structures. Compound 10
undergoes a quasireversible one-electron oxidation with an E1/2
value of 0.46 V compared with its DPVP analog for which
E1/2 = 0.53 V.5 Compound 10 is slightly easier to oxidize as it
possesses the better electron donor ligand DCVP as compared
to DPVP. It was also shown that when a dichloroetahane
1
1
Scheme 9
Fig. 5 Structural drawing of the cation of 12 showing the atom
numbering scheme (20% probability ellipsoids). Hydrogen atoms have
◦
˚
been omitted for clarity. Selected bond lengths (A) and angles ( ):
Ru(1)–P(1), 2.346(3); Ru(1)–N(1), 2.074(8); Ru(1)–C(25), 1.855(12);
Ru(1)–C(average), 2.236(11); C(25)–O(1), 1.156(12); N(1)–C(26),
1.133(11), N(1)–Ru(1)–P(1), 88.1(2); C(25)–Ru(1)–P(1), 88.3(3);
Ru(1)–P(1)–C(11), 112.5(4).
Scheme 8
9 6
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3

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In their studies on the coordination modes of phospho-
les, Nelson and co-workers showed that coordinated 3,4-
dimethyl-1-phenylphosphole (DMPP) is capable of undergoing
[4 + 2] Diels–Alder reactions with a variety of dienophiles.11
The coordination of the phosphole to a transition metal
activates the cyclic diene towards [4 + 2] cycloaddition.
Also, coordination of a dienophile, such as DPVP, activates
the dienophile towards [4 + 2] cycloaddition.11 Accordingly,
5
5
we reacted [(g -MeC5H4)Ru(CO)(CH3CN)(DPVP)]PF6 and
5
[(g -C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6 (12) with DMPP, as
shown in Scheme 10, and obtained [4 + 2] Diels–Alder adducts.
1
The 31P{ H} NMR spectra of the reaction mixtures show four
doublet resonances corresponding to two diastereomers in the
ratios: 13A : 13B, 1.2 : 1 and 14A : 14B, 2 : 1. Recrystallization
from nitromethane/diethyl ether allowed separation of these
isomers. Isomers 13A and 14A were characterized by elemental
1
1
analyses, 1H, 13C{ H}, and 31P{ H} NMR spectroscopy, IR
spectroscopy and X-ray crystallography. The 31P{ H} NMR
1
Fig. 6 Structural drawing of the cation of 13A showing the atom
spectra show two doublet resonances at 141.06 and 69.81 ppm
for 13A and 142.88 and 72.67 for 14A. IR spectra of those
isomers show strong carbonyl bands mCO at 1982 cm−1 (13A)
and 1969 cm−1 (14A). Views of the geometries of the cations of
13A and 14A are shown in Figs. 6 and 7, respectively. In the
two structures, the geometry around the ruthenium center is
numbering scheme (20% probability ellipsoids). Hydrogen atoms have
◦
˚
been omitted for clarity. Selected bond lengths (A) and angles ( ):
Ru(1)–P(1), 2.313(2); Ru(1)–P(2), 2.2752(19); Ru(1)–C(33), 1.867(9);
Ru(1)–C(average), 2.243(9); P(2)–C(10), 1.854(7); C(33)–O(1), 1.127(9);
P(1)–Ru(1)–P(2), 80.80(7); P(1)–Ru(1)–C(33), 92.4(3); C(7)–P(2)–C(10),
81.1(3); Ru(1)–C(33)–O(1), 177.6(8).
5
5
pseudo-octahedral with the g -C5Me5 and g -MeC5H4 rings, the
asymmetric bidenate phosphine and the CO group completing
the coordination sphere.
Fig. 7 Structural drawing of the cation of 14A showing the atom
numbering scheme (30% probability ellipsoids). Hydrogen atoms
˚
have been omitted for clarity. Selected bond lengths (A) and an-
gles (◦): Ru(1)–P(1), 2.302(2); Ru(1)–P(2), 2.322(2); Ru(1)–C(37),
1.865(8); Ru(1)–C(average), 2.254(8); P(1)–C(11), 1.848(7); C(37)–O(1),
1.137(8); P(1)–Ru(1)–P(2), 80.35(7); P(1)–Ru(1)–C(37), 90.1(2);
C(11)–P(1)–C(14), 80.3(3); Ru(1)–C(37)–O(1), 174.2(7).
in the steric effects between two regioisomers the higher the
diastereoselectivity.
Scheme 10
Catalytic studies
Metal catalyzed hydration of alkynes is an important route
to carbonyl compounds that are often precursors in many
useful processes. The addition of water to terminal alkynes
when following Markovnikov’s rules produces ketones; the anti-
Markovnikov addition yields aldehydes.12 We have conducted
In principle, two regioisomeric adducts A and B could be
formed in these reactions with one predominating, but in
some cases only one regioisomeric adduct was formed.11 The
regioselectivity is mainly governed by the steric effects posed in
the transition state between the emerging norbornene ligand
and the CO ligand. Molecular models demonstrate that the
intramolecular steric interactions in the transition states for
the formation of the regioisomers 13A and 14A are smaller
than for the formation of the regioisomers 13B and 14B;
therefore regioisomers 13A and 14A should predominate in
these [4 + 2] cycloaddition reactions. This assumption has been
proved by X-ray crystallography. Because this regioselectivity
is mainly affected by steric effects, the bigger the difference
5
5
5
tests with [(g -MeC5H4)Ru(CO)(CH3CN)(DPVP)]PF6 , [(g -
5
1
C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6 (12), [(g -C5H5)Ru(g -
3
5
1
3
DCVP)(g -DCVP)]PF6 (1), [(g -MeC5H4)Ru(g -DCVP)(g -
5
1
3
DCVP)]PF6 (2) and [(g -MeC5H4)Ru(g -DPVP)(g -DPVP)]
PF65 as catalysts for the hydration of phenylacetylene (eqn. (1)).
(1)
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3
9 7

View Article Online
Table 2 Ruthenium catalyzed hydration of phenylacetylene
Catalyst
Method
% Dimers
% Trimers
Comments
5
[(g -MeC5H4)Ru(CO)(CH3CN)(DPVP)]PF6
A
A
B
B
B
trace
trace
26.4
88.5
60.7
—
—
73.6
11.5
39.3
mostly starting material
mostly starting material
1 dimer 2 trimers
3 dimers 1 trimer
2 dimers 2 trimers
5
[(g -Me5C5)Ru(CO)(CH3CN)(DPVP)]PF6
5
1
3
[(g -C5H5)Ru(g -DCVP)(g -DCVP)]PF6
5
1
3
[(g -MeC5H4)Ru(g -DCVP)(g -DCVP)]PF6
5
1
3
[(g -MeC5H4)Ru(g -DPVP)(g -DPVP)]PF6
5
5
Neither acetophenone nor phenylacetaldehyde was detected.
Instead phenylacetylene dimers and trimers were identified
(Scheme 11) by GC/MS. We were unable to separate and fully
characterize each of these compounds which have been noted
before as products of similar reactions.13 Table 2 shows the results
of the catalytic reactions.
phere. [(g -Me5C5)Ru(CO)(Br)(DPVP)],8 [(g -MeC5H4)Ru-
(CO)2Br],5 [(g -MeC5H4)Ru(CH3CN)3]PF6,5 [(g -C5H5)Ru-
5
5
(CH3CN)3]PF6,14 [(g -C5Me5)RuCl2]2PF6,15 3,4-dimethyl-1-
5
phenylphosphole (DMPP),16 phenylisocyanide PhNC17 and
dicyclohexylvinylphosphine (DCVP)18 were synthesized by the
literature procedure. Acetonitrile was distilled from CaH2 prior
to use. Melting points were obtained using a Mel-Temp melting
1
1
point apparatus and are uncorrected. 1H, 13C{ H} and 31P{ H}
NMR spectra were recorded at 499.8 MHz, 125.7 MHz, and
202.3 MHz on a Varian Unity Plus 500 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.19 IR spectra were recorded on a Perkin-Elmer
Spectrum BX spectrometer. Cyclic voltammograms were
obtained at 25 ◦C 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 electrode was glassy carbon, the auxiliary
electrode was a platinum wire and the reference electrode
was Ag/AgCl (aqueous) separated from the cell by a Luggin
capillary. The Fc/Fc+ couple occurred at 508 mV20 under
the same conditions. GC/MS analyses were performed on a
Hewlet-Packard HP 5890 instrument. A HP-1 (cross linked
methyl siloxane) column was used. Elemental analyses were
performed by Galbraith Laboratories, Knoxville, TN.
B. Syntheses
Scheme 11 Possible PhC≡CH dimers and trimers.
Preparation of [(g5-C5H5)Ru(g1-DCVP)(g3-DCVP)]PF6 (1).
A 250 mL, three-neck round-bottom flask was charged with
2.2 g (5.1 mmol) of [(g -C5H5)Ru(CH3CN)3]PF6 and 120 mL
Concluding remarks
5
of freshly distilled acetonitrile. The whole was stirred under
a nitrogen atmosphere for 30 min. Then 2.4 mL (10.7 mmol)
of DCVP was added and the mixture was stirred at room
temperature overnight. Solvent was removed leaving a brown,
oily residue. This residue was dissolved in CH2Cl2 and passed
through a silica gel column packed with hexane and eluted with
CH2Cl2. Recrystallization from CH2Cl2–MeOH–diethyl ether
gave 2.92 g (76% yield) of yellow crystals.Mp: 95–97 ◦C. Anal.
We have synthesized and characterized twelve new ruthe-
nium complexes including the new phosphaallyl complexes
5
1
3
5
[(g -C5H5)Ru(g -DCVP)(g -DCVP)]PF6 (1) and [(g -MeC5H4)
1
3
Ru(g -DCVP)(g -DCVP)]PF6 (2). We have found that com-
pounds 1 and 2 are much more stable than their DPVP analogs.
The enhanced stability of these phospaallyl complexes is a result
of the better donor ability of DCVP than DPVP and the greater
steric bulk of the cyclohexyl than the phenyl group. Attempted
5
1
3
syntheses of the [(g -C5Me5)Ru(g -DCVP)(g -DCVP)]PF6 and
5
3
the carbonylphosphaallyl complexes [(g -MeC5H4)Ru(CO)(g -
5
3
DCVP)]PF6 and [(g -C5Me5)Ru(CO)(g -DPVP)]PF6 failed. The
5
5
two compounds [(g -MeC5H4)Ru(CO)(CH3CN)(DPVP)]PF6
5
and [(g -C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6 (12) undergo
[4 + 2] Diels–Alder cycloaddition reactions with DMPP with
only modest diastereoselectivity. The catalytic tests for the hy-
dration of phenylacetylene failed to produce aldehyde or ketone
but instead produced dimers and trimers of phenylacetylene with
relatively poor selectivity.
Experimental
calc. for C33H55F6P3Ru: C, 52.12; H, 7.24. Found: C, 51.98;
1
3
H, 7.11%. H NMR (CDCl3): d 5.97 (dd, J(PH) = 30.0 Hz,
A. Reagents and physical measurements
2
3J(HaHc) = 13.0 Hz, 1H, Hc), 5.81 (ddd, J(PH) = 20.5 Hz,
3
All chemicals were reagent grade and were used as received from
commercial sources (Aldrich, Fisher Scientific, Acros Organics,
GFS Chemicals, Strem Chemicals) or synthesized as described
below. All syntheses were conducted under a nitrogen atmos-
3J(HaHb) = 18.5 Hz, J(HaHc) = 13.0 Hz, 1H, Ha), 5.64 (dd,
3J(HaHb) = 18.5 Hz,3J(PH) = 13.5 Hz, 1H, Hb), 5.10 (s, 5H,
2
3
3
ꢀ
ꢀ
ꢀ
ꢀ
Cp), 3.91 (app tdd, J(PH) = J(Ha Hc ) = 10.8 Hz, J(Ha Hb ) =
4
3
ꢀ
8.8 Hz, J(PH) = 1.5 Hz, 1H, Ha ), 3.30 (ddd, J(PH) = 33.5 Hz,
9 8
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3

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3
2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J(Ha Hb ) = 8.8 Hz, J(Hb Hc ) = 1.5 Hz, 1H, Hb ), 2.2–1.0 (m,
3
3
ꢀ
ꢀ
44H, 4 × C6H11), 1.57(dddd, J(PH) = 13.5 Hz, J(Ha Hc ) =
10.8 Hz, J(PH) = 8.5 Hz, J(Hb Hc ) = 1.5 Hz, 1H, Hc ). 31P{ H}
5
2
1
ꢀ
ꢀ
ꢀ
2
1
NMR (CDCl3): d 41.80 (d, J(PP) = 37.3 Hz, 1P, g -DCVP),
26.10 (d, 2J(PP) = 37.3 Hz, 1P, g -DCVP), −145.00 (sept.,
3
1J(PF) = 714 Hz, 1P, PF6−). 13C{ H} NMR (CDCl3): d 130.61
1
1
2
ꢀ
ꢀ
(d, | J(PC) = 31.8 Hz, Ca ), 129.02 (d, J(PC)| = 6.0 Hz, Cb ),
1
81.55 (app t, J(PC)| = 1.1 Hz, Cp), 39.67 (dd, | J(PC) = 26.1 Hz,
3
1
| J(PC) = 2.4 Hz, Ca), 37.06 (d, | J(PC) = 25.4 Hz, Ca), 36.69
2
4
1
ꢀꢀ
(app t, J(PC) = | J(PC) = 3.9 Hz, Cb ), 35.39 (d, J(PC) =
2
26.9 Hz, Ca), 34.32 (d, J(PC) = 9.4 Hz, Cb), 33.20 (s, Cb),
1
1
ꢀꢀ
32.56 (d, J(PC) = 20.7 Hz, Ca ), 32.22 (dd, | J(PC) = 14.6 Hz,
5
1
3
lated in the raction of [(g -C5H5)Ru(g -DCVP)(g -DCVP)]PF6
with HC≡C–C(OH)Ph2. Anal. calc. for C29H36F6OP2: C, 60.42;
3
| J(PC) = 3.0 Hz, Ca), 30.38 (s, Cb), 29.43 (s, Cb), 29.40 (s, Cb),
3
29.20 (s, Cb), 29.04 (s, Cb), 28.98 (s, Cb), 27.56 (d, | J(PC) =
1
H, 6.24. Found: C, 60.22; H, 6.17. H NMR (acetone-d6): d
12.1 Hz, Cc), 27.28 (d, 3J(PC) = 12.1 Hz, Cc), 27.24 (s, Cd), 26.96
(d, 3J(PC) = 8.7 Hz, Cc), 26.75 (d, 3J(PC) = 12.4 Hz, Cc), 26.60
(d, 3J(PC) = 10.2 Hz, Cc), 26.50 (d, 3J(PC) = 14.3 Hz, Cc), 26.38
(d, 3J(PC) = 10.8 Hz, Cc), 26.23 (d, 3J(PC) = 11.2 Hz, Cc), 26.15
(s, Cd), 25.57 (s, Cd), 25.33 (s, Cd). IR (PF6 region, Nujol, cm−1):
2
4
4
7.45 (ddd, J(PH) = 40.5 Hz, J(HaHb) = 8.0 Hz, J(HaHc) =
1.5 Hz, 1H, Ha), 7.40 (m, 10H, Ph), 6.95 (ddd, 2J(PH) = 32.5 Hz,
4J(HaHb) = 8.0 Hz, J(HbHc) = 2.0 Hz, 1H, Hb), 6.62 (ddd,
3
3J(PH) = 32.5 Hz, 3J(HbHc) = 2.0 Hz, 4J(HaHc) = 1.5 Hz, 1H,
Hc), 5.98 (1H, OH), 3.10 (m, 1H, Ha), 2.82 (m, 1H, Ha), 2.10
(m, 2H, Hc), 1.83 (m, 4H, Hc), 1.71 (m, 2H, Hc), 1.45 (m, 8H,
840. E1/2 = 0.395 V vs. Fc/Fc+
.
Hb), 1.28 (m, 4H, Hd). 31P{ H} NMR (acetone-d6): d 64.1 (s,
1
Preparation of [(g5-MeC5H4)Ru(g1-DCVP)(g3-DCVP)]PF6·
1P), −145.00 (sept., 1J(PF) = 708 Hz, 1P, PF6−). 13C{ H} NMR
1
CH2Cl2 (2). A 250 mL, three-neck round-bottom flask was
2
(acetone-d6): d 172.70 (d, | J(PC) = 14.7 Hz, C2), 153.77 (d,
5
charged with 2.6 g (5.8 mmol) of [(g -MeC5H4)Ru(CH3CN)3]PF6
2
| J(PC) = 10.4 Hz, C3), 143.64 (s, Ci), 129.39 (s, Cm), 129.11 (s,
and 120 mL of freshly distilled acetonitrile. The whole was
stirred under a nitrogen atmosphere for 30 min. Then 2.8 mL
(12.5 mmol) of DCVP was added and the mixture was stirred
at room temperature overnight. Solvent was evaporated leaving
a brown, oily residue. This residue was dissolved in CH2Cl2
and passed through a silica gel column packed with hexane
and eluted with CH2Cl2. Recrystallization from CH2Cl2–hexane
gave 2.65 g (53% yield) of yellow crystals. Mp: 228–230 ◦C. Anal.
calc. for C35H59Cl2F6P3Ru: C, 48.91; H, 6.87. Found: C, 48.76;
H, 6.80%. For the exo isomer only: 1H NMR (CD2Cl2): d 5.98
1
Cp), 128.46 (s, Co), 117.97 (d, | J(PC) = 67.6 Hz, C1), 110.29 (d,
1
1
| J(PC) = 71.6 Hz, C4), 31.20 (d, | J(PC) = 43.1 Hz, Ca), 30.33
1
3
(d, | J(PC) = 40.1 Hz, Ca), 27.09 (d, | J(PC) = 3.0 Hz, Cc), 27.02
3
(d, | J(PC) = 3.1 Hz, Cc), 26.75 (s, Cb), 26.64 (s, Cb), 25.88 (s,
Cd), 25.86 (s, Cd).
Preparation of [(g5-MeC5H4)Ru(DCVP)2(CO)]PF6 (4).
Method A. A 100 mL, three-neck round-bottom flask was
5
1
charged with 0.28 g (0.3 mmol) of [(g -MeC5H4)Ru(g -DCVP)-
3
(g -DCVP)]PF6·CH2Cl2 and 50 mL of 1,2-dichloroethane. The
3
3
(dd, J(PH) = 30.0 Hz, J(HaHb) = 13.0 Hz, 1H, Hb), 5.81
(ddd, 2J(PH) = 21.0 Hz, 3J(HaHc) = 18.8 Hz, 3J(HaHb) =
13.0 Hz, 1H, Ha), 5.67 (dd, 3J(HaHc) = 18.8 Hz,3J(PH) =
solution was brought to reflux and bubbled with CO for 5 days.
Solvent was removed in vacuo leaving 0.21 g (81%) of yellow
product.
3
2
ꢀ
ꢀ
13.5 Hz, 1H, Hc), 3.20 (app dtd, J(Ha Hc ) = 10.5 Hz, J(PH) =
Method B. A 100 mL, three-neck round-bottom flask
3
4
ꢀ
ꢀ
ꢀ
J(Ha Hb ) = 9.0 Hz, J(PH) = 2.0 Hz, 1H, Ha ), 2.84 (ddd,
5
1
was charged with 0.43 g (0.5 mmol) of [(g -MeC5H4)Ru(g -
3
3
2
ꢀ
ꢀ
ꢀ
ꢀ
J(PH) = 33.0 Hz, J(Ha Hb ) = 9.0 Hz, J(Hb Hc ) = 2.0 Hz,
3
DCVP)(g -DCVP)]PF6·CH2Cl2 and 40 mL of a 1 : 1 ClCH2CH2-
ꢀ
ꢀ
1H, Hb ), 2.2–1.0 (m, 45H, 4·C6H11, Hc ), 1.61 (s, 3H, CH3Cp).
Cl/MeOH mixture. The whole was stirred under a nitrogen
atmosphere for 30 min. Then 0.2 mL (1.8 mmol) of PhC≡CH
was added and the whole was heated under reflux for 4 days
(change of color was observed: yellow to orange to red). Solvents
were removed leaving a reddish brown, oily residue. This residue
was dissolved in CH2Cl2 and passed through a silica gel column
packed with hexane and eluted with CH2Cl2. The first yellow
fraction contained mostly PhC≡CH dimers, and the second
orange fraction 0.20 g of carbonyl compound (50% yield). Mp:
90–92 ◦C. Anal. calc. for C35H57F6OP3Ru: C, 52.43; H, 7.12.
31P{ H} NMR (CD2Cl2): d 38.49 (d, J(PP) = 37.5 Hz, 1P, g -
1
2
1
2
3
DCVP), 23.86 (d, J(PP) = 37.5 Hz, 1P, g -DCVP), −148.11
(sept., 1J(PF) = 711 Hz, 1P, PF6−). 13C{ H} NMR (CD2Cl2): d
1
1
2
ꢀ
130.95 (d, | J(PC) = 32.1 Hz, Ca ), 129.78 (d, J(PC)| = 6.0 Hz,
ꢀ
Cb ), 99.94 (app t, J(PC)| = 1.8 Hz, Cpq), 84.14 (Cp), 82.31 (d,
J(PC) = 4.8 Hz, Cp), 80.42 (d, J(PC) = 5.3 Hz, Cp), 79.42 (Cp),
1
3
40.13 (dd, | J(PC) = 26.0 Hz, | J(PC) = 2.4 Hz, Ca), 39.74 (app t,
2
4
1
ꢀꢀ
J(PC) = | J(PC) = 4.3 Hz, Cb ), 36.99 (d, J(PC) = 25.0 Hz, Ca),
1
1
ꢀꢀ
36.79 (d, J(PC) = 19.9 Hz, Ca), 36.02 (d, J(PC) = 27.0 Hz, Ca ),
1
34.81 (Cb), 34.74 (Cb), 33.81 (Cb), 33.14 (dd, | J(PC) = 14.6 Hz,
1
Found: C, 52.24; H, 7.01%. H NMR (CDCl3): d 6.01 (m, 4H,
3J(PC) = 3.4 Hz, Ca), 30.87 (Cb), 30.03 (Cb), 30.00 (Cb), 29.90
3
Ha,b), 5.61 (m, 2H, Hc), 5.26 (app t, | J(HH) + 4J(HH)| =
3
(Cb), 29.62 (Cb), 29.60 (Cb), 28.07 (d, J(PC) = 11.9 Hz, Cc),
3
4
3.5 Hz, 2H, Cp), 5.04 (app t, | J(HH) + J(HH)| = 3.0 Hz,
27.91 (d, 3J(PC) = 12.1 Hz, Cc), 27.61 (Cd), 27.47 (d, 3J(PC) =
18.4 Hz, Cc), 27.24 (d, 3J(PC) = 15.6 Hz, Cc), 27.21 (d, 3J(PC) =
14.3 Hz, Cc), 27.10 (d, 3J(PC) = 19.1 Hz, Cc), 27.02 (d, 3J(PC) =
19.9 Hz, Cc), 26.81 (Cd), 26.75 (d, 3J(PC) = 14.8 Hz, Cc), 26.11
2H, Cp), 2.09 (s, 3H, CH3Cp), 1.80 (m, 12H, Cy), 1.25 (m, 10H,
1
Cy). 31P{ H} NMR (CDCl3): d 37.75 (s, 2P, DCVP), −145.00
(sept., J(PF) = 712 Hz, 1P, PF6−). 13C{ H} NMR (CDCl3): d
1
1
205.15 (t, | J(PC) = 17.1 Hz, CO), 130.62 (AXXꢀ, J(PC)| =
2
1
4
(Cd), 25.92 (d, J(PC) = 1.4 Hz, Cd), 11.46 (CH3Cp). IR (PF6
2
3
ꢀ
35.1 Hz, | J(PP) = 25.6 Hz, | J(PC) = 2.3 Hz, Ca ), 129.16 (s,
region, Nujol, cm−1): 839.
ꢀ
Cb ), 106.36 (t, J(PC) = 1.9 Hz, Cpq), 87.11 (Cp), 86.29 (Cp),
2
1
3
40.25 (AXXꢀ, J(PP) = |25.6 Hz, J(PC) = 24.0 Hz, J(PC) =
5.0 Hz, Ca), 38.08 (AXXꢀ, 2J(PP) = |25.6 Hz, 1J(PC) = 24.1 Hz,
3J(PC) = 0.8 Hz, Ca), 29.30 (Cb), 28.88 (Cb), 28.46 (Cb), 28.21
5
= =
Attempted preparation of [(g -MeC5H4)(DCVP)2Ru C
=
C CPh2)]PF6; Formation of (3). A 100 mL, three-neck round-
bottom flask was charged with 0.31 g (0.4 mmol) of [(g -
5
3
5
(Cb), 26.91 (app T, | J(PC) + J(PC)| = 11.8 Hz, Cc), 26.86 (app
1
3
MeC5H4)Ru(g -DCVP)(g -DCVP)]PF6·CH2Cl2 and 50 mL of
1,2-dichloroethane. The whole was stirred under a nitrogen
atmosphere for 30 min. Then 0.19 g (0.9 mmol) of HC≡C–
C(OH)Ph2 was added and the mixture was refluxed for 9 days
(change of color was observed: yellow to orange to red to pur-
ple). Recrystallization from CH2Cl2–hexane gave 0.1 g of color-
less crystals of the phosphonium salt.The same product was iso-
3
5
3
T, | J(PC) + J(PC)| = 12.8 Hz, Cc), 26.77 (app T, | J(PC) +
3
5
5J(PC)| = 10.1 Hz, Cc), 26.30 (app T, | J(PC) + J(PC)| =
10.6 Hz, Cc), 25.81 (Cd), 22.47 (Cd), 13.19 (CH3Cp). IR (CO
region, CH2Cl2, cm−1): 1966, IR (PF6 region, Nujol, cm−1): 831.
5
=
Preparation of [(g -MeC5H4)Ru(DCVP)2(C CH2)]PF6 (5).
A 100 mL, three-neck round-bottom flask was charged
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3
9 9

View Article Online
5
1
3
with 0.32 g (0.4 mmol) of [(g -MeC5H4)Ru(g -DCVP)(g -
DCVP)]PF6·CH2Cl2 and 40 mL of a 1 : 1 ClCH2CH2Cl/MeOH
mixture. The whole was stirred under a nitrogen atmosphere for
30 min. Then 0.2 mL (1.4 mmol) of HC≡CSiMe3 was added
via syringe and the whole was heated under reflux for 5 days.
Solvents were removed leaving a brown-green oily residue.
This residue was dissolved in CH2Cl2 and passed through a
silica gel column packed with hexane and eluted with CH2Cl2.
Recrystallization from acetone–diethyl ether gave 0.25 g of
reddish-brown product in 83% yield. Mp: 70–72 ◦C. Anal. calc.
for C36H59F6P3Ru: C, 54.07; H, 7.38. Found: C, 53.92; H, 7.29%.
1H NMR (CDCl3): d 6.22 (ddd, 2J(PH) = 21.0 Hz, 3J(HaHc) =
was added. The mixture was heated under reflux for 9 days.
Solvent was removed leaving a brown oily residue. This residue
was dissolved in CH2Cl2 and passed through a silica gel column
packed with hexane and eluted with CH2Cl2. Solvent was
evaporated leaving 0.24 g (77% yield) of brown microcrystals.
Mp: 80–82 ◦C. Anal. calc. for C40H60F6NP3Ru: C, 55.68; H, 6.96.
1
Found: C, 55.54; H, 6.83%. H NMR (CDCl3): d 7.43 (m, 2H,
Hm), 7.34 (m, 1H, Hp), 7.19 (m, 2H, Ho), 6.03 (m, 4H, Ha,b), 5.58
(m, 2H, Hc), 5.23 (s, 5H, Cp), 1.85 (m, 24H, Cy), 1.25 (m, 20H,
1
Cy). 31P{ H} NMR (CDCl3): d 39.70 (s, 2P, DCVP), −144.76
1
1
(sept., J(PF) = 713 Hz, 1P, PF6−). 13C{ H} NMR (CDCl3):
d 164.41 (t,| J(PC) = 20.2 Hz, CN), 131.86 (AXXꢀ,1J(PC)| =
2
3
3
2
3
ꢀ
18.8 Hz, J(HaHb) = 12.8 Hz, 2H, Ha), 6.00 (dd, J(PH) =
34.4 Hz, | J(PP) = 25.7 Hz, | J(PC) = 1.2 Hz, Ca ), 129.87
3
3
ꢀ
33.5 Hz, J(HaHb) = 12.8 Hz, 2H, Hb), 5.61 (dd, J(HaHc) =
(Cm), 129.23 (Ci), 128.26 (Cp), 128.15 (Cb ), 124.84 (Co), 83.58 (t,
3
3
2
18.8 Hz, J(PH) = 15.5 Hz, 2H, Hc), 5.91 (app t, | J(HH) +
J(PC) = 2.6 Hz, Cp), 40.51 (AXXꢀ,1J(PC)| = 23.9 Hz, | J(PP) =
4J(HH)| = 3.0 Hz, 2H, Cp), 5.03 (app t, | J(HH) + J(HH)| =
25.7 Hz, | J(PC) = 5.3 Hz, Ca), 37.91 (AXXꢀ,1J(PC)| = 25.4 Hz,
3
4
3
2
3
=
3.0 Hz, 2H, Cp), 3.84 (s, 2H, C CH2), 2.12 (s, 3H, CH3Cp),
| J(PP) = 25.7 Hz, | J(PC) = −1.1 Hz, Ca), 29.53 (Cb), 29.03
1.75 (m, 12H, Cy), 1.18 (m, 10H, Cy). 31P{ H} NMR (CDCl3): d
(Cb), 28.52 (Cb), 28.14 (Cb), 27.14 (AXXꢀ, | J(PC)| + J(PC)| =
1
2
4
40.68 (s, 2P, DCVP), −145.00 (sept., 1J(PF) = 714 Hz, 1P, PF6−).
10.9 Hz, Cc), 26.97 (AXXꢀ, | J(PC)| + J(PC)| = 12.8 Hz, Cc),
2
4
13
1
2
4
29.63 (AXXꢀ, | J(PC)| + J(PC)| = 12.8 Hz, Cc), 26.57 (AXXꢀ,
=
=
C{ H} NMR (CDCl3): d 321.59 (Ru C), 207.25 (C CH2),
2
3
2
4
129.46 (AXXꢀ, 1J(PC)| = 35.9 Hz, | J(PP) = 23.5 Hz, | J(PC) =
| J(PC)| + J(PC)| = 10.2 Hz, Cc), 25.91 (Cd), 25.86 (Cd). IR (NC
region, CH2Cl2, cm−1): 2096, IR (PF6 region, CH2Cl2 film, cm−1):
840.
ꢀ
ꢀ
2.6 Hz, Ca ), 128.91 (s, Cb ), 108.96 (t, J(PC) = 2.5 Hz, Cpq), 89.96
(Cp), 88.45 (Cp), 41.63 (AXXꢀ, J(PC) = 41.1 Hz, J(PP) =
1
2
23.5 Hz, 3J(PC) = −10.8 Hz, Ca), 37.44 (app T, | J(PC) +
1
Preparation of [(g5-C5H5)Ru(DCVP)2(CO)]PF6 (8).
100 mL, three-neck round-bottom flask was charged with
A
3J(PC)| = 25.1 Hz, Ca), 29.38 (Cb), 28.93 (Cb), 28.51 (Cb), 27.85
3
5
(Cb), 26.93 (app T, | J(PC) + J(PC)| = 12.4 Hz, Cc), 26.91 (app
5
1
3
0.21 g (0.3 mmol) of [(g -C5H5)Ru(g -DCVP)(g -DCVP)]PF6
and 50 mL of 1,2-dichloroethane. The solution was brought
to reflux and bubbled with CO for 3 days. Solvent was removed
in vacuo leaving 0.17 g (77% yield) of yellow microcrystalline
product. Mp: 100–102 ◦C. Anal. calc. for C34H55F6OP3Ru: C,
51.84; H, 6.99. Found: C, 51.67; H, 6.82%. 1H NMR (CDCl3):
d 6.0 (m, 4H, Ha,b), 5.59 (m, 2H, Hc), 5.31 (s, 5H, Cp), 2.0–
3
5
3
T, | J(PC) + J(PC)| = 11.1 Hz, Cc), 26.71 (app T, | J(PC) +
5J(PC)| = 10.4 Hz, Cc), 26.06 (app T, | J(PC) + J(PC)| =
3
5
=
10.7 Hz, Cc), 25.81 (Cd), 25.68 (Cd), 12.23 (CH3Cp). IR (C C
region, CH2Cl2, cm−1): 1621, IR (PF6 region, Nujol, cm−1): 832.
Preparation of [(g5-MeC5H4)Ru(DCVP)2(PhNC)]PF6 (6).
A 100 mL, three-neck round-bottom flask was charged
5
1
3
1
0.8 (m, 44H, 4·C6H11). 31P{ H} NMR (CDCl3): d 37.94 (s, 2P,
with 0.32 g (0.4 mmol) of [(g -MeC5H4)Ru(g -DCVP)(g -
DCVP)]PF6·CH2Cl2 and 40 mL of 1,2-dichloroethane. The
whole was stirred under a nitrogen atmosphere and then 0.5 mL
(4.8 mmol) of PhNC was added. The mixture was heated
under reflux for 9 days. Solvent was removed leaving a brown
oily residue. This residue was dissolved in CH2Cl2 and passed
through a silica gel column packed with hexane and eluted
with CH2Cl2. Solvents were evaporated leaving 0.26 g (79%) of
yellow product. Mp: 85–87 ◦C. Anal. calc. for C41H62F6NP3Ru:
C, 56.16; H, 7.08. Found: C, 56.02; H, 6.93%. 1H NMR (CDCl3):
d 7.45 (m, 1H, Hm), 7.43 (m, 1H, Hm), 7.36 (m, 1H, Hp), 7.20 (m,
1H, Ho), 7.17 (m, 1H, Ho), 6.04 (m, 4H, Ha,b), 5.88 (m, 2H, Hc),
5.17 (s, 2H, Cp), 4.91 (s, 2H, Cp), 2.11 (s, 3H, CH3Cp), 1.84 (m,
1
1
DCVP), −145.00 (sept., J(PF) = 713 Hz, 1P, PF6−). 13C{ H}
2
NMR (CDCl3): d 203.67 (t,| J(PC) = 17.6 Hz, CO), 130.46
(AXXꢀ,2J(PP)| = 22.3 Hz, | J(PC) = 37.4 Hz, | J(PC) = 0.5 Hz,
1
3
ꢀ
2
ꢀ
ꢀ
Ca ), 129.46 (s, Cb ), 86.33 (s, Cp), 40.28 (AXX , J(PP)| =
1
3
22.3 Hz, | J(PC) = 29.4 Hz, | J(PC) = 0.05 Hz, Ca), 38.04
(AXXꢀ,2J(PP)| = 22.3 Hz, | J(PC) = 23.7 Hz, | J(PC) = 1.3 Hz,
1
3
Ca), 29.99 (s, 2Cb), 29.34 (s, Cb), 28.96 (s, Cb), 28.45 (AXXꢀ,
2
4
| J(PC)| + | J(PC)| = 10.4 Hz, Cc), 26.91 (m, Cc), 26.85 (m, Cc),
26.71 (s, Cd), 26.36 (AXXꢀ, | J(PC)| + | J(PC)| = 10.4 Hz, Cc),
25.79 (s, Cd). IR (CO region, CH2Cl2 film, cm−1): 2051, 1962, IR
(PF6 region, CH2Cl2 film, cm−1): 841.
2
4
1
Attempted preparation of [(g5-C5Me5)Ru(g1-DCVP)(g3-
DCVP)]PF6 by reaction of [(g5-Me5C5)RuCl2]2 with Zn, DCVP
and NH4PF6 (9). A 100 mL, three-neck round-bottom flask
24H, Cy), 1.28 (m, 20H, Cy). 31P{ H} NMR (CDCl3): d 39.56
1
(s, 1P, DCVP), 39.27 (s, 1P, DCVP), −144.94 (sept., J(PF) =
714 Hz, 1P, PF6−). 13C{ H} NMR (CDCl3): d 164.37 (t,| J(PC) =
1
2
5
2
was charged with 1.0 g (1.6 mmol) of [(g -Me5C5)RuCl2]2, 2.6 g
20.6 Hz, CN), 132.03 (AXXꢀ,1J(PC)| = 28.0 Hz, | J(PP) =
3
ꢀ
1
(40 mmol) of Zn dust and 30 mL of freshly distilled acetonitrile.
The whole was stirred vigorously under a nitrogen atmosphere
for 2 hours (a change of color was observed: brown to green
to red). The excess Zn was removed by filtration and then
1.5 mL (6.7 mmol) of DCVP was added. The mixture was stirred
at room temperature overnight and then 0.8 g (4.9 mmol) of
NH4PF6 in 10 mL of MeOH was added. Solvents were removed.
Recrystallization from acetone–diethyl ether–hexane gave 0.2 g
of colorless crystals in 8% yield.Mp: 355–357 ◦C. Anal. calc.
ꢀ
26.2 Hz, | J(PC) = 4.4 Hz, Ca ), 131.77 (AXX , J(PC)| =
2
3
ꢀ
29.3 Hz, | J(PP) = 26.2 Hz, | J(PC) = 3.3 Hz, Ca ), 129.94
ꢀ
(Cm), 129.80 (Cm), 129.25 (Ci), 128.23 (Cp), 128.11 (Cb ), 127.87
ꢀ
(Cb ), 124.80 (Co), 124.55 (Co), 104. 22 (Cpq), 83.54 (Cp), 83.50
(Cp), 83.13 (Cp), 81.81 (Cp), 40.44 (AXXꢀ,1J(PC)| = 25.9 Hz,
| J(PP) = 26.2 Hz, | J(PC) = 2.7 Hz, Ca), 38.06 (AXXꢀ,1J(PC)| =
2
3
2
3
24.3 Hz, | J(PP) = 26.2 Hz, | J(PC) = 0.2 Hz, Ca), 37.84
(AXXꢀ,1J(PC)| = 24.3 Hz, | J(PP) = 26.2 Hz, | J(PC) = 1.6 Hz,
2
3
Ca), 29.47 (Cb), 29.40 (Cb), 28.96 (Cb), 28.86 (Cb), 28.46 (Cb),
28.36 (Cb), 28.16 (Cb), 28.07 (Cb), 27.07 (AXXꢀ, | J(PC)| +
3
5J(PC)| = 10.2 Hz, Cc), 26.92 (AXXꢀ, | J(PC)| + J(PC)| =
3
5
10.9 Hz, Cc), 26.87 (AXXꢀ, | J(PC)| + J(PC)| = 7.5 Hz, Cc),
3
5
26.43 (AXXꢀ, | J(PC)| + J(PC)| = 10.6 Hz, Cc), 25.86 (Cd),
25.82 (Cd), 15.04 (CH3Cp). IR (NC region, CH2Cl2, cm−1): 2091,
IR (PF6 region, CH2Cl2 film, cm−1): 844.
3
5
Preparation of [(g5-C5H5)Ru(DCVP)2(PhNC)]PF6 (7).
100 mL, three-neck round-bottom flask was charged with
0.27 g (0.4 mmol) of [(g -C5H5)Ru(g -DCVP)(g -DCVP)]PF6
and 40 mL of 1,2-dichloroethane. The whole was stirred under
a nitrogen atmosphere and then 0.5 mL (4.8 mmol) of PhNC
A
for C28H52F12P4: C, 45.37; H, 7.02. Found: C, 45.25; H, 6.94. 1H
2
3
NMR (acetone-d6): d 3.13 (m, | J(PH)| + | J(PH)| = 5 Hz, 8H,
5
1
3
2
3
3
ꢀ
Ha,a ), 2.90 (app qt, J(PH)| = J(HaHb)| = 12.0 Hz, J(HaHb)| =
3.0 Hz, 4H, Ha), 2.17 (m, 8H, Hb)|, 1.88 (m, 8H, Hc)|, 1.73 (m,
12H, Hb,c|)|, 1.45 (m, 4H, Hc)|, 1.37 (m, 8H, Hd)|. 31P{ H} NMR
1
1 0 0
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3

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(acetone-d6): d 24.80 (s, 2P, P+), −145.00 (sept., 1J(PF) = 709 Hz,
1P, DCVP), −145.0 (sept., 1J(PF) = 711 Hz, 1P, PF6−). IR (CO
region, CH2Cl2, cm−1): 1984, IR (CN region, CH2Cl2, cm−1):
2360, 2342.
1
2P, PF6−). 13C{ H} NMR (acetone-d6): d 31.11 (AXXꢀ,1J(PC)| =
3
4
40.7 Hz, | J(PP) = 16.2 Hz, | J(PC) = 0.2 Hz, Ca), 26.70
(AXXꢀ,3J(PP)| = 16.2 Hz, | J(PC) = 12.6 Hz, | J(PC) = 0.9 Hz,
3
6
Preparation of [(g5-C5Me5)Ru(CO)(CH3CN)(DPVP)]PF6
(12). A 250 mL, three-neck round-bottom flask was charged
Cc), 26.32 (AXXꢀ, | J(PC)| + | J(PC)| = 3.5 Hz, Cb), 25.62
2
5
(AXXꢀ, | J(PC)| + J(PC)| = 1.8 Hz, Cd), 9.43 (AXXꢀ,1J(PC)| =
4
7
5
with 2.19 g (3.9 mmol) of [(g -Me5C5)Ru(CO)(Br)(DPVP)] and
3
2
ꢀ
44.6 Hz, | J(PP) = 16.2 Hz, | J(PC) = −4.6 Hz, Ca,a ). IR (PF6
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 1.20 g (4.7 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-yellow residue was dissolved in CH2Cl2 and passed
through a silica gel column packed with hexane and eluted with
CH2Cl2. Recrystallization from CH2Cl2–hexane gave 1.82 g of
pure product in 70% yield. Mp: 185–190 ◦C. Anal. calc. for
C27H31F6NOP2Ru: C, 48.90; H, 4.68. Found: C, 48.56; H, 4.39%.
1H NMR (CDCl3): d 7.46 (m, 8H, Ph), 7.36 (m, 2H, Ho), 6.22
(ddd, 2J(PH) = 22.0 Hz, 3J(HaHc) = 18.0 Hz, 3J(HaHb) =
region, Nujol, cm−1): 840.
Preparation of [(g5-MeC5H4)Ru(CO)(Br)(DCVP)] (10).
A
100 mL, three-neck round-bottom flask was charged with 1.0 g
5
(3.2 mmol) of [(g -MeC5H4)Ru(CO)2Br], 40 mL of benzene and
1 mL (4.5 mmol) of DCVP. This solution was then brought
to reflux under a nitrogen atmosphere. A tenth-molar amount
5
21
(40 mg) of the catalyst [(g -C5H5)Fe(CO)2]2 was added to the
refluxing mixture. The reaction progress was monitored by IR
spectroscopy in the CO region. After 2 hours of reflux the
reaction was complete (bands at 1996 cm−1 and 2045 cm−1
disappeared). Solvent was removed leaving a brown, oily residue.
This residue was dissolved in CH2Cl2 and passed through a
silica gel column packed with hexane and eluted with CH2Cl2.
Recrystallization from hot isopropanol gave 1.35 g of red crystals
in 83% yield. Mp: 103–105 ◦C. Anal. calc. for C21H31BrOPRu: C,
49.28; H, 6.06. Found: C, 49.13; H, 6.00%. 1H NMR (CD2Cl2):
d 6.37 (ddd, 3J(HaHc) = 18.5 Hz, 3J(HaHb) = 12.5 Hz, 2J(PH) =
3
3
12.0 Hz, 1H, Ha), 6.20 (dd, J(PH) = 40.0 Hz, J(HaHb) =
3
3
12.0 Hz, 1H, Hb), 5.49 (dd, J(PH) = 20.0 Hz, J(HaHc) =
18.0 Hz, 1H, Hc), 2.20 (s, 3H, CH3CN), 1.65 (d, J(PH) =
1
1.5 Hz, 15H, 5CH3Cp*). 13C{ H} NMR (CDCl3): d 202.83 (d,
| J(PC) = 18.6 Hz, CO), 133.04 (d,2J(PC)| = 10.9 Hz, Co), 132.55
2
2
1
ꢀ
(d, J(PC) = 10.7 Hz, Co), 131.66 (s, Cb ), 131.27 (d, J(PC) =
3
3
1
15.0 Hz, 1H, Ha), 5.99 (ddd, J(PH) = 35.0 Hz, J(HaHb) =
ꢀ
48.1 Hz, Ca ), 131.10 (s, Cp), 131.07 (s, Cp), 130.80 (d, J(PC)| =
2
3
48.9Hz, Ci), 130.10 (d,1J(PC) = 48.6Hz, Ci), 129.00 (d, 3J(PC) =
10.9 Hz, Cm), 128.91 (d, 3J(PC) = 10.7 Hz, Cm), 127.89 (s, CN),
97.48 (d, J(PC) = 1.6 Hz, Cp*), 9.40 (s, 5CH3Cp*), 3.57 (s,
12.5 Hz, J(HbHc) = 1.5 Hz, 1H, Hb), 5.80 (ddd, J(HaHc) =
18.5 Hz,3J(PH) = 16.5 Hz, J(HbHc) = 1.5 Hz, 1H, Hc), 5.01
2
(m, 1H, H2Cp), 4.85 (m, 2H, H2Cp), 4.71 (m, 1H, H1Cp), 2.09
CH3CN). 31P{ H} NMR (acetone-d6): d 39.20 (s, 1P, DPVP),
1
(m, 2H, Ha), 2.02 (d, J(PH) = 1.0 Hz, 3H, CH3Cp), 1.85 (m,
1
8H, Hb), 1.29 (m, 12H, Hc,d). 31P{ H} NMR (CD2Cl2): d 31.35
1
−145.0 (sept., J(PF) = 707 Hz, 1P, PF6−). IR (CO region,
1
2
(s, 1P, DCVP). 13C{ H} NMR (CD2Cl2): d 205.44 (d, | J(PC) =
CH2Cl2, cm−1): 1970, IR (CN region, Nujol, cm−1): 2319, 2284.
1
ꢀ
ꢀ
19.9 Hz, CO), 132.66 (d, J(PC)| = 18.0 Hz, Ca ), 131.57 (s, Cb ),
110.04 (d, J(PC)| = 2.6 Hz, Cpq), 86.32 (d, J(PC) = 1.5 Hz,
C1Cp), 82.57 (s, C2Cp), 80.40 (d, J(PC) = 5.4 Hz, C1Cp), 77.77
Preparation of [(g5-MeC5H4)Ru(CO)(DMPP)(DPVP)]PF6
Diels–Alder adduct (13). A 100 mL, three-neck round-
5
1
1
bottom flask was charged with 0.43 g (0.7 mmol) of [(g -
(s, C2Cp), 37.94 (d, J(PC) = 25.3 Hz, Ca), 37.67 (d, J(PC) =
3
MeC5H4)Ru(CH3CN)(CO)(DPVP)]PF6 and 50 mL of 1,2-
dichloroethane. The whole was stirred under a nitrogen atmo-
sphere for 40 min., and then 0.2 mL (1.1 mmol) of DMPP was
added via syringe. The mixture was refluxed for 3 days (change
of color was noticed: yellow to orange). Recrystallization from
CH2Cl2–hexane gave 0.22 g of yellow crystals (diastereoisomers
13A and 13B in 1.2 : 1 ratio) in 39% yield. Recrystallization
from CH3NO2–diethyl ether resulted in formation of 0.12 g of
diastereomer 13A in 21% yield.Mp: 180 ◦C (decomp.). Anal.
28.3 Hz, Ca), 29.41 (s, Cb), 29.21 (d, J(PC) = 2.0 Hz, Cc),
29.09 (s, Cb), 28.79 (s, Cb), 27.82 (d, 3J(PC) = 2.0 Hz, Cc), 27.73
3
3
(s, Cb), 27.64 (d, J(PC) = 11.8 Hz, Cc), 27.49 (d, J(PC) =
11.3 Hz, Cc), 26.95 (d, 4J(PC) = 1.3 Hz, Cd), 26.83 (d, 4J(PC) =
1.4 Hz, Cd), 13.89 (d, J(PC) = 0.6 Hz, CH3Cp). IR (CO region,
CH2Cl2, cm−1): 1948. E1/2 = 0.46 V vs. Fc/Fc+
.
Preparation of [(g5-MeC5H4)Ru(CO)(CH3CN)(DCVP)]PF6
(11). A 250 mL, three-neck round-bottom flask was charged
5
with 1.25 g (2.4 mmol) of [(g -MeC5H4)Ru(CO)(Br)(DCVP)]
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 0.7 g (2.8 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-yellow residue was dissolved in CH2Cl2
and passed through a silica gel column packed with hexane and
eluted with CH2Cl2. Recrystallization from CH2Cl2–he◦xane gave
0.72 g of yellow crystals in 48% yield. Mp: 142–145 C. Anal.
calc. for C23H31F6NOP2Ru: C, 44.91; H, 5.04. Found: C, 44.76;
calc. for C35H33F6O1.5P3Ru: C, 53.46; H, 4.20. Found: C, 53.51;
H, 4.06%. H NMR (CD3NO2): d 7.96 (m, 2H, Ho), 7.72 (m,
2H, Ho), 7.67 (m, 3H, Hm,p), 7.58 (m, 3H, Hm,p), 7.50 (m, 3H,
Hm,p), 7.44 (m, 2H, Ho), 5.41 (m, 1H, Cp), 4.84 (m, 2H, Cp),
1
1
H, 4.96%. H NMR (CD2Cl2): d 6.18 (m, 2H, Ha,b), 5.81 (m,
1H, Hc), 5.29 (m, 1H, Cp), 5.15 (m, 1H, Cp), 5.05 (bs, 1H,
Cp), 4.85 (m, 1H, Cp), 2.36 (d, 5J(PH) = 1.0 Hz, 3H, CH3CN),
2.08 (m, 2H, Ha), 1.97 (d, J(PH) = 1.5 Hz, CH3Cp), 1.84 (m,
3
4
4.77 (m, 1H, Cp), 3.79 (dd, J(H1H2) = 2.0 Hz, J(H1H5) =
2.0 Hz, 1H, H1), 3.42 (ddddd, J(PH) = 41.0 Hz,3J(H2H4) =
3
1
8H, Hb), 1.30 (m, 12H, Hc,d). 13C{ H} NMR (CD2Cl2): d 202.03
8.5 Hz, 2J(PH) = 6.5 Hz, 3J(H2H3) = 2.0 Hz, 3J(H1H2) =
2
2
4
3
ꢀ
(d, | J(PC) = 17.2 Hz, CO), 134.49 (d, J(PC)| = 1.5 Hz, Cb ),
2.0 Hz, 1H, H2), 3.19 (dd, J(H1H5) = 2.0 Hz, J(H3H5) =
1
ꢀ
129.53 (s, CN), 128.99 (d, J(PC) = 38.3 Hz, Ca ), 110.34 (d,
1.5 Hz, 1H, H5), 1.97 (m, 2H, H3,4), 1.84 (s, 3H, CH3), 1.78 (s,
1
J(PC) = 2.5 Hz, Cp), 85.61 (s, Cp), 85.25 (s, Cp), 80.62 (d,
J(PC) = 3.6 Hz, Cp), 79.13 (s, Cp), 38.06 (d, 1J(PC) = |25.9 Hz,
Ca), 37.65 (d, 1J(PC) = 29.5 Hz, Ca), 28.80 (d, 2J(PC) = 2.0 Hz,
Cb), 28.66 (s, Cb), 28.49 (d, 2J(PC) = 2.5 Hz, Cb), 28.39 (s, Cb),
3H, CH3), 1.58 (s, 3H, CH3). 31P{ H} NMR (CD3NO2): d 141.06
2
2
(d, J(PP) = 37.0 Hz, 1P, P7), 69.81 (d, J(PP) = 37.0 Hz, 1P,
P2), −145.0 (sept., 1J(PF) = 707 Hz, 1P, PF6−). 13C{ H} NMR
1
2
2
(CD3NO2): d 201.95 (dd, | J(PC) = 16.5 Hz, | J(PC) = 13.2 Hz,
3
3
2
1
27.36 (d, J(PC) = 2.8 Hz, Cc), 27.26 (d, J(PC) = 2.9 Hz,
CO), 138.36 (d, | J(PC) = 2.3 Hz, C5), 134.73 (d, | J(PC) =
Cc), 27.17 (d, 3J(PC) = 2.4 Hz, Cc), 26.48 (d, 4J(PC) = 1.3 Hz,
40.9 Hz, Ci), 134.13 (d, | J(PC) = 11.4 Hz, Co), 131.78 (d,
2
4
4
3
Cd), 26.44 (d, J(PC) = 1.5 Hz, Cd), 13.12 (d, J(PC) = 0.6 Hz,
| J(PC) = 2.4 Hz, Cp), 131.70 (d, | J(PC) = 3.6 Hz, C6), 131.44
2 1
CH3Cp), 4.30 (s, CH3CN). 31P{ H} NMR (CD2Cl2): d 48.53 (s,
(d, | J(PC) = 10.6 Hz, Co), 131.30 (d, | J(PC) = 10.6 Hz, Ci),
1
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3
1 0 1

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2
4
131.04 (d, | J(PC) = 9.8 Hz, Co), 131.03 (d, | J(PC) = 2.4 Hz,
Cp), 130.97 (d, | J(PC) = 2.8 Hz, Cp), 130.73 (dd, | J(PC) =
4
1
3
3
16.1 Hz, | J(PC) = 1.4 Hz, Ci), 129.17 (d, | J(PC) = 10.9 Hz,
3
3
Cm), 128.95 (d, | J(PC) = 10.2 Hz, Cm), 128.91 (d, | J(PC) =
10.3 Hz, Cm), 107.07 (d, J(PC) = 1.1 Hz, Cpq), 89.27 (s, Cp),
87.35 (d, J(PC) = 3.3 Hz, Cp), 87.15 (s, Cp), 85.90 (d, J(PC) =
3.0 Hz, Cp), 56.65 (dd, | J(PC) = 35.3 Hz, 2J(PC) = 13.7 Hz, C1),
1
1
49.60 (dd, | J(PC) = 33.1 Hz, 3J(PC) = 1.4 Hz, C4), 32.51 (dd,
| J(PC) = 37.1 Hz, 2J(PC) = 31.8 Hz, C2), 31.11 (dd, | J(PC) =
1
2
2
2
17.3 Hz, J(PC) = 2.9 Hz, C3), 13.59 (dd, | J(PC) = 2.8 Hz,
4J(PC) = 1.6 Hz, CH3(6)), 13.37 (d, | J(PC) = 3.5 Hz, CH3(5)),
2
11.81 (s, CH3Cp). IR (CO region, CH2Cl2, cm−1): 1982.
Preparation of [(g5-C5Me5)Ru(CO)(DMPP)(DPVP)]PF6
Diels–Alder adduct (14). A 250 mL, three-neck round-
bottom flask was charged with 0.88
g (1.3 mmol) of
5
[(g -C5Me5)Ru(CH3CN)(CO)(DPVP)]PF6 and 100 mL of
1,2-dichloroethane. The whole was stirred under a nitrogen
atmosphere for 40 min., and then 0.4 mL (2.1 mmol) of
DMPP was added via syringe. The mixture was refluxed
for 3 days (change of color was noticed: yellow to orange).
Recrystallization from CH2Cl2–hexane gave 0.43 g of yellow
crystals (diastereoisomers 14A and 14B in 2 : 1 ratio) in 40%
yield. Recrystallization from CH3NO2–diethyl ether resulted
in formation of 0.30 g of diastereomer 14A in 28% yield. Mp:
275 ◦C (decomp.). Anal. calc. for C37H41F6OP3Ru: C, 54.84; H,
5.06. Found: C, 54.66; H, 4.91%. 1H NMR (acetone-d6): d 7.90
(m, 2H, Ho), 7.74 (m, 4H, Hm), 7.61 (m, 3H, Hp), 7.53 (m, 4H,
Ho,m), 7.32 (m, 2H, Ho), 4.17 (dd, 3J(H1H2) = 2.1 Hz, 4J(H1H5) =
3
2.0 Hz, 1H, H1), 3.45 (ddddd, J(PH) = 40.0 Hz,3J(H2H4) =
8.0 Hz, 2J(PH) = 6.5Hz, 3J(H1H2) = 2.1 Hz, 3J(H2H3) =
4
3
1.5 Hz, 1H, H2), 3.06 (dddd, J(H1H5) = 2.0 Hz, J(H3H5) =
2
3
4.0 Hz, J(PH) = 0.8 Hz, J(H4H5) = 0.5 Hz,1H, H5), 1.86
(app tdd,2J(H3H4) = J(PH) = 14.0 Hz, J(H3H5) = 4.0 Hz,
3J(H2H3) = 1.5 Hz, 1H, H3), 1.80 (m, H4), 1.75 (s, 3H, CH3),
1.54 (s, 15H, 5CH3Cp*), 1.45 (d,4J(PH) = 0.5 Hz, 3H, CH3).
3
3
31P{ H} NMR (acetone-d6): d 142.88 (d, J(PP) = 35.1 Hz,
1
2
2
1P, P7), 72.67 (d, J(PP) = 35.1 Hz, 1P, P2), −144.77 (sept.,
1J(PF) = 707 Hz, 1P, PF6−). 13C{ H} NMR (acetone-d6): d
1
2
2
205.44 (dd, | J(PC) = 16.8 Hz, | J(PC) = 12.6 Hz, CO), 139.90
2
2
(d, | J(PC) = 2.4 Hz, C5), 135.44 (d, | J(PC) = 11.2 Hz, Co),
2
133.60 (d, | J(PC) = 10.1 Hz, Co), 133.05 (s, C6), 132.90 (d,
2
1
| J(PC) = 9.4 Hz, Co), 132.20 (d, | J(PC) = 42.5 Hz, Ci), 132.19
1
4
(d, | J(PC) = 41.9 Hz, Ci), 132.12 (d, | J(PC) = 2.5 Hz, C1),
131.91 (d, | J(PC) = 2.3 Hz, Cp), 130.30 (d, | J(PC) = 10.7 Hz,
4
3
3
3
Cm), 129.85 (d, | J(PC) = 9.9 Hz, Cm), 129.70 (d, | J(PC) =
1
3
9.4 Hz, Cm), 128.91 (dd, | J(PC) = 40.7 Hz, | J(PC) = 2.8 Hz,
1
Ci), 100.42 (app t, J(PC) = 1.1 Hz, Cp*), 57.38 (dd, | J(PC) =
2
1
32.5 Hz, | J(PC) = 13.8 Hz, C1), 51.68 (dd, | J(PC) = 33.2 Hz,
3
2
2
| J(PC) = 1.3 Hz, C4), 35.15 (dd, | J(PC) = 37.2 Hz, | J(PC) =
1
2
29.5 Hz, C3), 33.04 (dd, | J(PC) = 12.8 Hz, | J(PC) = 2.9 Hz,
3
4
C2), 15.11 (app t, | J(PC) = | J(PC) = 2.5 Hz, C6), 13.68 (d,
3J(PC) = 3.3 Hz, C5), 9.86 (s, 5CH3Cp*). IR (CO region,
CH2Cl2, cm−1): 1969.
C. Ruthenium catalyzed hydration of phenylacetylene
Method A. A solution containing 2.5 mol% of the catalyst
and 2 mL of phenylacetylene in 10 mL of 95% ethanol was
heated at reflux overnight. Then the solution was cooled to room
temperature and dried over anhydrous magnesium sulfate. After
filtration, the remaining mixture was analyzed by GC/MS.
Method B. A solution containing 1.4 mol% of the catalyst
and 1 mL of phenylacetylene in 15 mL of isopropanol and
3 mL of water was heated at reflux overnight. Then the solution
was cooled to room temperature and dried over anhydrous
magnesium sulfate. After filtration, the remaining mixture was
analyzed by GC/MS.
The results are given in Table 2.
1 0 2
D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3

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D. X-Ray crystallographic studies
Transition Metal Complexes, Wiley Interscience, New York, 2nd edn.,
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.
3 H. L. Ji, J. H. Nelson, A. De Cian, J. Fischer, L. Solujic and E. B.
Milosavljevic, Organometallics, 1992, 11, 401.
4 L. P. Barthel-Rosa, K. Maitra, J. Fischer and J. H. Nelson,
Organometallics, 1997, 16, 1714.
5 D. Duraczynska and J. H. Nelson, Dalton Trans., 2003, 449.
6 (a) M. I. Bruce, Chem. Rev., 1998, 98, 2797; (b) M. I. Bruce, Chem.
Rev., 1991, 91, 197.
7 (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.
8 H. D. Hansen, Ph.D. Dissertation, University of Nevada, Reno, 2001.
9 H. D. Hansen and J. H. Nelson, Organometallics, 2000, 19, 4740 and
references therein.
10 J. N. Brown and L. M. J. Trefonas, Heterocycl. Chem., 1972, 35.
11 (a) L. Solujic, E. B. Milosavljevic, J. H. Nelson, N. W. Alcock and
J. Fisher, Inorg. Chem., 1989, 28, 3453; (b) S. Affandi, J. H. Nelson
and J. Fisher, Inorg. Chem., 1989, 28, 4536; (c) D. Bhaduri, J. H.
Nelson, C. L. Day, R. A. Jacobson, L. Solujic and E. B. Milosavljevic,
Ogranometallics, 1992, 11, 4069; (d) H. L. Ji, J. H. Nelson, A. De
Cian, J. Fischer, L. Solujic and E. B. Milosavljevic, Organometallics,
1992, 11, 1840; (e) J. H. Nelson, in Phosphorus - 31 NMR Spectral
Properties in Compound Characterization and Structural Analysis, ed.
L. D. Quin and J. G. Verkade, VCH, Deerfield Beach, FL, 1994, pp.
203–214; (f) K. D. Redwine, V. J. Catalano and J. H. Nelson, Syn.
React. Inorg. Met.-Org. Chem., 1999, 29, 395; (g) K. Maitra, V. J.
Catalano and J. H. Nelson, J. Am. Chem. Soc., 1997, 119, 12560;
(h) K. D. Redwine and J. H. Nelson, J. Organomet. Chem., 2000, 613,
177; (i) K. Y. Ghebreyessus and J. H. Nelson, J. Organomet. Chem.,
2003, 669, 48.
Single crystals of 1, 2, 3, 9, 10, 11, 12, 13B and 14B were obtained
as follows: slow diffusion of hexane into a CH2Cl2 solution (2,
3, 11 and 12), slow diffusion of diethyl ether into a CH2Cl2–
MeOH solution (1), slow diffusion of diethyl ether–hexane into
an acetone solution (9), slow diffusion of diethyl ether into a
nitromethane solution (13A and 14A) and slow crystallization
from hot isopropanol (10). Compound 13A is a disordered hemi
etherate and solvent hydrogens were not included. The crystals
of 2, 12, 13A and 14A were mounted on glass fibers, coated with
epoxy, and placed on a Siemens P4 diffractometer. Intensity data
were taken in the x mode with graphite-monochromated Mo-Ka
˚
radiation (k = 0.71073 A). Three check reflections, monitored
every 100 reflections, showed random (< 2%) variation during
the data collections. The data were corrected for Lorentz,
polarization effects, and absorption (using an empirical model
derived from azimuthal data collections). Scattering factors
and corrections for anomalous dispersion were taken from a
standard source.22 For 1, 3 and 9 data collection was carried out
on a Bruker SMART diffractometer with the crystal mounted
in a nitrogen stream at 100 K. The structures were solved by
direct methods and refined by full-matrix least-squares on F2.
Calculations were performed within the Siemens SHELXTL
Plus23 software package on a PC. The structures were solved by
direct or Patterson methods. 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 A. The data were refined by
the method of full matrix least-squares on F2. Final cycles of
refinement converged to the R1(F) and xR2(F2) values given in
Table 3, where x−1 = r2(F) + 0.001F2.
12 (a) M. Tokunaga, T. Suzuki, N. Koga, T. Fukushima, A. Horiuchi
and Y. Wakatsuki, J. Am. Chem. Soc., 2001, 123, 11917; (b) M.
Tokunaga and Y. Wakatsuki, Angew. Chem. Int. Ed., 1998, 37, 2867;
(c) T. Suzuki, M. Tokunaga and Y. Wakatsuki, Org. Lett., 2001, 3,
735.
CCDC reference numbers 248575–248583.
See http://www.rsc.org/suppdata/dt/b4/b413446j/ for crys-
tallographic data in CIF or other electronic format.
13 (a) T. Straub, A. Haskel, T. G. Neyroud, M. Kapon, M. Botoshansky
and M. Eisen, Organometallics, 2001, 20, 5017; (b) T. Straub, A.
Haskel and M. Eisen, J. Am. Chem. Soc., 1995, 117, 6364; (c) H. Y.
Rhyoo, B. Y. Lee, H. K. B. Yu and Y. K. Chung, J. Mol. Cat., 1994,
92, 41; (d) W. Baidossi, N. Goren, J. Blum, H. Schumann and H.
Hemling, J. Mol. Cat., 1993, 85, 153; (e) J. Wendt, U. Klinger and H.
Singer, Inorg. Chim. Acta, 1991, 183, 133.
Acknowledgements
We are grateful to the donors of the Petroleum Research Fund,
administered by the American Chemical Society, for financial
support.
14 T. P. Gill and K. R. Mann, Organometallics, 1982, 1, 485.
15 U. Koelle and J. Kossakowski, Inorg. Synth., 1992, 29, 225.
16 A. Breque, F. Mathey and P. Savignac, Synthesis, 1981, 983.
17 T. Shingaki and M. Takebayashi, Bull. Chem. Soc. Jpn., 1963, 617.
18 K. Y. Ghebreyessus and J. H. Nelson, Syn. React. Inorg. Met.-Org.
Chem., 2003, 33, 1329.
19 K. Stott, J. Stonehouse, J. Keeler, T. L. Hwang and A. Shaka, J. Am.
Chem. Soc., 1995, 117, 4199.
20 R. R. Gagne, C. A. Koval and G. C. Lisnesky, Inorg. Chem., 1980,
19, 2854.
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D a l t o n T r a n s . , 2 0 0 5 , 9 2 – 1 0 3
1 0 3